Artificial Molecular Machines

Sundus Erbas-Cakmak; David A Leigh; Charlie T McTernan; Alina L Nussbaumer

doi:10.1021/acs.chemrev.5b00146

. 2015 Sep 8;115(18):10081–10206. doi: 10.1021/acs.chemrev.5b00146

Artificial Molecular Machines

Sundus Erbas-Cakmak ¹, David A Leigh ^1,^*, Charlie T McTernan ¹, Alina L Nussbaumer ¹

PMCID: PMC4585175 PMID: 26346838

1. Introduction

The widespread use of molecular machines in biology has long suggested that great rewards could come from bridging the gap between synthetic molecular systems and the machines of the macroscopic world. In the last two decades, it has proved possible to design synthetic molecular systems with architectures where triggered large amplitude positional changes of submolecular components occur. Perhaps the best way to appreciate the technological potential of controlled molecular-level motion is to recognize that nanomotors and molecular-level machines lie at the heart of every significant biological process. Over billions of years of evolution, nature has not repeatedly chosen this solution for performing complex tasks without good reason. When mankind learns how to build artificial structures that can control and exploit molecular level motion and interface their effects directly with other molecular-level substructures and the outside world, it will potentially impact on every aspect of functional molecule and materials design. An improved understanding of physics and biology will surely follow.

The first steps on the long path to the invention of artificial molecular machines were arguably taken in 1827 when the Scottish botanist Robert Brown observed the haphazard motion of tiny particles under his microscope.^1,2 The explanation for Brownian motion, that it is caused by bombardment of the particles by molecules as a consequence of the kinetic theory of matter, was later provided by Einstein, followed by experimental verification by Perrin.^3,4 The random thermal motion of molecules and its implications for the laws of thermodynamics in turn inspired Gedankenexperiments (“thought experiments”) that explored the interplay (and apparent paradoxes) of Brownian motion and the Second Law of Thermodynamics. Richard Feynman’s famous 1959 lecture “There’s plenty of room at the bottom” outlined some of the promise that manmade molecular machines might hold.^5,6 However, Feynman’s talk came at a time before chemists had the necessary synthetic and analytical tools to make molecular machines. While interest among synthetic chemists began to grow in the 1970s and 1980s, progress accelerated in the 1990s, particularly with the invention of methods to make mechanically interlocked molecular systems (catenanes and rotaxanes) and control and switch the relative positions of their components.⁷⁻²⁴

Here, we review triggered large-amplitude motions in molecular structures and the changes in properties these can produce. We concentrate on conformational and configurational changes in wholly covalently bonded molecules and on catenanes and rotaxanes in which switching is brought about by various stimuli (light, electrochemistry, pH, heat, solvent polarity, cation or anion binding, allosteric effects, temperature, reversible covalent bond formation, etc.). Finally, we discuss the latest generations of sophisticated synthetic molecular machine systems in which the controlled motion of subcomponents is used to perform complex tasks, paving the way to applications and the realization of a new era of “molecular nanotechnology”.

1.1. The Language Used To Describe Molecular Machines

Terminology needs to be properly and appropriately defined and these meanings used consistently to effectively convey scientific concepts. Nowhere is the need for accurate scientific language more apparent than in the field of molecular machines. Much of the terminology used to describe molecular-level machines has its origins in observations made by biologists and physicists, and their findings and descriptions have often been misinterpreted and misunderstood by chemists. In 2007 we formalized definitions of some common terms used in the field (e.g., “machine”, “switch”, “motor”, “ratchet”, etc.) so that chemists could use them in a manner consistent with the meanings understood by biologists and physicists who study molecular-level machines.¹⁴

The word “machine” implies a mechanical movement that accomplishes a useful task. This Review concentrates on systems where a stimulus triggers the controlled, relatively large amplitude (or directional) motion of one molecular or submolecular component relative to another that can potentially result in a net task being performed. Molecular machines can be further categorized into various classes such as “motors” and “switches” whose behavior differs significantly.¹⁴ For example, in a rotaxane-based “switch”, the change in position of a macrocycle on the thread of the rotaxane influences the system only as a function of state. Returning the components of a molecular switch to their original position undoes any work done, and so a switch cannot be used repetitively and progressively to do work. A “motor”, on the other hand, influences a system as a function of trajectory, meaning that when the components of a molecular motor return to their original positions, for example, after a 360° directional rotation, any work that has been done is not undone unless the motor is subsequently rotated by 360° in the reverse direction. This difference in behavior is significant; no “switch-based” molecular machine can be used to progressively perform work in the way that biological motors can, such as those from the kinesin, myosin, and dynein superfamilies, unless the switch is part of a larger ratchet mechanism.¹⁴

1.2. The Effects of Scale

Machines need to be designed according to the environment in which they are intended to operate. The significance and consequences of random thermal motion, heat dissipation, solvation, momentum, inertia, gravity, etc., differ significantly at the molecular and macroscopic levels, meaning that nanoscale machines cannot simply mimic the mechanisms of their macroscopic brethren.

The forces with the greatest influence on dynamics in the nanoworld are not those we commonly rely on in the macroscopic world. For large objects, inertial terms, which depend on the mass of the particle, dominate motion. As particle size decreases to or below the micrometre scale, viscous forces and Brownian motion become dominant while momentum and gravity become increasingly irrelevant. This effect can be quantified by the Reynolds number (R) for a particle of radius a, velocity v in a medium of density ρ and viscosity μ:^25,26

1

Because the Reynolds number decreases with radius, molecular-sized machines typically operate under low Reynolds number conditions. Furthermore, the larger surface:volume ratio of small particles makes them increasingly adhesive, decreasing mobility. These effects must be carefully considered in the design of molecular machines.¹⁴

1.3. Thought Machines Exploring Brownian Motion

Molecular motors rely on exploiting random thermal fluctuations for directional motion by employing ratchet mechanisms. Thought experiments such as Maxwell’s demon,^27,28 Smoluchowski’s trapdoor,²⁹ and Feynman’s ratchet-and-pawl³⁰ have investigated potential ways to cause the directional motion of Brownian particles.³¹

The Second Law of Thermodynamics states that the entropy of an isolated system tends to increase, leading to an equilibrium distribution with maximum entropy. To achieve any distribution other than the thermodynamic equilibrium, work must be done on the system. Various thought experiments have been proposed that attempt to violate this premise and drive a system away from equilibrium without expending work. In the Maxwell’s Demon thought experiment, particles in a container are sorted by an “intelligent gatekeeper”, the “demon” (Figure 1).³² Gas particles are distributed in a container partitioned into two sections in an isolated system. The spontaneous formation of a heat or pressure gradient would lead to a decrease in entropy and thus violate the Second Law. The gatekeeper is able to detect the velocity of each particle and can control the gate accordingly. The demon allows particles with higher than average speeds (shown in red in Figure 1a) to pass from the right section to the left, but not from the left to the right. The opposite holds for slower particles (shown in blue in Figure 1a). The gatekeeper thus causes a nonuniform distribution of particles between the two sections, creating a temperature gradient. Similarly, a demon capable of detecting the direction of the particle and opening the gate accordingly can concentrate particles in one section and thus generate a pressure gradient (Figure 1b). If the gate is frictionless, then in both cases a nonequilibrium distribution has been achieved seemingly without doing work, which would violate The Second Law. The solution to the apparent paradox lies in considering the information required by the demon to know when to open the door. As the demon must measure the velocity or direction of each particle approaching the door³³ and cannot have infinite memory,³⁴ at some point the demon must “forget” this information. The destruction of information has a minimum enthalpic cost associated with it³⁵ as has been experimentally verified,³⁶ which always exceeds the decrease in entropy in the container. Thus, a local decrease in entropy is paid for by a generalized increase upon information deletion.

Maxwell’s demons. (a) A “temperature demon” sorts particles according to velocity, generating a temperature gradient. (b) A “pressure demon” sorts particles according to their direction of movement, generating a pressure gradient.³⁷

Smoluchowski proposed a system that did not rely on an intelligent observer based on a spring-loaded one-way gate, opened by thermal fluctuations (Figure 2a).^29,38,39 However, directional transport was proven to be impossible in this system as the gate is unable to dissipate energy from collisions with gas particles. This leads to ever longer open periods for the gate and so to equilibration of the particles across the container.

(a) In Smoluchowski’s Trapdoor, a spring-loaded gate separates the two sections of a container. The lack of energy dissipation leads to a longer duration of opening and thus a uniform particle distribution between the sections.²⁹ (b) Feynman’s ratchet-and-pawl device. The asymmetry of the teeth of the ratchet cog was intended to drive directional movement. However, when T₁ = T₂, the rotation is nondirectional.³⁰

In Feynman’s ratchet-and-pawl, the asymmetric cog teeth could have allowed directional rotation powered by Brownian motion (Figure 2b).^30,40−44 Although in line with the second law, no work could be extracted when T₁ = T₂ (the pawl is at the same temperature as the rest of the device and thus fluctuates between open and closed states and so fails to act as a ratchet), but work can be done when T₁ > T₂. This is an important point for the design of nanoscale machines. As the system moves from a nonequilibrium state toward equilibrium (T₁ = T₂), directional work can be done. Hence, if a nonequilibrium situation can be created, its relaxation can drive directional motion. In other words, an energy input is required to do work and to break detailed balance (see section 4.4).

1.4. Inspiration from Nature

Perhaps the most important lesson to learn from biological systems is that molecular machines are viable and can perform extremely complex tasks. In nature, molecular machines play a vital role, being involved in almost every major biological process and allowing a vast array of chemical and mechanical tasks to be accomplished.⁴⁵⁻⁴⁷ The ways in which nature has overcome the problems of scale, Brownian motion, viscosity, nonequilibrium distribution and environment provide some general directions for the design of molecular machines.

Cellular processes are compartmentalized by lipid barriers, which allow nonequilibrium distributions to be built up and maintained. A range of molecular machines control the transport of various charged and polar species across these membranes using relay channels or mobile carrier entities.⁴⁸⁻⁵⁰ This transfer can be driven by passive diffusion down a concentration gradient or by the generation of an electrochemical gradient (where a species is moved against its concentration gradient but down another gradient, such as electrical potential). If the motion is driven by the coupled transport of another system, the two species can migrate in either the same (symport) or opposite (antiport) directions across the membrane. Highly selective transport across lipid bilayers is made possible by the large number of specific channels and carriers in biological systems driven by the relaxation of transmembrane electrochemical gradients toward thermodynamic equilibrium.

These electrochemical gradients are maintained by only a few ion pumps, most commonly ATPases that hydrolyze ATP and generate directional transport using the resulting release of energy. Although the mechanism of directional motion in these motor proteins is not yet fully understood, conformational changes leading to altered binding affinities seem to be particularly important.⁵¹⁻⁶⁰ Access to the binding sites of these pumps is often “closed” by conformational changes after ion binding to increase the directionality of the process.^58,61

Proton pumping across membranes is a particularly important process as it creates the proton motive force that drives ATP synthases’ production of ATP, which in turn powers a large variety of active transport processes. This proton generated transmembrane potential is most commonly created by electron transport chains where redox reactions are used to separate charges across a membrane.⁶⁰ Proton pumping powered directly by light, as in bacteriorhodopisin (where cis/trans isomerization leads to directionality), is less common.⁶²⁻⁶⁷ Interlocked structures are often exploited in biology to help ensure high sequentiality, for example, in the ribosome,⁶⁸⁻⁷⁰ and various DNA polymerases.⁷¹

Biological molecular machines are used to transport cargo about a cell (e.g., kinesin), to power the movement of organisms (e.g., bacterial flagellar motors), to synthesize proteins (e.g., the ribosome), and to separate strands of DNA (e.g., helicases). There are many crucial differences between these machines and those familiar to us in the macroscopic world, in terms of both the tasks they accomplish and the manner in which they do so. Several concepts pertinent to the synthesis of artificial molecular machines can be extrapolated from these natural machines.

(1)
Biological machines cannot use thermal gradients due to the rapid dissipation of heat at the scale on which they operate.
(2)
Biological motors often use chemical energy from favorable bond forming/breaking events (e.g., ATP hydrolysis), or concentration gradients to drive their operation.
(3)
Biomachines operate in solution and on surfaces under high viscosity conditions.
(4)
Biological machines exploit Brownian motion rather than fight against it. They “ratchet” the random thermal motion of their components and substrates. Brownian motion also ensures the rapid mixing of machines, fuel, and substrates.
(5)
Friction is irrelevant in such a viscous medium, where constant Brownian motion ensures the mobility of individual parts.
(6)
Mobile biomachines, such as kinesin, often operate along tracks to reduce the available degrees of freedom of the machine. Kinetic association of the machine on track for the duration of operation is vital to achieve directed transport.
(7)
Noncovalent interactions are often significant features of the structure and operation of biological systems.
(8)
Biomachines are often made by self-assembly processes from a limited range of basic motifs such as amino acids, lipids, nucleic acids, and saccharides.
(9)
Compartmentalization is often required to allow systems to be maintained and operate away from equilibrium.
(10)
Small binding events can often cause large conformational changes.

Although biological molecular machines are of a level of complexity unattainable by the current generation of molecular machines, they are constricted by the evolutionary processes that gave rise to them and the environment in which they operate. Natural selection ensures that the first successful solution to a problem tends to be retained, and improved gradually over many iterations. These restrictions, in terms of chemistry, and solutions, do not apply to manmade systems. Biomachines also operate in a highly cluttered environment and thus must exhibit an extremely high tolerance to collisions with unrelated/unreactive species. Additionally, the study of less elaborate artificial systems may well give rise to a greater understanding of the sophisticated biological systems that inspired them. Nonequilibrium statistical mechanics can provide a more precise understanding of the basic mechanisms and processes used by the current crop of molecular machines and will be explored in the next section.

1.5. Directional Transport and Work under Brownian Motion

The Principle of the Detailed Balance provides important constraints on the relationship between equilibrium and rate constants. An understanding of this concept is important in the field of synthetic molecular machines and for the design of potential mechanisms for directional motion.⁷²⁻⁷⁴ The Principle of the Detailed Balance states that, at equilibrium, each transition has an equal probability (and thus rate) of occurring in a forward or reverse direction (e.g., k₁= k_–1). This means that at equilibrium no net flux is generated across any barrier and no task can be performed. This rules out the maintenance of an equilibrium by a cyclic process such as A → B → C → A; rather each substrate must be in equilibrium with every other that it is in exchange with, that is, A⇆ B + B ⇆ C + C ⇆ A instead. It follows that Smoluchowski’s trapdoor could not operate as it would break the Principle of Microscopic Reversibility. Breaking detailed balance is a requirement of doing work at the length scales on which Brownian motion occurs.⁷⁵ Stochastic pumping breaks detailed balance using an oscillating parameter to generate net flux and maintain a nonequilibrium steady state, and is seen in nature, for example, in the ATPases.^76,77 Several theoretical frameworks have been developed to explain various fluctuation driven transport modes such as stochastic pumping, which govern transport in Brownian motors and ratchets.⁷⁸⁻¹²⁶ Some particularly relevant examples are discussed below.

1.6. Ratchet Mechanisms

Brownian ratchet mechanisms fall into two general classes: energy ratchets (pulsating and tilting ratchets are subcategories of energy ratchets) and information ratchets.^127−129

1.6.1. Pulsating Ratchets

In pulsating ratchets, potential-energy minima and maxima are varied in a periodic or stochastic manner with no reference to the position of the particle on the potential-energy surface.¹²⁸ The simplest form is an on–off ratchet where the potential is repeatedly turned on and off more rapidly than the diffusion of the Brownian particles over their potential energy surface. This results in the net directional transport of particles across the surface (Figure 3).

An on–off ratchet: (a) the particles are located in an energy minima, (b) the potential is turned off so that diffusion can occur for a short time, and (c) the potential is turned on again. As the potential is asymmetric, particles have a greater probability of being trapped in an adjacent well to the right of the original one than to the left. (d) Relaxation into the local energy minima leads to the average position of the particles moving to the right.¹²⁸

A flashing ratchet is a subtype of the pulsating ratchet, consisting of a repeating series of maxima and minima. The sequential lowering and raising of parts of this potential energy surface leads to directional transport (Figure 4).

A flashing ratchet. In (a) and (c), the particle starts in a green or orange well, respectively. Raising this energy minima while lowering the adjacent maxima and minima triggers movement by Brownian motion (b) to (c) or (d) to (e). By continuously varying the relative heights of the energy barriers and minima of the energy wells, the particle can be directionally transported.¹²⁸

An asymmetric potential energy surface is not strictly necessary to generate a pulsating ratchet.¹²⁸ A periodic array of local minima traveling at a constant velocity (i.e., a traveling wave) can be used to form a traveling potential ratchet. In terms of realistic systems, the traveling potential ratchet mechanism has most relevance for the field-driven processes discussed in section 5 and the self-propulsion mechanisms of section 6.

1.6.2. Tilting Ratchets

In a tilting ratchet, the underlying potential energy surface remains unchanged, and detailed balance is broken by the application of an unbiased driving force to the particles, such as heat.¹²⁸ When the applied force is heat, the ratchets are also referred to as temperature or diffusion ratchets (Figure 5). In its simplest form, the mechanism is very similar to that of the on–off ratchet. Here, particles cannot cross the energy maxima at low temperature, but a brief increase in temperature allows the diffusion of particles across the surface. A lowering of temperature traps this movement in a manner similar to the on–off pulsating ratchet leading to directional transport. The period of raised temperature must be brief to prevent general diffusion, which would destroy any directionality initially gained.

A temperature or diffusion ratchet. (a) The particles are located in an energy minima on the potential-energy surface, with energy barriers ≫k_BT₁. (b) The temperature is increased so that the height of the barriers is ≪k_BT₂, and free diffusion is allowed to occur for a short time. (c) As the temperature is lowered again, the asymmetric potential energy surface means that the particles have a greater probability of being trapped to the right of their initial position. (d) Relaxation to the local energy minima.¹²⁸

Directional motion can also be achieved by the application of a periodic directional force to an asymmetric potential energy surface in a rocking ratchet. Although the net driving force averages to zero, directional motion is driven by exploiting the asymmetry of the potential energy surface (Figure 6).

A rocking ratchet. (a) Particles are located in an energy minima on the potential energy surface. (b) A directional force is applied to the left. (c) An equal and opposite directional force is applied to the right. (d) Removal of the force and relaxation to an energy minima leads to the average position of the particles moving to the right.¹²⁸

Similarly, in a fluctuating force ratchet, the applied driving force is randomly generated and varies stochastically. Finally, in an asymmetric tilting ratchet, the particles lie on a symmetric potential energy surface, but the applied potential provides the required asymmetry. For example, in a rocking ratchet, the tilt in one direction would be longer than in the other.

1.6.3. Information Ratchets

Energy ratchets operate by the application of an external force or the modulation of a potential energy surface irrespective of the particle’s position.¹²⁸ Information ratchets, on the other hand, rely on raising or lowering an energy barrier according to the position of the particle on the potential energy surface (Figure 7). This results in the distribution of particles being driven away from equilibrium. This process requires information transfer from the particle to the potential-energy surface, in a manner reminiscent of Maxwell’s demon.

An information ratchet. In (a) and (d) the dotted lines represent the transfer of information about the position of the particle. (b) The position of the particle lowers the energy barrier to movement to the right-hand well but not the left. (c) The particle moves by Brownian motion.¹²⁸

1.6.4. Language Necessary To Describe the Operation of Molecular Machines

Four terms are useful for describing the relationship of the components/substrates of molecular machines in terms of dynamics: balance, linkage, ratcheting, and escapement.⁷⁵ Having the components/substrates in a state of “balanced/unbalanced” or “linked/unlinked” plays a crucial role in determining whether or not a machine can perform a task. “Balance” is the thermodynamically preferred distribution of a particle (or submolecular component) in a molecular system. The trigger for net transportation comes from the balance being broken (i.e., the system being in a nonequilibrium state) (section 4.4). “Linkage” is the communication necessary for the transport of a particle between parts of the machine. However, the ability to exchange a particle between two parts of a machine does not necessarily allow a task to be performed, as a driving force is also required. Linking and unlinking operations are not limited to the addition or removal of steric bulk. They refer to any action that has an influence on the rate of a reaction. The movement of a particle up an energy gradient is described as ratcheting. It involves capturing the transitory positional displacement of a particle through the imposition of a kinetic energy barrier. Escapement is the counterpart to ratcheting in which the lowering of a kinetic energy barrier allows a ratcheted substrate to relax from a statistically unbalanced system toward a thermodynamic sink.

2. Controlling Motion in Covalently Bonded Molecular Systems

2.1. Controlling Conformational Changes

2.1.1. Correlated Motion through Nonbonded Interactions

At room temperature, organic compounds typically fluctuate between rapidly equilibrating stereoisomeric structures through the perturbation (rotation, lengthening, and shortening) of covalent bonds. The relative stability and energy barrier to interconversion of configurational and conformational isomers depend on intramolecular and intermolecular interactions. The rotational and vibrational freedom of a single substituent of a molecule is not only determined by its connectivity, shape, and size, but also its interactions with neighboring substituents.^130−133 For example, Mislow et al. demonstrated the steric influence of neighboring groups on rotation as part of their work on molecular propellers such as compound 1 where two or more aryl rings are attached to a single atomic center (Z) (Figure 8). The rotation of one aryl ring about a C–Z axis is sensed by the other rings. Mislow suggested that the motion of the rings is coupled in the sense that none of the rings move independently of the others and described such correlated motion as “sympathic”.^{130,134−138}

Chemical structure of a triaryl molecule as an example of a molecular propeller.^130,139

Öki’s group conducted pioneering investigations into restricted rotation about sterically hindered single bonds in molecules such as 9-arylfluorenes and triptycenes.^140−149 These molecules showed very high rotational barriers, and, in some cases, it was possible to isolate the rotational isomers (rotamers). Inspired by this work, Mislow and Iwamura simultaneously introduced the concept of dynamic gearing of proximate substituents in crowded molecules in molecular analogues of propellers and bevel gears.^150−167 The first molecular bevel gear consisted of two 9-triptycyl groups joined through their bridge head carbons to a central atom (Figure 9). Experimental and theoretical studies confirmed that the triptycyl groups are tightly intermeshed and undergo correlated disrotatory motion.^150,156

(a) Molecular bevel gear 2, consisting of two 9-triptycyl groups joined through a bridge head carbon to a central atom.¹⁵⁰ (b) X-ray structure of the molecular bevel gear (side view). (c) X-ray structure of the molecular bevel gear (top view). Adapted with permission from ref (156). Copyright 1984 American Chemical Society.

Many other examples of dynamic gearing have since been published including a range of triptycene derivatives,^168−174 metallocene-based gears,^175,176 conformationally restricted amides,^177−181 and a series of propeller molecules and other molecules with selective rotation,^{132,133,139,182−194} such as 1,2-di-o-tolylnaphthalene moieties.^195,196

The sandwich-shaped trinuclear silver(I) complex [Ag₃(3)₂] (Figure 10) developed by Shionoya and co-workers^197−199 is an example of a different type of a rotational device. The complex consists of two disk-shaped ligands, 3, consisting of three thiazolyl or 2-pyridyl ligands and three p-tolyl groups attached to a central benzene ring. The three p-tolyl groups force the neighboring ligands to adopt a nonplanar arrangement with respect to the central aromatic ring, and make the coordination sites more accessible for silver(I) cations. The exterior rings tilt at 30° in the same sense and thus form helical structures with P and M geometries. A change from P to M helicity, and vice versa, was induced by 120° relative rotation of the ligand in these complexes (Figure 10). These observations were further studied using a heterotopic system [Ag₃(3)(4)] consisting of a hexa-monodentate ligand 4 and a tris-monodentate thiazolyl ligand 3, which complex three silver(I) cations.²⁰⁰ In the case of the hexa-monodentate thiazolyl ligand 4, only every second ring is coordinated to a silver cation. Correlated flipping motion of the coordinating rings (and ligand exchange) results in the conversion from M to P and a 60° rotation of the two disks (Figure 10d).

(a) Chemical structure of tris-monodentate disk shaped ligand 3 and hexakis-monodentate ligand 4. (b) Schematic representation of complex [Ag₃(3)₂] shown as its M-helical enantiomer. (c) X-ray structure of complex [Ag₃(3)₂].¹⁹⁷ (d) Schematic representation of the flipping motion of the rings attached to the disks and subsequent ligand exchange from 1-A, 3-E, and 5-C in M to 1-B, 3-F, and 5-D in P. The direction of rotation in the M to P transition is opposite to that of a subsequent P to M′ transition.²⁰⁰ Reprinted with permission from refs (197) and (200). Copyright 2003 and 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Related heterotopic complexes were later used to transform the rotational motion of the sandwich-shaped trinuclear silver(I) complex into translational motion using a molecular crank mechanism. In molecular crank 5, a [2]rotaxane was attached as a translational segment (Figure 11).²⁰¹

(a) Schematic illustration of a crank mechanism that translates linear motion into rotary motion in cylinder engines. (b) Schematic representation of a molecular crank mechanism. (c) Chemical structure of a synthetic molecular crank 5.²⁰¹ Reprinted with permission from ref (201). Copyright 2010 Royal Society of Chemistry.

Recently, Anderson et al. reported a zinc-porphyrin macrocycle coordinated by two templates containing multiple pyridines (wheels) forming a caterpillar track complex.²⁰² NMR exchange spectroscopy (EXSY) experiments showed that the ring underwent correlated motion with correlated motion of the templating “wheels”.

The examples shown in this section clearly show the influence that steric interactions can have on submolecular motion. However, at equilibrium, these motions are nondirectional, even during a partial rotation.

2.1.2. Stimuli-Induced Control of Conformation about a Single Bond

An early example of controlled random rotary motion about a single bond was provided by Kelly et al.,^203−205 who utilized a cation binding event to halt the free rotation of a triptycene moiety in “molecular brake” 6 (Scheme 1). The two pyridine groups must be coplanar to maximize binding with Hg²⁺, thus raising the energy barrier to rotation by “putting a stick in the spokes”. Sulfur oxidation has similarly been used to inhibit free rotation in 7 with mono- or dioxidation significantly slowing the rotation.²⁰⁶ Rotation about a single bond has also been promoted by substrate protonation by Shimizu and co-workers in 8.²⁰⁷ Protonation of the quinoline nitrogen led to an increase in the rate of rotation by 7 orders of magnitude, through a proposed hydrogen-bonding stabilization of the rotation transition state (Scheme 1). The same group observed that utilizing an acetate guest’s hydrogen-bonding interactions to “turn on” rotation provided a more modest accelerating effect.²⁰⁸ Again, this was suggested to be via a lowering of the energy of the rotational transition state. Other examples have also been reported.^209,210

Singlet oxygen has been used to promote rotation in combination with thermal relaxation in a system based on rotation between the cis and trans isomers of 9 (Scheme 2). Reaction with singlet oxygen forms the cis-substituted 9,10-endoperoxide selectively. Thermal reversion generates the cis-anthracene, which upon extensive heating furnishes the more thermodynamically stable trans-anthracene 9, completing the cycle.²¹¹

Kelly and co-workers reported an attempt to create a Feynman adiabatic ratchet-and-pawl.^212−214 The design utilized a helicene pawl whose inherent helical chirality was intended to bias the rotation of the triptycene cog. Although this design realizes an asymmetric potential energy surface, ¹H NMR showed no directional bias with equal rates of rotation in both directions. This is in line with Feynman’s thought experiment²¹⁵ and illustrates that the rate of rotation depends solely on transition state energy and temperature, and not on the shape of the barrier to rotation. State functions, for example, free energy, do not depend on the system’s history (Figure 12).

(a) Kelly’s ratchet-and-pawl 10. (b) Enthalpy change on rotation of helicene. Reprinted with permission from ref (212). Copyright 1997 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The key factor required to break detailed balance and allow directional motion of the triptycene cog is an energy input to drive the system away from equilibrium. Although a rapid periodic variation in temperature could in theory cause the system to act as a temperature ratchet, it would be very difficult to verify this experimentally. As such, Kelly et al. instead proposed the modified structure 11,^216,217 where a chemical reaction drives the system from equilibrium (Scheme 3). The helicene pawl oscillates in the energy minima between blades, and, ignoring the amine group, all three minima are identical. Formation of the isocyanate from reaction with phosgene activates the system. In the course of random fluctuations, sometimes the helicene is close enough to the isocyanate to react. After reaction, the helicene is trapped part way up the energy barrier; that is, the helicene is “ratcheted” part way to rotation. Random thermal fluctuations may then overcome the smaller barrier to rotation, and the urethane can be cleaved to give overall 120° rotation. This machine is a landmark achievement in the realization of chemically fueled directed rotation in molecular machines and demonstrates most of the basic tenants of a directional motor. However, attempts to modify the rotor to allow 360° rotation have thus far failed.²¹⁸

Mock and Ochwat have proposed a minimal molecular motor in which epimerization of a stereogenic center, that is, a formal 180° rotation, is driven by the hydration of a ketenimine fuel.²¹⁹ A biaryl lactone motif reported by Branchaud has been used to control motion about a single bond in a nondirectional rotor based on the facially selective ring opening of a chiral lactone.²²⁰ They later improved on this system to report 180° directional rotation.²²¹ Feringa et al. achieved full 360° directional motion about a single bond in a related biaryl system (Scheme 4).^222,223 Rotation was driven by four sequential chemical “power strokes” with felicity of rotation for each step being between 90% and 100%. The cycle involved four conformationally restricted intermediates, 12–15, with 12 and 14 locked by covalent bonds, and 13 and 15 locked by their steric bulk. Although 13 and 15 are free to dynamically equilibrate between helical forms, the chiral information in the reducing agent is used to discriminate between them and thus drive directional motion. The first step involved asymmetric ring opening with the (S)-CBS reagent, and regioselective protection of the resulting phenol with an allyl group. After oxidation and PMB deprotection with spontaneous lactonization, 180° rotation was achieved. Another stereoselective ring opening and regioselective phenol protection as the PMB ether followed, before oxidation and ring closure furnished the product of 360° rotation in high fidelity. Additionally, rotation in the opposite sense can be achieved by utilizing the (R)-CBS reagent and reversing the order of PMB/allyl protection.

Scheme 4 — Rotation is restricted in A and C by covalent bonds, although helical inversion is allowed, and in B and D by nonbonded interactions, with directional control of rotation being provided by stereospecific covalent bond cleavage.²²²

2.1.3. Stimuli-Induced Conformational Control in Organometallic Systems

Control of the rotary motion of ligands in metal sandwich or double-decker complexes is somewhat conceptually similar to controlling rotation around covalent single bonds. Aida and co-workers demonstrated that porphyrin ligands in double decker complexes such as 16 can rotate with respect to each other depending on the central metal atom and their steric bulk (Figure 13a).^224,225 Studies on a variety of metal complexes found that the central metal had an influence on the speed of rotation.²²⁶ Complexes synthesized from two D_2h symmetry porphyrin free-bases are chiral, and therefore their rotary motion corresponds to enantiomerization and can thus be studied by CD spectroscopy. Racemization can be induced by protonation or reduction of the metal center. The second reduces π–π interactions between the two ligands as a consequence of the larger ionic radius of the metal center.²²⁷

(a) X-ray crystal structure of porphyrin double decker complex 16 with cerium(IV). Reprinted with permission from ref (228). Copyright 1989 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. (b) Representation of the cooperative binding of guest molecules to porphyrin double decker complex 17.²²⁹

It was shown that the rotation of the cerium(IV) bis[tetrakis(4-pyridyl)porphyrinate] 17 could be suppressed by successive cooperative guest binding of dicarboxylic acids (Figure 13b).^229,230 The double decker complex shows a large allosteric effect in this molecular recognition event (once rotation has been suppressed by the first guest molecule, guest binding becomes increasingly favorable). Further guest molecules have been tested such as β-dicarboxylate anions,²³¹ potassium ions,²³² mono- and oligosaccharides,^233−235 and silver cations.²³⁶ In the case of silver ions, it was shown that their cooperative binding leads to a progressive and nonlinear increase in the rate of rotation.^237−244 The rotation of a similar cerium double decker complex has been monitored on a single molecule level, by the attachment of a bead visible under optical microscopy.²⁴⁵

Ever more complicated systems such as multidecker pophyrin complexes²⁴⁶ and mechanically interlocked porphyrin systems like 18 have been synthesized (Figure 14).^247−249 The latter consist of cerium(IV) or lanthanum(III) bis(porphyrinate) double decker complexes and one or two orthogonal porphyrin molecules. In these “molecular gears”, the rotation of the top and side units could be partially coupled through mechanical interactions between the different units. A folding ruler based on similar principles has been reported.²⁵⁰ A dodecanuclear four level complex that mimics a double ball bearing has also been synthesized.²⁵¹

Cerium(IV) bis(porphyrinate) double decker (top unit) and a rhodium(III) porphyrin-based side cog. The two units are connected through a coordination bond between rhodium(III) and a pyridyl group.²⁴⁹

Ferrocene is a prototypical sandwich complex with an iron atom symmetrically aligned between two C₅H₅ (cyclopentadienyl) rings.^252,253 The barrier to rotation of the two rings about the C₅ axis is very small in the gas phase. Using electrospray ionization and theoretical studies, it was shown that ferrocene derivative 19^2– can serve as a two-state rotary switch, which works through proton transfer (Scheme 5). Differing electrostatic interactions lock 19^2– and [19·H]⁻ in two different conformations. The trans conformation of 19^2– is more stable because of Coulombic repulsion between the negative charges, while the cis conformation of [19·H]⁻ is stabilized through hydrogen bonding (Scheme 5).

This finding was followed by studies of many more ferrocene derivatives, and the control of their rotary motion through different stimuli such as electron transfer and photochemistry.^254,255 Ferrocene-based rotors have recently been used to form self-assembled nanostructures.²⁵⁶

Metallocarboranes tend to have rather high barriers to rotation around the metal–ligand axis, but some complexes, for example, nickel complex [Ni(20)₂], can be used as electrochemically controlled rotary switches (Figure 15).^257−261

(a) Dicarbollide ligand 20^2–. (b) Metallocarborane [Ni(20)₂], an electrochemically controlled rotary switch.²⁶¹

2.1.4. Stimuli-Induced Conformational Control over Several Covalent Bonds

In biological systems, host–guest binding is often used to induce conformational and functional changes. These changes can vary from small, localized, bond deformations to long-range rearrangements across multiple covalent bonds. These deformations are frequently used to alter binding at distal sites, that is, allosteric regulation. There are several synthetic examples where host–guest binding causes a sufficiently large amplitude change to merit discussion in this Review. Some of the earliest examples of allosteric receptors came from Rebek and co-workers.²⁶² For example, the binding of tungsten by negative allosteric receptor 21 reduces the receptor’s affinity for potassium ions, as in this more rigid conformation binding to potassium would induce a degree of strain (Scheme 6).^263,264 The positive allosteric receptor 22 developed by the same group depends on the initial mercury binding event preorganizing the linked receptor for a second, more favorable binding event.²⁶⁵ These early examples have sired an extraordinary and diverse array of synthetic allosteric receptors.^{262,264,266−279}

Organic guests can also cause large-scale changes to host molecules, as they maximize favorable interactions such as in molecular tweezer 23 (Figure 16) where the distance between sidewalls halves on binding certain guests.^280,281 A large amplitude change was observed in the flexible system 24 with an extended conformation being exchanged for a more rigid “sandwich” form to maximize guest binding.²⁸² Guest-induced change is also observed in clip 25 where the sa form predominates in solution in the absence of a guest, but the aa form dominates in the presence of a suitable guest (Figure 16).^283−285 This system has been further modified in 26 where the binding of a potassium ion to each crown ether preorganizes the system for organic guest binding with increased affinity.²⁸⁶

(a) Molecular tweezer 23, arrows indicate direction of contraction. (b) Clip 25, where the aa form is favored in the presence of a guest. (c) Clip 26, where ion binding enhances guest affinity. (d) Crystal structure of uncomplexed and complexed 24.^{282,283,286,287} X-ray crystal structure reprinted with permission from ref (282). Copyright 2007 American Chemical Society.

Metal coordination has been used by Lehn et al. to switch from an arrangement where parallel anthracene units can bind electron-poor 2,4,7-trinitro-9-fluorenone (TNF) in a tweezer-like manner, to an open form 27 (Scheme 7). Here, coordination of copper in a bidentate manner by the aromatic nitrogens causes a rotation about the heterocyclic axis and opens the guest binding cavity, preventing TNF coordination. In related 28, zinc coordination is a prerequisite of TNF binding.²⁸⁸

A notable example of chelation control of conformation was provided by trisaccharide 29 (Scheme 8). Although the tetra-equatorial isomer is the dominant form in solution,²⁸⁹ the addition of Pt(II) led to coordination, and a preference for the tetra-axial form, the better to bind the metal ion. This process could be reversed by removal of the Pt(II) with excess NaCN.^290,291 This process has been replicated with a variety of cyclic substrates using both metal ion binding^292−294 and pH variation.^295−297 Sauvage reported the collapse of a porphyrin containing [4] rotaxane on copper removal.²⁹⁸ Haberhauer’s molecular hinge, 30, based on a 2,2′-bipyridine motif, is another example of large amplitude motion controlled by coordination of a metal ion. In this case, the open system was free to rotate over 180° with its rotation being constrained by an inflexible backbone. Upon coordination of Cu(II), the hinge shut. Upon copper removal, the hinge was again able to open, but only in one direction due to the constraints of the backbone.²⁹⁹ A light-driven switch and a chirality pendulum based on a similar system have been reported by the same group.^300,301

Cavitands derived from resorcin[4]arenes have been shown to undergo large conformational changes between open “kite” and closed “vase” forms of 31 (Scheme 9).³⁰² Because of solvation effects, the kite form is normally favored at lower temperatures and the vase at higher.^302−304 However, this change has also been achieved using protonation of or metal coordination to the quinoxaline nitrogens,^305−308 or by altering the design to incorporate redox-active centers.^309,310 Substitution of the cavitand with amide groups can lead to stabilization of the vase form by dimerization or guest complexation.^311−320 As an alternative to coordination of a guest causing a change in conformation, complexation can be intramolecular as in macrocycle 32 reported by Stoddart et al. The system rests in the self-complexed form until reduction of the cyclophane decreases subcomponent interactions, followed by release of the system to an unrestrained, unencapsulated form.^321−326 A similar system, 33, was realized by Feringa and Qu³²⁷ with directional rotation inhibited in the complexed state, but allowed when uncomplexed (Scheme 9).

Scheme 9 — Reprinted with permission from refs (321) and (327). Copyright 1997 and 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hamilton and co-workers introduced conformational switch 34 (Scheme 10) where in the initial state the equilibrium is mildly biased toward the benzamide station (1.3:1). Upon protonation of the dimethylamine with TFA, a dramatic reversal of this bias is observed (1:99).³²⁸ The oxidation of a copper center has been used to trigger coupled rotation and copper exchange between two independent switches (based on the structure shown in Scheme 45).³²⁹

Oligomeric systems have been used to great effect in generating large-scale conformational changes, often exploiting the helical secondary structures that can be formed by many species.^330−367 Polyamide 35 resides in a helical arrangement, but protonation of four diaminopyridine units causes a dramatic extension to the linear form of 35 (Scheme 11). Further protonation leads to another helical form, and the system can be returned to its initial form by deprotonation.³³⁰ An extension of this system was shown to expand from 12.5 to 57 Å upon protonation.³⁶⁸ An alternating pyridine and pyrimidine oligomer formed helices (due to the favored disposition of neighboring rings being transoid), but upon addition of Pb(II) to 36, coordination led to a linear form with a concurrent increase in length from 7.5 to 38 Å (Scheme 12). This process could be made switchable by sequestering the Pb(II) until needed in pH responsive cryptand 37.³⁶⁹ A similar process has been achieved using Ag(I) to modulate expansion.³⁷⁰

An interesting recent example was provided by Stadler and Lehn³⁷¹ where a linear and a helical domain were synthesized in the same molecule. In this two-domain system, coordination of Pb(II) led to the unfurling of the helical domain with concurrent curling of the linear portion of the molecule. Upon removal of Pb(II), the system reverted to its original state, thus representing a reversible device where an extension process is coupled to a furling one, on both complexation and decomplexation of a metal ion.

2.2. Controlling Configurational Changes

Changes in configuration, especially cis/trans isomerization, have been used in many molecular systems to control motion.³⁷² Although the sometimes small amplitude motion is not always useful for the design of molecular machines, it represents an interesting tool for inducing directional motion in synthetic and supramolecular systems. The most prominent examples of this type of system are the photoisomerization of stilbenes and azobenzenes,^373−377 the reversible electrocyclization of diarylethenes,^378−382 the photochromic reactions of fulgides,^383,384 the interconversion of spiropyrans with merocyanin,³⁸⁵ as well as chiroptical switching of overcrowded alkenes.^386−388 In recent years, this topic has become an extensive area of research, and a wide range of applications exploiting switchable systems have been proposed and realized.^389−395 Most of these applications rely on intrinsic electronic and spectroscopic changes on interconversion between the two species, but some use small configurational changes in a more mechanical fashion, and the resulting devices can be seen as molecular machines.

Configurational changes, especially the photoisomerization of azobenzenes, have been used to induce changes in the structures of biologically relevant molecules such as antibiotics, peptides, and DNA,^{374,396−406} but also as part of small-molecule systems such as molecular scissors, tweezers, and other molecular machines.^407−412 Some of them will be introduced in the following section.

Molecular scissors 38, described by Aida and co-workers, consist of an azobenzene unit and a ferrocene unit (Scheme 13a).^413,415 The open and closed forms were interconverted by photoisomerization of the double bond of the azobenzene unit, which led to an angular change of 49° around the cyclopentadienyl rings of the ferrocene. Another example was the synthesis of the molecular hinge 39 where two xanthene rings were connected by −N=N– linkers (Scheme 13b).⁴¹⁴ Photoisomerization at 366 nm from the trans/trans, which is almost planar, to the cis/cis state resulted in a change of approximately 90° in the angle between the two aromatic rings. Reisomerization could be achieved by irradiation at 436 nm. Azobenzenes have been used for the construction of photoswitchable azo-macrocycles.^389,416 Azo-macrocycles have found applications in host–guest chemistry as they can selectively and reversibly bind ions. Cyclic azobenzenes have been used to switch on or off the rotation of subunits.^417,418 A recent example showed that the rotation of a 2,5-dimethylbenzene rotor in the cyclic azobenzene 40 could be switched off in the E-isomer of the azobenzene, while rotation was allowed in the Z-isomer (Figure 17).

(a) Chemical structure of a molecular brake 40 with a 2,5-dimethylbenzene unit as the rotor. (b) X-ray crystal structure. (c) Schematic representation of this photoinduced molecular brake. X-ray crystal structure reprinted with permission from ref (418). Copyright 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Azobenzenes have also been used to control motion in molecular shuttles (see also section 4.3) and to control the threading and dethreading rate of a macrocycle when attached to the ends of a thread. In a recently published example, E → Z photoisomerization of azo-end groups slowed the threading–dethreading of a ring and turned the pseudorotaxane into a kinetically inert rotaxane.⁴¹⁹

The substitution of an alkene can lead to steric overcrowding around a double bond. When the substituents are large enough, the planarity of the double bond can be disrupted and a variety of twisted and folded conformations can be adopted, including helices. The area where the substituents come into close proximity is often referred to as the fjord region. These types of compounds still undergo photoisomerization and can be used as chiroptical molecular switches.^386,420,421 Feringa et al. have developed several molecular motors exploiting overcrowded alkenes as chiroptical molecular switches.^422−428 The first generation of this molecular motor (Scheme 14, compound 41) featured two identical halves connected by a central double bond.^429−436 Each of the halves had a stereocenter, which was crucial to controlling the rotational process. Rotation of 360° around the double bond was repetitive and directional. Two light induced cis–trans isomerizations led to a 180° rotation and were each followed by thermally controlled helicity inversion, which effectively blocked reverse rotation. The cis–trans photoisomerization was evident from ¹H NMR, and the simultaneous exchange of P to M was detected by circular dichroism (CD). A number of different structures have been synthesized to optimize the rotation process and to explore the limits of the system.^437−444

Scheme 14 — (i) Photochemical isomerization leaves substituents in the unstable equatorial conformation (M,M)-(*cis*)-41-unstable. (ii) Steric strain is released by a thermally activated helicity inversion leading to (P,P)-(*cis*)-41-stable. (iii) Photoisomerization from *cis* to *trans*. (iv) Helical inversion completes a full rotation.⁴²⁹

In the second generation of Feringa’s molecular motor 42, two halves that are not identical were connected by a central double bond.^445−447 One half was replaced by a tricyclic aromatic group and there was only one stereogenic center present, but the rotation operated according to the same principles as the first generation motor 41 (Figure 18). Some dramatic enhancements of rotary speed were achieved in the second generation of motors.^{428,448−453}

Comparison of the general structures for the first (41) and second (42) generations of Feringa’s molecular motors.⁴²⁵

Feringa and co-workers have shown that transmission of molecular rotation from one part of a molecule to another is possible. In motor 43, a xylyl unit was attached to the lower half of an overcrowded alkene-based switch. By switching between the cis- and trans-forms, the rotation of the xylyl group could be controlled (Figure 19).^454,455 Imines have recently been used as directional light-driven rotors by Lehn and Greb.⁴⁵⁶

It has long been known that irradiation of hydrazones can induce E → Z isomerization around the imine bond (C=N). However, the Z-isomer is usually thermodynamically unstable and thus short-lived.^457,458 Intramolecular hydrogen bonding in various hydrazone derivatives can kinetically stabilize the Z-isomer, which is formed by irradiation.^459−461 The Aprahamian group has studied the E/Z isomerization of hydrazones using chemical switching inputs such as protons and zinc ions.^462−467

In their original system, E→ Z isomerization was induced by protonation of a pyridyl ring that initially acts as an intramolecular hydrogen-bond acceptor in the E-isomer (Scheme 15, compound (E)-44).^468,470 In the Z-isomer, the carbonyl oxygen stabilizes the Z-H⁺ form of the molecule because the pyridyl unit is no longer available as a hydrogen-bond acceptor. Upon deprotonation, the process is reversed. However, the Z-isomer is metastable, and as a consequence the removal of the proton does not lead to an immediate change. The thermodynamically more stable E-isomer reappears with time. The Aprahamian group has also replaced the naphthalene unit with a quinoline unit (see (E)-45), thus introducing an additional hydrogen-bond acceptor and an additional metal ion binding pocket next to the hydrazone.⁴⁶⁹ In this system, a Zn²⁺ ion now triggers E → Z isomerization. The most recent system showed that on addition of Zn²⁺ to (E)-46 and (E)-47, a switching cascade could be initiated.⁴⁷¹ Coordination of Zn²⁺ to (E)-46 lowers the pK_a of the imidazole N–H by 3 units and allows the protonation of (E)-47, which in turn allows switching of this moiety. Without metal coordination, the imidazole is not acidic enough to catalyze switching in (E)-47, making this sequence an elegant example of one switching event acting as the input for another, in one pot. Because the stator and rotor are held in fixed relative positions, the switches developed by Aprahamian and co-workers represent very promising tools for the control of directional motions in molecular machines (Scheme 16). A hydrazone switch has been used to dope a liquid crystal with the color of the liquid changing upon switching.⁴⁷²

Scheme 15 — (a) Protonation of the pyridyl nitrogen of compound (E)-44 induces E → Z isomerization.⁴⁶⁸ (b) The quinoline unit in (E)-45 provides a binding site for a Zn²⁺ ion, which is now the trigger for E → Z isomerization.⁴⁶⁹

3. Controlling Motion in Supramolecular Systems

The use of supramolecular systems in molecular machines is challenging as competing processes such as the association and dissociation of subcomponents from and to the bulk must be controlled.^473,474 These processes can interfere with the integrity and/or processivity of the machine unless the binding is part of the motion generation process itself or the effect of unbound elements is restricted. If host–guest interactions are used to assemble a machine, then exchange with free hosts or guests in solution should be avoided to maintain the integrity and kinetic stability of the machine. Disassembly or exchange can, in certain cases, be intentionally exploited for functional purposes and to provide communication with external species. Controlled motion in supramolecular systems must be built on cooperative interactions of individually weak but collectively strong noncovalent interactions.

In biology, large-scale molecular motion generated upon guest binding is a common process. Acetylcholine neurotransmitters are among such guests and bind to a transmembrane channel receptor, inducing a large conformational change, resulting in the controlled flux of ions through the membrane.⁴⁷⁵ In this case, any guests in the bulk can act as an inducer of molecular motion and at the same time as a messenger of the microenvironment enabling dynamic communication with the surroundings. The stabilities of most biological functional assemblies are well maintained by restriction of bulk exchange. If this was not so, rapid exchange of the ribosome complex or individual subunits of the ribosome during protein synthesis would detach the enzyme from the substrate mRNA and release a partially synthesized peptide, unlikely to be of any use. However, mRNA and the ribosome form a kinetically stable complex, subunit exchange with the bulk is restricted, and the enzyme processively produces large proteins.⁴⁷⁶

3.1. Guest Binding Generating, or Assisted by, Large-Scale Intramolecular Motion

Considering the above discussion, molecular machines and devices based on noncovalent assemblies require careful design. The relatively large molecular level motions generated upon guest binding are of great importance in the design of practical molecular machines. Guest-induced molecular motion has been widely studied in the literature with organic compound,⁴⁷⁷ anion,⁴⁷⁸ cation,^479−481 metal,^{464,471,482,483} or proton guests.^484,485 Switches based on pseudorotaxanes have also been reported.^486−518 These supramolecular complexes display interesting operational properties that are useful for device development.^{495,519−564} These switches can be used to build relatively sophisticated devices such as the molecular tweezers 23–26.^{280,281,287,288,565−575} This concept conventionally refers to receptors having a cavity with two binding motifs. The binding pocket can either readily encapsulate the guest (lock and key type) or evolve to a more suitable conformation upon guest binding (induced fit type). Molecular machines can be regulated by responsive tweezers, with motion induced and regulated through an external stimulus such as the binding of guest molecules.

One of the earliest examples of a molecular machine was a “molecular tweezer” based on the photoisomerization-dependent binding of cations in a crown ether-bearing azobenzene, developed by Shinkai et al. (Scheme 17).^575,576 The open trans form can bind smaller cations such as Na⁺ selectively, whereas the cis form prefers to bind larger Rb⁺ ions by forming a sandwich complex with the cation. Moreover, the cis isomer can be stabilized by the sandwich complex in the presence of Rb⁺, and the photostationary state biased toward the cis isomer, causing the molecule to relax to the trans isomer much more slowly. Hence, in addition to photoisomerization-dependent changes in the affinity of the receptor, guest binding can alter the kinetics of the photoisomerization process.

Intercalation of electron-poor aromatic guests by molecular tweezers having two π-systems has also been explored by several groups.^577−581 The binding and release of the guest is modulated by the motion of the receptor components. Intramolecular motion has been induced allosterically by means of various stimuli including metals,^582−584 anions,^585,586 electrochemical reduction,⁵⁸⁷ and pH change.⁵⁷³ 2,6-Substituted pyridine 49 has been shown to change conformation upon protonation of the pyridine, such that the methoxy groups form hydrogen bonds with the pyridinium proton (Scheme 18).⁵⁷³ This hydrogen bonding results in a rotation around the single bond moving the naphthyl moieties away from each other. Intramolecular motion results in the release of the hydrophobic drug mitoxanthron, which had been bound by π–π interactions between two naphthyl receptors.

Extracting work from machines depending solely on supramolecular interactions would be difficult due to the rapid exchange of bound and unbound guests. However, some supramolecular host–guest systems are moderately stable and might be suitable for use in the assembly of molecular devices. A methylviologen (compound 50, MV²⁺) and a trans-azobenzene derivative (compound 51, trans-AB) were encapsulated by a cucurbit[8]uril (CB[8]) host (Figure 20). Each guest has distinct properties: MV²⁺ is redox active, and the azobenzene can be isomerized to its cis-form (cis-AB) on irradiation.⁵⁸⁸ One electron reduction of methylviologen (MV^+•) results in a binary encapsulation of the reduced species in the host and trans-AB is kicked out. Photoisomerization of azobenzene to its cis-isomer results in its ejection due to steric repulsion. Therefore, the initial heteroternary complex of MV²⁺, trans-AB, and CB[8] can be orthogonally switched to give two distinct complexes. In one complex, one-electron reduction of MV²⁺ forces out the azobenzene to form a homoternary complex (MV^+•)₂CB[8], while in the other photoisomerization of the azobenzene ejects cis-AB, while MV²⁺ stays encapsulated to form (MV²⁺)CB[8].

Orthogonal exclusion of an azobenzene and a viologen encapsulated by CB[8].⁵⁸⁸

These three distinct, stimuli-dependent, modes of complexation allow greater control over molecular behavior. To transfer this to the macroscopic world, thiol-functionalized trans-azobenzenes were attached to a gold surface. Upon complexation by CB[8], together with the fluorescently labeled MV²⁺, the surface became fluorescent, and due to the charged nature of viologen, a substantial increase in wettability was observed. Upon irradiation, the azobenzene was kicked out as its cis isomer, returning the surface to a nonfluorescent, hydrophobic state, after the unbound fluorescent viologen–CB[8] complex was washed away from the surface. The orthogonal control of switching processes is a vital tool for the creation of even more complex molecular devices, especially in memory device construction.⁵⁸⁸

One of the interesting emerging properties of supramolecular host–guest systems is the stimuli-dependent expansion and contraction of molecular constructs. This behavior will be revisited in rotaxane systems in section 8. In double-stranded helicate 52 (bridged by spiroborates at each end), sodium ion-induced reversible extension and contraction was observed with an accompanying directional twisting (Figure 21).⁵⁸⁹ In the presence of Na⁺, the molecule was forced to twist its central tetraphenol moiety to better coordinate the cation. The handedness of the helicate was preserved during this process. This process could be reversed by the sequestration of Na⁺ by [2.2.1]cryptand.

Na⁺-induced twisting in helicate 52. Reprinted with permission from ref (589). Copyright 2010 Nature Publishing Group.

The tetraphenolic central compartment could be replaced by two porphyrins to create a hydrophobic cavity for aromatic guests to stack inside.⁵⁹⁰ Upon intercalation of electron-deficient aromatic guests between the porphyrin rings, the distance between the two porphyrin units increased from 4.1 to 6.8 Å. This expansion in the central region induced a rotation, which reduced the torsion angle, and, due to steric constraints, the capping spiroborates unwound in a directional manner, demonstrating the first guest-induced rotary motion with accompanying corkscrewing motion. Guest control of screw motion, involving simultaneous linear translation and rotation, has been reported.⁵⁹¹ In this case, the guest acted as a template for the formation of helicates based on hydrogen bonding and biased the formation of one of the two equilibrium structures.

Stimulus-driven molecular level conformational change and subsequent control over the binding affinity of guest molecules have been used to regulate anion concentration in solution.^592−594 Flood et al. developed a triazole-based foldamer bearing an azobenzene moiety in the structure (Figure 22).⁵⁹⁵ Hydrogen bonding between the triazole units and a chloride anion together with π-stacking within the foldamer backbone kept the anion buried in the interior.^{592,596−602} Photoisomerization of the azobenzene moieties disrupted the stacking, inducing unfolding and releasing the anions. This photoinduced release and capture of anions is completely reversible. Calculated K values in acetonitrile decrease significantly from 3000 to 380 M^–1 upon irradiation with UV-light. In addition, the conductivity of the irradiated sample increased due to release of anions into solution. Helical inversion caused by ion binding has also been observed.⁶⁰³ Stimuli responsive switches have great potential in drug release and ion-cargo transport applications. Nitschke et al. have reported a complex system, where the addition of various signal molecules to a helical complex led to a cascade of changes in the self-assembled system and various product distributions could be formed.⁶⁰⁴

Control of anion concentration in solution by a photoresponsive foldamer. Reprinted with permission from ref (595). Copyright 2010 American Chemical Society.

In the above examples, binding properties are regulated by an external stimulus or by allosteric control. Large-scale molecular motions regulated by guest binding are of particular interest in molecular machine design, because the presence of the regulator acts as a chemical communication between the environment and the machine. This dynamic interaction would allow the development of smart molecular machinery that performs advanced operations dependent on the chemical environment, or perhaps allows communication between machines.

3.2. Intramolecular Ion Translocation

The molecular basis for the conversion (in archea) of photon energy into more useful potential energy relies on proton translocation between a photoisomerized retinal molecule and the amino acid residues on the protein scaffold in which it is buried. This process occurs with a well-defined directionality, leading to light-mediated directional proton pumping across a membrane.^384,605 In supramolecular systems, for accurate translocation to take place, the ion to be translocated should be more kinetically available for intramolecular motion than the bulk ion. An electrochemical gradient cannot be achieved if each ion acceptor takes ions from the bulk. Ion translocation can be controlled by changing the affinity of organic receptors or metal centers for the ion of interest, through external stimuli such as light or reduction/oxidation.⁶⁰⁶ In the case of proton transfer, some molecules have distinct photophysical properties such as a change in the pK_a of the molecule in the excited state, which enables rapid dissociation of the proton from one part of the molecule and reassociation with another, intramolecular acceptor, in an “excited-state intramolecular proton transfer” (ESIPT).⁶⁰⁷ This process has been extensively studied using 2-(2-hydroxyphenyl)-benzothiazole (HBT, Scheme 19).⁶⁰⁸ Fast proton transfer from the hydroxyl group to the nearby thiazole nitrogen takes place upon excitation of the molecule to generate a cis-keto form with a distinct, solvent-dependent, spectroscopic character. In this molecule, intramolecular hydrogen bonding mediates this fast proton transfer between different regions of the molecule.

Metals having more than one stable oxidation state can be translocated by oxidation or reduction or incorporated into a scaffold along with other ions that can be translocated. For either process, the molecule should bear more than one binding site, with different affinities, to drive the motion of the ion. Flexible receptors are most often used for ion translocation, but rigid aromatic systems can be suitable as well. These processes are usually accompanied by a visible color change due to changes in absorption after a change in the oxidation state of the metal, or due to ligand exchange. The reversible translocation of a chloride anion from a Cu(II) center to a Ni(III) center was an early example of a flexible system (Scheme 20a).⁶⁰⁹ The concentration-independent nature of the process indicated that anions translocate from the Cu(II) center in an intramolecular fashion rather than via exchange with the bulk.

Work by Mirkin et al. showed reversible intramolecular shuttling of a chloride anion from a bisurea binding site to Rh(I) in the presence of carbon monoxide (Scheme 20b).⁶¹⁰ The hydrogen-bonding ability of the urea was further enhanced by attaching electron-withdrawing 3,5-bis(trifluoromethyl)benzyl groups. Rh(I) adopts a distorted square-planar geometry with these phosphine and thioether ligands, as shown by the crystal structure. Initially, chloride was encapsulated between the urea tweezers. With the aid of polar solvents (dimethyl sulfoxide or dimethylformamide) and in the presence of CO, chloride was translocated to Rh(I) with accompanying CO coordination. The Rh–S bonds were cleaved concurrently. Translocation was driven by both the weakening of hydrogen-bonding interactions in the urea and the more favored and less distorted geometry adopted at the Rh center with the new ligands. This is an important example of ion translocation in view of the fact that it involves two different types of interaction (hydrogen bonding and metal–ligand coordination) to enable shuttling and may open a path to the development of further molecular devices by the orthogonal control of these two interactions.

The first intramolecular cation translocation driven by auxiliary redox reactions was reported by Shanzer et al.⁶¹¹ A triple-stranded helical scaffold was used with ditopic hydroxamate and bpy ligands, which bind preferentially to Fe(III) and Fe(II), respectively (Scheme 21). Chemical reduction of Fe(III) with ascorbic acid relocated the cation to the bpy ligand with a visually observable color change from pale brown to violet-red. Reversibility was obtained by oxidation with (NH₄)₂S₂O₈. Even though the process takes place slowly (minutes to hours), the overall movement of the cation is intramolecular.

Several other examples of anion and cation translocation between ligands separated by flexible linkers have been investigated.^{480,612−614} Metals are also known to translocate over rigid sp² hybridized carbon surfaces.⁶¹⁵ Sandwich complexes of two dipalladium units (four palladium nucleii arranged in two separate regions) clustered between π-conjugated ligands showed redox-driven reversible translocation, resulting in a tetrapalladium complex (Scheme 22).⁶¹⁶ In a complex with further extended conjugation, redox reaction conditions resulted in reversible carbon–carbon formation between the dipalladium clusters. This barrier (the new C–C bond) built by the mobility driving force used in the first complex (redox reaction) prevented translocation in the second complex and hence confined the metals to their original positions.

Supramolecular host–guest systems with distinct stimuli responsive switching behavior, guest sorting character, and emergent photophysical properties have been developed with implications for the design of molecular machines. To enable controlled mechanical motion, these systems should be kinetically stable enough to avoid exchange of components with the bulk on the time scale of the operation. Mechanically bonded molecular assemblies are viable candidates for machine architectures, considering their stable interlocked structure, and the relative ease of controlling their mobility.

4. Shuttling in Rotaxanes: Inherent Dynamics

Motion in rotaxanes is constrained by the nature of the mechanical bond. Very limited motion is permitted orthogonal to the axle, while a “shuttling” motion “powered” by random Brownian motion can be observed along the axle (as bounded by large stoppers). As the templating methods typically used to form interlocked structures normally leave recognition motifs,^23,617−676 it is rare, although not unknown, to form a rotaxane without residual interactions between thread and macrocycle.^{504,672,677−689} These residual interactions are typically viewed as “stations” on the rotaxane, and the shuttling of the macrocycle between these stations grants a useful handle in these molecules. The rates of shuttling between stations and their occupancy can be controlled by the strength of station–macrocycle interactions.

4.1. Shuttling in Degenerate, Two-Station, Molecular Shuttles

The first two-station degenerate [2]rotaxane 61 was reported by Stoddart et al. and exhibited temperature-dependent shuttling between the two equivalent hydroquinol groups, as shown by ¹H NMR.⁶⁹⁰ Many rotaxanes based on similar macrocycles and stations have since been reported.^691,692 Similar processes are observed in the amide rotaxanes 62–64 where two diglycine units are separated by various linkers. In 62–64, rapid shuttling of the macrocycle between the degenerate stations was observed at 298 K. Only when the linker was replaced with a bulky N-tosyl group was shuttling inhibited (removal of the tosyl group restored rapid shuttling) (Scheme 23).⁶⁹³

As movement between the binding sites must involve at least partial rupture of the hydrogen-bonding network, the migration can be represented by the simplified energy diagram in Figure 23. Hydrogen-bonding solvents have been shown to disrupt macrocycle–thread interactions in single station rotaxanes,⁶⁹⁴ and here addition of 5% [D₄]methanol increased the rate of shuttling 100-fold, consistent with lowering the energy barrier to migration by disrupting station–macrocycle interactions and thus raising ground-state energies.^{693,695−697} The effect of water on the rate of shuttling has been investigated and was found to be greatly superior to that of other protic solvents.⁶⁹⁸ This effect was attributed to the ability of water to form three-dimensional hydrogen-bonding networks.

Idealized model of binding in degenerate molecular shuttles. Barrier height is dependent on the energy required to break interactions between macrocycle and station and a distance-dependent diffusional component.¹⁴

The use of a phenol/phenolate central group where the formation of a phenolate/cation pair significantly slowed shuttling⁶⁹⁹ has also been explored. Cleavage of a nitrogen protecting group has been used to induce degenerate shuttling.⁷⁰⁰ A large barrier to shuttling could be introduced in 65 where the dimerization of the rotaxane, as templated by Cu(I) addition, prevented shuttling (Scheme 24). This could be reversed by copper removal with an ion-exchange resin.^701,702 Berna and co-workers have recently reported a system in which the binding of a guest hydrogen-bond acceptor–donor–acceptor molecule to the thread led to the trapping of the macrocycle to the linker region between the two stations.⁷⁰³ Upon removal, by external complexation, of the guest, interstation shuttling was restored. Control of shuttling rate has also been achieved by the oxidation/reduction of hydrogen-bonding stations⁷⁰⁴ and by photochemical ring contraction of a macrocycle.⁷⁰⁵

4.2. Physical Models of Degenerate, Two-Station Rotaxanes

A decrease in the rate of shuttling was observed upon lengthening the alkyl chain of 63 as compared to 62, the magnitude of which corresponds to an increase in activation barrier of ca. 5 kJ mol^–1. This effect was attributed to the increased distance the macrocycle must travel between binding stations.⁶⁹³ This process can be modeled by considering the macrocycle as a particle confined to a one-dimensional potential energy surface (the mechanically interlocked nature of the rotaxane preventing significant motion of the macrocycle orthogonal to the thread). Assuming that thread–macrocycle interactions between stations are negligible leads to the energy profile shown in Figure 24. The rate of escape from the station energy well can then be modeled by an Arrhenius equation with a contribution from a distance-dependent diffusion factor to the overall rate of shuttling. A quantum mechanical treatment of this system has found that, as the lengthening of the spacer has no effect on the activation for breaking the hydrogen bonds, the effect on the rate of shuttling is due to the widening of the overall potential energy well. This leads to a greater density of states per unit energy, thermal population of a greater number of energy levels, and thus a larger partition function and activation energy.⁷⁰⁶ An alternate explanation of the dependence of shuttling rate on linker length was proposed by Brouwer and Günbaş who proposed that shuttling in a similar system was facilitated by hydrogen bonding between the macrocycle and the station to which it is not currently bound.⁷⁰⁷ As the linker length increases, this bridging conformation becomes increasingly entropically unfavorable. Some support for this proposal comes from recent examples from Hirose et al. and Sissel and co-workers,^708,709 and Stoddart and co-workers,⁷¹⁰ who in different systems with rigid spacing units found no correlation between spacer length and shuttling rate.

Idealized potential energy surface for macrocycle shuttling in a degenerate, two-station molecular shuttle.

4.3. Stimuli Responsive Molecular Shuttles

Molecular motion in mechanically interlocked and thus kinetically stable rotaxanes can be controlled using multiple binding sites with affinities for the macrocycle that vary under different conditions. The conditions can be modified by electrochemical redox processes, light, pH, and environmental changes. Once detailed balance is broken by the applied stimulus, as with temperature difference in Feynmann’s ratchet-and-pawl, useful mechanical work can be done, provided there is an additional operation to prevent it being undone. By weakening the existing interaction or increasing the affinity of a competing binding site, the macrocycle can be driven to shuttle to a new equilibrium position. For a reverse or further translational motion to take place, a new stimulus is required to perturb the new equilibrium.

4.3.1. Stimuli Responsive Molecular Shuttles with Single Binding Site

Shuttling in a single binding site system can be obtained by reducing the affinity of either the macrocycle for the station or the station to the macrocycle, by the application of an external stimuli. Light controlled switching was observed in a rotaxane made from a “bluebox” macrocycle, an electron-rich dioxyerene station, and redox-active ferrocenyl stoppers.⁷¹¹ Light-induced electron transfer from the station to the macrocycle was accompanied by electron hole transfer to one of the ferrocenyl stoppers, thereby inducing unfolding of the rotaxane and shuttling of the macrocycle away from the station. Photodriven shuttling in single station rotaxanes was also observed with the increase of steric bulk generated upon photoisomerization of an azobenzene or stilbene station.^712,713 Among these examples, directional shuttling of cyclodextrin (CD) on a symmetrical thread is of particular importance due to the fact that it serves as a ratchet for a directional bias maintained purely by the asymmetric nature of the CD rims.⁷¹³ Shuttling was biased to the direction that locates the 6-rim of the CD in a position facing the central stilbene unit (Scheme 25).

Solvent-dependent shuttling is generally achieved by switching between hydrogen-bonding and non-hydrogen-bonding solvents.⁷¹⁴ Hydrogen bonding between macrocycle and thread is weakened in the presence of a competing solvent. In a peptide-based rotaxane with a benzyl amide macrocycle, hydrogen-bonding interactions were weakened by addition of MeOH (Scheme 26).⁷¹⁵ Because of a solvent-induced relocation of the macrocycle, the chiral center located on the thread now had an influence on the macrocycle. The original system could be restored in CHCl₃. More recently, a rotaxane based on a pillar[5]arene macrocycle was shown to shuttle upon either solvent exchange or heating.⁷¹⁶ This system was found to form supramolecular gels in pure DMSO, and in a similar system this shuttling was exploited to form a solvent-driven molecular spring.⁷¹⁷

4.3.2. Stimuli Responsive Molecular Shuttles with Two or More Binding Sites

At a given temperature, the macrocycle of a rotaxane distributes itself among the existing stations according to the binding affinity of each. Perturbation of the binding energies of any of the stations results in the redistribution of the macrocycle toward a new equilibrium state, as driven by thermal motion. Changing the position of the macrocycle in a well-determined way is possible, by making the binding affinity of the less occupied station more favorable (Figure 25, transformation of station B to B′),¹⁴ or by destabilizing the interaction between the most occupied station and the macrocycle (Figure 25, transformation of station A to A′). Stimuli responsive modification of the macrocycle can also drive such shuttling processes. Redox, pH, light, and microenvironment (temperature, solvent, etc.) switches are commonly used to control translational movement in rotaxane architectures, and will be discussed in the following sections.

Potential energy diagram of a rotaxane-based bistable molecular shuttle.¹⁴

4.3.2.1. pH-Driven Molecular Shuttles

Variation in pH is one of the most useful stimuli used to drive translational motion in rotaxanes because hydrogen bonding, electrostatic, and ion–dipole interactions can be effectively controlled by protonation or deprotonation. Indeed, the first molecular shuttle developed by Stoddart et al. depended on acid-driven relocation of the electron poor, positively charged, cyclophane macrocycle from a protonated benzidine station to a biphenol station (Scheme 27).⁷¹⁸ Initially, under neutral pH and at 229 K, the macrocycle preferentially rested on the benzidine station (with 84:16 distribution), stabilized by donor–acceptor interactions. Upon protonation of this station, a decrease in the strength of the interaction and an increased electrostatic repulsion caused the macrocycle to relocate to the other station with a new equilibrium distribution of more than 98:2 in favor of the biphenol station. Complexation of the cyclophane macrocycle in similar systems has inspired a variety of computational research.^719−728

A relatively low temperature was required to obtain an acceptable distribution bias in favor of the benzidine station under neutral conditions. This necessitated the development of a system, which exclusively resided on one station under standard conditions. Positional discrimination with a ratio of more than 98:2 was obtained in a rotaxane composed of a dibenzocrown ether macrocycle and ammonium-bipyridinium and ammonium-triazole stations. This interaction has been exploited in many systems.^729−743 In a structurally similar rotaxane dimer, pH-induced contraction and expansion was made to function as a “molecular muscle”.^744−746 The pH-dependent relocation of an amide-based macrocycle from a succinamide to an hydroxyl-cinnamate station was observed, with enhanced hydrogen bonding between the deprotonated cinnamate derivative and the macrocycle.⁷⁴⁷ Rotaxanes in which repositioning to another station was driven by macrocycle protonation have been reported.^748,749 Shuttling of a metal–macrocycle complex from one ligand to another on a rotaxane as a result of protonation of one of the ligands has been investigated.⁷⁵⁰ The pH-driven shuttling of cucurbit[7]uril between bipyridinium and carboxylate stations has recently been reported.⁷⁵¹ Attempts were made to couple this motion to an oscillating pH background reaction, but the pH oscillation was rapidly damped in this case. Autonomous translocation is an important concept in molecular machine design, but requires further research.

4.3.2.2. Redox-Driven Molecular Shuttles

Rotaxanes with electron donor–acceptor units or transition metal complexes can be controlled by redox chemistry, provided that redox potentials of the interacting units are carefully chosen.^752−756 After the redox process, the products should be stable on the shuttling time scale, and rapid charge recombination must be prevented. Redox control processes can be chemical, electrochemical, or photochemical.

An early example of redox-mediated shuttling was reported by Leigh et al. and took advantage of a redox-active naphthalimide, which was introduced at one end of the thread. The amide-based macrocycle migrated from a succinimide station to the napthalamide station upon one-electron reduction of the naphthalamide (Scheme 28).^757−759 Increased electron density on the imide carbonyl of the naphthalamide station outcompeted the succinimide station, and the macrocycle rested almost exclusively at the naphthalamide station. The shuttling was reversible and could be performed through photochemical excitation accompanied by reduction with an external electron donor.

Benzidine, tetrathiafulvalene, viologen, naphthalimide, and dioxynaphthalene derivatives have been widely used as redox-active stations.^760−777 Redox-induced changes in the coordination preference of transition metal complexes bound to the macrocycle have also been used to drive biased Brownian motion toward different stations.⁷⁷⁸ A tristable rotaxane has been reported where the position of the macrocycle over each of the three stations could be controlled solely using electrochemistry.⁷⁷⁹

4.3.2.3. Ion-Driven Molecular Shuttles

The presence of ions usually affects the conformation and stability of the macrocycle on a station by either interfering with the existing hydrogen bonding, ion–dipole, and dipole–dipole interactions or by sterically disfavoring the binding. This effect can be strong enough to drive translocation of the macrocycle to another station on the thread. In crown ether-based macrocycles, metal ions can be chelated by the macrocycle and thus alter the affinity of the macrocycle for their binding sites, and in some cases induce shuttling. Lithium was reported to mediate the shuttling of crown ether-based macrocycles from a naphthalimide station to a pyromellitic diimide, presumably due to stronger ion–dipole interactions with this station in the presence of a cation.⁷⁸⁰ Shuttling could be reversed by the addition of an excess of [18]crown-6, which sequestered the lithium cation, returning the macrocycle to its original equilibrium distribution. Rather than interacting directly with the macrocycle or a station, ions can bind to another position on the rotaxane and affect the affinity of the macrocycle with either station. Shuttling under similar allosteric control was observed using a bis(2-picolyl)amine stopper that chelates cadmium ions.^781,782 Binding to the nearby station was disrupted in the presence of cadmium, and the macrocycle repositioned itself to the distal station. Cadmium could be removed by cyanide complexation to reverse the process.

Chloride coordination to a palladium complex was reported to drive shuttling from a triazole station to a pyridinium station (Scheme 29).⁷⁸³ In the absence of chloride anions, the palladium metal was chelated by the macrocycle with the fourth coordinate site being occupied by the triazole unit on the thread. Addition of chloride to the solution as its tetrabutylammonium salt resulted in displacement of the triazole ligand and the macrocycle detached from the station. When this occurred, the crown-ether moiety of the macrocycle was free to interact with the pyridinium station, which promoted translocation. The process could be reversed by addition of AgPF₆. Metal-free, anion-induced shuttling between naphthalimide and triazolium stations was also reported in which shuttling could be monitored by UV–vis spectroscopy.⁷⁸⁴ Iodide addition has been used to induce shuttling in a halogen/hydrogen-bonding rotaxane.⁷⁸⁵

In separate work, a shift in fluorescence was obtained by chloride-induced displacement of a macrocycle from a central squaraine station to either of two weakly binding degenerate stations.⁷⁸⁶ In a tristable rotaxane bearing urea, ammonium, and phosphine oxide (listed in descending binding ability) stations on the thread, macrocycle shuttling could be induced by the binding of an acetate anion to the urea and subsequently to the ammonium site, which sequentially blocked these higher affinity stations and forced the macrocycle to bind to the weakly coordinating phosphine oxide station.⁶⁶⁹ Similarly, the binding of a macrocycle to a guanidinium station was found to be inhibited by PO₄^3– addition.⁷⁸⁷ In the presence of Zn²⁺, the macrocycle preferentially bound the central 2,2′-bipyridyl station. In the presence of PO₄^3–, but not Zn²⁺, the macrocycle moved to the weakly coordinating carbamate station. Copper removal followed by guest complexation between porphyrins in the two macrocycles has been used to drive shuttling of a [3]rotaxane.⁷⁸⁸

4.3.2.4. Shuttling Induced by Reversible Covalent Modification

Dynamic covalent bond formation and reversible reactions are important tools in the synthesis of supramolecular devices and machines. This is due to the ability to control their stability and lability by varying external conditions. These chemical tools enable shuttles to do work by “compartmentalizing” the macrocycle on a station and acting as a physical barrier to prevent random Brownian motion reversing the desired translational motion during re-equilibration steps. This phenomenon will be discussed in detail in the following sections.

Reaction-based shuttling can be achieved in several ways. A station can be blocked by introducing a new chemical group, or destabilizing the binding of a macrocycle for steric or electronic reasons. The macrocycle can be chemically trapped on one station. Shuttling between hydrogen-bonding stations has been controlled by Diels–Alder and retro-Diels–Alder reactions, which block and unblock the better-binding fumaramide station.⁷⁸⁹ In another example, photoinduced heterolytic cleavage of a C–O bond in a diaryl cycloheptatriene generated a positively charged tropylium station, and thus repelled the cationic cyclophane macrocycle, displacing it to a different station.^790,791 Oxidation or reduction of sulfoxide-based stations and subsequent changes in the hydrogen bonding to a benzylic amide macrocycle have also been used to control shuttling.⁶²⁷

Kawai et al. reported intrarotaxane imine formation between a diamino macrocycle and two formyl groups at one of the stations. This reaction locked the macrocycle at the station and maintained a positional discrimination (Scheme 30).⁷⁹² Hydrolysis of the imine in wet CDCl₃ in the presence of acid released the macrocycle from the station and also protonated the amino moieties, making the polyether station more favorable due to hydrogen bonding and ion–dipole interactions. Shuttling of the macrocycle could also be promoted by heating and cooling. This entropy-driven shuttling was possible because of the release of two water molecules on formation of the imine bonds. The entropic favorability of the imine state could be more easily overcome at lower temperatures by enthalpic contributions.

As with fumaramides, trans-azodicarboxamide modules have chemical structures preorganized for strong hydrogen bonding with benzylic amide-based macrocycles. The interaction of the macrocycle with the trans-azodicarboxamide station is stronger than that with the succinamide station. Induced shuttling of a macrocycle to the less favored succinamide station could be achieved chemically by blocking the favored station by reaction with triphenylphosphine (Scheme 31).⁷⁹³ This bulky substituent drove the macrocycle away from the station. Under subsequent Mitsunobu reaction conditions, in the presence of a carboxylic acid and an alcohol, the triphenylphosphonium was cleaved from the station as triphenylphosphine oxide. After oxidation, the macrocycle returned to its initial position.

4.3.2.5. Photodriven Molecular Shuttles

Photoinduced shuttling is an attractive mode of control over translational motion due to the ease of stimuli introduction and removal. Moreover, if the back reaction or operation is spontaneous and does not require an additional input, then the overall process becomes autonomous; shuttling will occur as long as energy is supplied in the form of light. However, instead of a continuous light source, flashes of light must be used to prevent the system reaching and staying at a steady-state distribution. Although photodriven shuttling can be an efficient approach, the kinetics of translation and photochemical processes have to be carefully considered. If the photoinduced process involves a redox reaction, then rapid charge recombination can take place before positional displacement of the macrocycle. To avoid this, either excited states with a long lifetime are required or external reagents must be used to reduce or oxidize the species.

In a carefully designed shuttle reported by Stoddart et al., translational switching was obtained by one-electron reduction of a viologen station by a ruthenium trisbipyridine stopper (Figure 26).⁷⁹⁴ Relatively slow back electron transfer permitted ca. 10% of the macrocycle to reposition to the dimethyl viologen station on each electron transfer. Continuous irradiation maintained a 95:5 distribution of the macrocycle in favor of the dimethyl viologen station. The system equilibrated back to the original viologen position once irradiation ceased with spontaneous back electron transfer allowing reversion.

Photoinitiated redox-driven shuttling in a [2]-rotaxane initiated by (i) irradiation and (ii) subsequent reduction of viologen station. (iii) Competing back electron transfer from one-electron reduced viologen to Ru³⁺. (iv, v) With continuous irradiation the macrocycle shuttles to the dimethylviologen station. (vi) Ceasing illumination restores the macrocycle to its original position.⁷⁹⁴

Alongside the photoinduced redox reactions discussed above, improved excited-state hydrogen-bonding interactions⁷⁹⁵ and the photoisomerization of stilbene,⁷⁹⁶ azobenzene,⁷⁹⁷ and other olefinic moieties leading to altered hydrogen bonding or steric bulk creation have also been used to drive shuttling processes.⁷⁹⁸ Absorbance and fluorescence has been used to monitor the progress of shuttling along the rotaxane in some of these systems.^16,799−801 Likewise, other photochromic compounds such as spiropyrans have been exploited to control molecular shuttles, by switching between photoisomers that form hydrogen bonds of different strengths.⁸⁰²

4.3.2.6. Molecular Shuttles Driven by Changes in the Microenvironment

The term “microenvironment” usually refers to the temperature and solvent system. The easiest way to control shuttling via solvent choice is through the disruption of hydrogen-bonding interactions between the macrocycle and the station. Several examples of macrocycle relocation induced by a change in solvent polarity or rotaxane solvation have been reported.⁸⁰³ In some cases, solvent molecules facilitate a shuttling process already driven by other stimuli.^698,797,804 For entropy-driven shuttles, the rearrangement of solvent molecules in or around the macrocycle is an important parameter controlling the shuttling process.

Rotaxanes bearing more than two stations and even polymeric rotaxanes driven by these stimuli have been reported.^797,805,806 In these shuttles, work is undone in each reverse shuttling. Directional shuttling via a ratchet mechanism has been achieved and will be discussed in the next section.

4.4. Compartmentalized Molecular Machines

Stimuli-responsive molecular shuttles are rotaxanes in which the net position of the macrocycle on the thread is controlled by external triggers (light, heat, electrons, chemical, pH, binding events, etc.). In general, these triggers change the properties of the binding sites and subsequently have an influence on macrocycle/thread interactions. In this section, various stimuli-induced mechanisms to create and control nonequilibrium conformations will be presented. Rotaxane succ1-74 has two identical stations, which are distinguishable due to the differing stoppers. The thread is divided into two compartments by a bulky silyl ether barrier, preventing the macrocycle from shuttling between the two stations.⁷⁵ By removing the silyl ether group, dynamic exchange of the macrocycle was enabled and the system moved toward equilibrium. This resulted in a 50:50 distribution of the macrocycle between the two stations. The operation is irreversible, because the attachment of the bulky silyl group again does not change the average position of the macrocycle, and will not restore the initial distribution of the macrocycle; the position of the macrocycle is not determined by the state of the machine. The machine starts in a statistically unbalanced state (the bulky silyl group prevented the macrocycle restoring balance by moving toward an equilibrium distribution). By “linking” the system, removing the bulky group, the machine could reach its equilibrium state, because free movement of the macrocycle was no longer prevented by the barrier. Therefore, the macrocycle had “escaped” to a lower energy distribution (Figure 27).

[2]Rotaxane 74 acts as an irreversible mechanical switch. The silyl ether is too bulky to allow macrocycle shuttling between the two succinamide stations.⁷⁵

Recently, Coutrot and co-workers synthesized a two-compartment molecular machine consisting of a dibenzo-24-crown-8 macrocycle and a thread with anilinium and monosubstituted pyridinium amide stations.⁸⁰⁷ The rotaxane was synthesized via CuAAC chemistry. Subsequent N-benzylation of the triazole moiety, which is located in the middle of the thread, was found to serve as a barrier as well as a third station for the macrocycle. Depending on which station the macrocycle was located, the N-benzylation of the triazole allowed trapping of the macrocycle in either the left or the right compartment.

The Leigh group has extended their initial system using the same design described above, but with two different stations 75 (a fumaramide station and succinamide station) (Figure 28).⁷⁵

Operation of a compartmentalized molecular machine, which corresponds to a two-state Brownian flip-flop. Operation steps: (a) Desilylation (80% aqueous acetic acid); (b) E → Z photoisomerization (hν at 312 nm); (c) resilylation (TBDMSCl); and (d) Z → E thermal isomerization (catalytic piperidine).⁷⁵

In this system, the exchange of the macrocycle between stations could be controlled by the introduction of a barrier in the middle of the thread (kinetic control) as well as by altering the binding affinity of the macrocycle to the two different stations (thermodynamic control). Initially, 85% of the macrocycle bound the fumaramide station and 15% the succinamide station. The system was still unlinked because of the kinetic barrier and therefore not in equilibrium. A balance-breaking stimulus (photoisomerization at 312 nm) generated a 49:51 E:Z photostationary state. Removal of the barrier, the linking stimulus, allowed the balance to be restored by the macrocycle equilibration. Restoring the barrier unlinked the system. The last step was Z → E olefin isomerization, which made the system statistically unbalanced, unlinked, and not in equilibrium. After one operational cycle of the machine, 56% of the macrocycles were located on the succinamide station. The thread had therefore changed the net position of the macrocycle. Because the succinamide station binds the macrocycle less strongly than the fumaramide station, this process has moved the macrocycle energetically uphill; that is, it has performed a ratcheting operation, transporting a particle away from equilibrium. This system and its function is an experimental realization of the transportation task required in Smoluchowski’s trapdoor and Maxwell’s pressure demon, which are discussed in the introduction (section 1) and are powered by chemical and light energy. Figure 29 shows a schematic representation of the four sequential steps performed by rotaxane 75 to transport the system energetically uphill: balance-breaking 1, linking, unlinking, balance breaking 2 (resetting the machine but not the substrate).

Initially the system is balanced (in proportion to the sizes of the two compartments), with an equal density of particles in the left and the right compartments. By changing the volume of the left-hand compartment, the system becomes statistically unbalanced. Opening the door allows the particle to redistribute according to the new size of the compartments. Closing the door ratchets the new distribution of the particles. Restoring the left compartment to its original size results in a concentration gradient of the Brownian particles across the two compartments. Here, the size of the compartment represents the energy level of the macrocycle-station system.⁷⁵

There are many different types of compartmentalized molecular machines, some of which have been described in this section. Three main machine types exist. First is the two-state (or multistate) Brownian switch, which is a machine that can reversibly change the distribution of a Brownian substrate between two distinguishable sites as a function of state of the machine. It does this by biasing the Brownian motion of the substrate (section 4.3). Second is a two-state (or multistate) Brownian flip-flop, a machine that can reversibly change the distribution of a Brownian substrate between two (or more) distinguishable sites and that can be reset without restoring the original distribution of the substrate. The distribution of the substrate cannot be determined from the state of the flip-flop, but rather it is determined by the history of the operation of the machine. Rotaxane 75 is an example of a two-state Brownian flip-flop. Third, a Brownian motor is a machine that can repetitively and progressively change the distribution of a substrate while the machine can be reset without restoring the original distribution of the substrate. The rotary motors designed by Feringa and co-workers are examples of this category of device. Additional examples will follow in section 4.5.

Brownian ratchet mechanisms fall into two general classes: energy ratchets and information ratchets (section 1). The above rotaxane is an energy ratchet in which the energy minima and maxima of the potential energy surface are varied without regard to the particle’s location. In the next section, examples of the second class of Brownian ratchets, information ratchets, will be explored where a barrier is raised or lowered according to the position of a Brownian particle on a potential energy surface, resulting in the particle distribution being directionally driven away from equilibrium.

4.4.1. Molecular Information Ratchets

An information ratchet, such as Maxwell’s pressure demon, requires knowledge of the position of each particle and is able to open the door if the particle is approaching from a certain direction. This positional sorting allows the accumulation of particles in one side of the container and thus results in a pressure gradient. The first example of a molecular information ratchet was described by Leigh and co-workers (Scheme 32).⁸⁰⁸ Molecular machine 76 consisted of a dibenzo-24-crown-8-based macrocycle, which was mechanically locked on a linear thread by bulky 3,5-di-t-butylphenyl stoppers. An α-methyl stilbene unit divided the thread into two compartments, both with ammonium binding stations. The rotaxane used photosensitized energy transfer from the macrocycle to the stilbene unit as the key step in changing the macrocycle distribution. When the stilbene unit adopted the E form, the macrocycle could move randomly along the full length of the thread by Brownian motion, while when the Z form is adopted, the macrocycle was trapped in one or the other of the two compartments. To keep the machine as the Z-isomer, it was operated in the presence of the photosensitizer PhCOCOPh. The sensitized photostationary state of α-methyl stilbene is 82:18 Z:E. Selective “gate opening” was achieved by photosensitized energy transfer from the macrocycle (which has a benzophenone (PhCOPh) moeity attached) to the stilbene unit. This led to a 55:45 Z:E ratio of the α-methyl stilbene. As energy transfer was distance dependent, this photosensitized transfer was more likely to happen when the macrocycle was in the blue compartment (Scheme 32). When the macrocycle was on the green station, intramolecular energy transfer from the macrocycle was not efficient and the gate stayed closed, biasing macrocyclic distribution. This is an example of using the positional information on a Brownian particle to break detailed balance, driving macrocycle distribution away from equilibrium.

Scheme 32 — (a) Gate closed, but energy transfer from the macrocycle is efficient. (b and c) Gate is open, allowing free shuttling of the macrocycle. (d) The macrocycle is on the green station, intramolecular energy transfer (ET) from the macrocycle is inefficient; intermolecular energy transfer from PhCOCOPh dominates (closing the gate).⁸⁰⁸

An alternate approach to a molecular information ratchet using chemical fuel to directionally transport a macrocycle was later published by Leigh and co-workers (Scheme 33).⁸⁰⁹ In this example, a phenyl ester attached to a chiral carbon center separated two degenerate fumaramide binding sites. The close proximity of the stations to the hydroxyl bearing carbon enabled the chiral center to influence the position of the macrocycle. At equilibrium, the macrocycle rested equally at either degenerate station. When a barrier was introduced by benzoylation with an achiral dimethylamino pyridine (DMAP) catalyst, an equal distribution of products was obtained. However, when the chiral DMAP-based catalyst (S)-79 was used, a 33:67 distribution in favor of the pro-(S)-fumaramide (S)-80 station was obtained. Using catalyst (R)-79 resulted in a reverse bias in the position of the macrocycle. Because the stations were identical, macrocycle relocation resulted in a decrease in entropy, with identical enthalpic interactions, and thus a ratcheting operation was achieved. Motion away from an enthalpically favored location was achieved in a similar rotaxane, but with fumaramide and succinamide stations of different binding strengths. Using the same chiral catalyst, 15% of the molecules were relocated to the enthalpically unfavored succinamide station.

This concept was further developed in the three-compartment, chemically driven, molecular information ratchet 82.⁸¹⁰ Here, the compartments contained fumaramide groups and were separated by hydroxyl groups (Scheme 34). The macrocycle could be efficiently trapped at either end of the track by sequential benzoylation of the hydroxyl groups in the presence of the chiral catalyst 83 resulting in a 1:21:79 distribution of the macrocycle. The steric barriers formed prevented the macrocycle from passing, and trapped the ring in a certain compartment. It was shown that the macrocycle had an influence on the rate of benzoylation of the hydroxyl groups on the thread resulting in acylation taking place preferentially far from the macrocycle. The distributional bias could be reversed with the enantiomeric catalyst 83, and when both chiral catalysts were used the macrocycle preferentially resided in the central station with a 10:77:13 distribution.

Directional translational motion along the axis of pseudorotaxane has also been reported (Figure 30).^553,811,812 Threading and dethreading of the macrocycle could be controlled by photochemical, chemical, or electrochemical redox reactions. The pseudorotaxane axis has three different chemical motifs responsible for directional translocation. The first is a 2-isopropylphenyl group, a neutral energy barrier at one side of the axle. An electron-rich 1,5-dioxynaphthaline occupied the center, and at the other end was a positively charged 3,5-dimethylpyridinium station. A tetracationic electron-poor cyclobis(paraquat-p-phenylene) macrocycle formed a π-complex with the electron-rich 1,5-dioxynaphthaline group. To form the complex, the macrocycle had to pass one of the energy barriers, and the neutral 2-isopropylphenyl moiety presented a lower energy barrier. Hence, threading took place selectively from this side of the axis. Upon one-electron reduction of the macrocycle, interaction with the 1,5-dioxynaphthaline station was weakened. Additionally, as a result of the reduced positive charge on the macrocycle, electrostatic repulsion from the pyridinium site became less potent, allowing the macrocycle to pass over this barrier with greatly reduced activation energy. Hence, once reduced, the macrocycle dethreaded over the pyridinium group. The macrocycle threaded and dethreaded in a directional manner via a ratcheting mechanism (flashing ratchet) acting on the potential energy surface of the pseudorotaxane axle. The same group later reported a flashing ratchet based on similar principles, in a pseudorotaxane with one stopper, where threading was driven by reduction, and dethreading slowly occurred after rapid shuttling away from a reoxidized bipyridinium station.⁸¹³ Recently, Credi et al. also reported the photodriven directional threading/dethreading of a crown ether macrocycle on an axle using a flashing ratchet mechanism.^814,815

Photodriven directional translational motion in pseudorotaxanes 86–87. Reprinted with permission from ref (811). Copyright 2013 American Chemical Society.

4.5. Controlling Rotational Motion in Mechanically Bonded Structures

An alternative way to extract work from mechanically interlocked structures would be to control the relative rotation of their components. The rate of macrocycle pirouetting can easily be controlled through temperature, electric field strength, light, structural freedom, or by altering its interaction using other chemical moieties or solvents.^{564,698,816−819} Nevertheless, controlling the directionality of this movement requires careful design.

4.5.1. Controlling Rotational Motion in Rotaxanes

The pirouetting frequency of a macrocycle around a thread depends strongly on the strength of the interactions between the macrocycle and the thread (and environment), which must be broken and reorganized during the movement of the macrocycle. The rate of macrocyclic pirouetting in some hydrogen-bonding rotaxanes can be controlled by changing the strength of an electric field, which alters the strength of the hydrogen bonds.^820−824 In some cases, direct manipulation of macrocycle/axle interactions can either restrict rotation or increase its frequency by weakening intracomplex interactions. The formation of weaker hydrogen bonds with maleamide units as compared to fumaramide units has been discussed in previous sections. Fumaramide preorganizes two hydrogen-bonding motifs to bind the macrocycle, leading to an increase in binding strength. On the other hand, the cis-form of this olefinic structure can only form hydrogen bonds with one site of the macrocycle. As a consequence, the station–macrocycle interactions are weaker, and thus rotation was observed to increase in frequency by 6 orders of magnitude on photoisomerization.⁸²⁵

Like photoisomerization-dependent disruption of hydrogen bonding,⁸²⁵ solvent choice can also play a role in controlling these noncovalent interactions and hence influence the rate of pirouetting in a rotaxane system.⁸²⁶ Comparison of the rate of exchange between axial (E₁) and equatorial (E₂) protons, which was determined by the pirouetting rate, showed that, as compared to heating in dry pyridine, the exchange was greatly accelerated when the pyridine contained 5% D₂O (Figure 31).^698,827 Addition of water sped up redox-driven shuttling in a different rotaxane system by hydrogen-bonding dependent “lubrication” of the mobile elements. Interestingly, other protic solvents (alcohols, nitromethane) had less effect on the pirouetting rate. This was attributed to the ability of water to form 3-D hydrogen-bonding networks. The effect on macrocycle–thread interactions of the sequential addition of single methanol molecules has been probed by IR spectroscopy of rotaxane-solvent clusters.^828,829

Effect of water on the rate of pirouetting of a macrocycle about an axle. Reprinted with permission from ref (698). Copyright 2013 Nature Publishing Group.

Besides hydrogen-bonding, cation-induced restraint of motion in a crown ether-based macrocycle has been reported with a corresponding increase in pirouetting rate upon demetalation.^{817,818,830−834} Redox-dependent switching between coordinating ligands on a macrocycle has been used to control rotational orientation of a macrocycle about a rotaxane axle.⁸¹⁸ In a hybrid organic–inorganic rotaxane, hydrogen bonding between fluorines on the macrocycle and ammonium stations resulted in slow shuttling but fast rotation.^835,836 This rapid rotation was attributed to the array of hydrogen-bonding interactions formed in which a new bond had already started to form before the original was completely broken.

4.5.2. Controlling Rotational Motion in Catenanes

The points discussed above for rotaxanes also apply to rotational motion in catenanes. In a catenane, the rate of rotation of one macrocycle with respect to the other depends on the strength of interactions between the two. Therefore, any stimuli altering this interaction should result in a change in rotational rate. The solvent dependence of the rate of macrocycle rotation in catenanes containing benzylic amides has been measured by NMR analysis and also by AFM-based single molecule measurement techniques.⁸³⁷ In the second method, catenanes with different intercomponent hydrogen-bonding ability were attached to poly(ethylene oxide) polymers and analyzed in dimethylformamide (DMF) and tetrachloroethane (C₂H₂Cl₄). As a measure of equilibrium conformational entropy, the persistence length of the polymer was analyzed for two different compounds in two different solvents to estimate the restriction of motion of the macrocycle in the catenane. In agreement with the NMR analysis, in a single molecule experiment using the AFM method, the mobility of the macrocycle was shown to be accelerated by polar solvents or by disrupting the hydrogen-bonding ability by chemical modification.

Ion exchange,^838−840 pH,^841−844 redox,^845−856 demetalation,^{842,857−869} light or redox-mediated ligand exchange of metals,^853,855,870 photochemical switching,^870−878 photoisomerization-dependent sequestering of macrocycle⁸⁷⁹ and solvent,^{826,880−882} photoisomerization-dependent change in hydrogen-bonding potency,⁸⁸³ and the self-assembly of liquid crystal phases⁸⁸⁴ have also been reported to control the rotation of the macrocycle in catenanes. However, directional rotation of one macrocycle with respect to another in a catenane structure has rarely been investigated. Directional rotation was achieved with a [3]catenane in which the presence of a third macrocyclic component helps to restrict the rotational freedom of the molecule (Figure 32).⁸⁸³ The large macrocycle on which the two small macrocycles rotate bears four different interaction sites: two fumaramide motifs with different binding affinities (light green and red, the methylated station has a lower affinity for steric reasons), one succinic amide ester (orange), and finally an amide group (dark green). A benzophenone unit is attached close to the first fumaramide station to enable selective photosensitized isomerization of this olefinic group through energy transfer using a higher wavelength than required for nonsensitized isomerization.

Directional circumrotation in a [3]catenane. (i) hν (350 nm), (ii) hν (254 nm), (iii) heating; or heating with catalytic ethylenediamine; or catalytic Br₂, hν (400–670 nm). Adapted with permission from ref (883). Copyright 2003 Nature Publishing Group.

Initially, in the absence of any stimuli, one of the macrocycles (blue) rests on the most favored fumaramide station, while the second macrocycle (purple) resides on the second most favored, the methyl-fumaramide station (Figure 32). Upon photosensitized isomerization of station A, hydrogen-bonding interactions between the blue macrocycle and the station weaken, and because the second most favored site is already occupied by the purple macrocycle, the blue macrocycle moves to the third most favored, succinimide amide ester station C. Further photoisomerization of the methyl-fumaramide station triggers the shuttling of the purple macrocycle to the final binding site, station D. The fumaramide stations are converted to the cis-isomers either by heating in the presence of a catalytic amount of ethylenediamine or via irradiation at 400–670 nm in the presence of a catalytic amount of Br₂. This time, however, the relative orientations of the macrocycles force repositioning to the newly formed fumaramide stations in the opposite, with respect to the initial, distribution. A second round of stimuli is necessary to fully reset the system and to bring the macrocycles back to their initial positions. The combination of control of station binding affinity and macrocycle position allowed directional rotation in this catenane.

A directional [2]catenane rotary motor has also been reported with a simpler chemical/photoinduced mode of operation and well-defined ratcheting mechanism.⁸⁸⁵ In this example, the balance breaking operation (to create a new equilibrium distribution) was photoisomerization of the fumaramide station. However, the macrocycle’s rotation to the new energy minima was blocked by two orthogonal protecting groups: an acid labile trityl and base labile tert-butyl-dimethylsilyl. Selective deprotection of one of these protecting groups allowed the movement of the macrocycle to the succinamide station in only one direction. For clockwise rotation, trityl deprotection was required. Under equilibrium conditions, the alcohol had to be protected once more to avoid the work being undone. Full rotation was attained by deprotection and reprotection of the tert-butyldimethylsilyl moiety with reisomerization of the fumaramide station. The sequence of deprotection–reprotection reactions could be reversed to achieve counter clockwise circumrotation. The repositioning of the macrocycle to its new equilibrium position was via only one of two degenerate pathways, and thus the system acts as a directional molecular rotor (Scheme 35).

5. Molecular Level Motion Driven by External Fields

In most synthetic molecular machines described to date, control over motion arises from the selective restriction of Brownian fluctuations through control of steric and noncovalent bonding interactions (via manipulation of chemical structure). The application of external fields can cause the bulk movement or orientation of a molecular species with electric field-directed alignment of liquid crystals being the most important technological application. Several research groups aim to use electromagnetic fields to control submolecular motion, with most examples concentrating on generating submolecular rotary motion. Molecular rotation involves passage over the minima and maxima of a torsional potential energy surface. An external field can either induce an excited state, where the torsional potential energy surface is altered, or interact with a permanent or induced molecular dipole and so orient the molecule in a particular direction. The interaction between the field and the rotor provides the energy necessary to surmount kinetic barriers and overcome energy dissipation and thermal randomization. To date, molecular dynamics simulations of molecular rotatory systems have dominated the field.^886−930 Only a few examples exist where theoretical studies have led to the synthesis of rotors and their examination under the influence of an electric field.

A recent example is the simulation of a single-molecule electric revolving door based on a phenyl-acetylene macrocycle published by Hsu, Li, and Rabitz.^931,932 The authors found, based on simulations, that the opened and closed-door states of 92, whose exchange was accompanied by significant conductance variation, could be operated by an external field. Furthermore, they proposed that due to the large on–off conductance ratio, the molecular machine could also serve as an effective switching device (Figure 33).

Schematic representation of an electric revolving door. (a) Door closed-switch on leading to high conductance. (b) Door open-switch off leading to low conductance.⁹³²

An earlier example of a computational investigation was published by Ratner and Troisi.^933,934 Compound 93 bound between two electrodes exhibited motion under the influence of an electric field (Scheme 36). The authors suggested that the system could find applications in molecular electronics and could be used to create switchable molecular junctions. Theoretical studies revealed that the conformers of 93 (which could be interchanged by an external field) also showed differences in conductance across the junction and could thus be used as a conformational molecular rectifier.^935−937

Scheme 36 — (a) High conductance predicted. (b) Low conductance predicted.⁹³⁴

Fujimura and co-workers undertook a series of theoretical studies into the mechanism of rotation in gas-phase directional chiral motors driven by picosecond pulses of a linearly polarized laser.^938−950 In one study, aldehyde 94 was examined as a chiral molecular motor with the formyl group as the rotor (Figure 34). They considered both enantiomers in their studies and came to the conclusion that directional motion originated from the asymmetric potential-energy surface of the chiral molecules and time-correlated forces created by laser-permanent dipole interactions.⁹⁴⁰ The process is reminiscent of a rocking Brownian ratchet (section 1.6.2), but here thermal energy is not required to surmount kinetic barriers.⁹⁵¹

One enantiomer of chiral molecule 94, in which directional rotational motion was driven by linearly polarized laser pulses and studied by quantum and classical mechanical simulations.⁹⁴⁰

Several examples of surface-mounted molecular rotors have been reported where motion could be driven by alternating electric fields or the absorption of pulses of light.^952−962 Michl and co-workers synthesized, on the basis of computational studies, a series of surface-mounted rotors.^963−965Figure 35 shows the structure of polar and nonpolar versions of their altitudinal rotor. Polar rotor 96 consisted of a 9,10-dihydrophenanthrene substituted by four fluorine atoms on the central ring and had a calculated dipole moment of 3.7 D. The nonpolar rotor was a 4,5,9,10-tetrahydropyrene whose D₂ symmetry precluded a dipole moment. X-ray photoelectron spectroscopy (XPS), scanning tunneling microscopy (STM), and IR spectroscopy showed that for a fraction of the molecules, the static electric field from an STM tip induced a change in the orientation of the polar rotor, but not in the nonpolar analogue.⁹⁶⁶ Several molecular dynamics simulations studying the influence of an electric field or a fluid flow on the rotation of a molecule fixed on a surface have been published by the same group.^967,968 One recent example simulated carborane-based molecular propellers and showed that they could be successfully driven at GHz rates by an oscillating electric field or by a flow of gas.⁹⁶⁹

Nonpolar 95 and dipolar 96 altitudinal rotors mounted on an Au(111) surface. Note that rotor and flanking aryl rings are arbitrarily shown perpendicular to the surface for clarity.⁹⁶⁶

Molecular machines in the solid state and condensed phase will be discussed in more detail in section 8.6.1. A number of research groups have been working in the field of crystalline molecular machines with the goal of creating new materials with interesting properties and that are responsive to external stimuli such as external electric fields.^970−975 Amphidynamic crystals are a form of condensed-phase matter with anisotropic molecular order and controlled dynamics, and they offer a good platform for the design of these new materials.⁹⁷⁶ Molecular rotors are one of the most promising molecular structures for the synthesis of amphidynamic crystals. Structural designs analogous to macroscopic gyroscopes and compasses are one possibility in the design of such molecular rotors. Several examples have been published consisting of a rotating unit linked to a shielding box or stator by an axle.^977−980 The shielding box generates the local free volume required for unhindered rotation in an otherwise densely packed environment. The study of the orientation of and dipole–dipole interactions in dipolar rotor arrays are important in understanding the dielectric properties of these materials and the dynamics of the dipolar rotors. Furthermore, materials containing dipolar rotors can be controlled and reoriented by external electromagnetic fields or optical stimuli.^981,982 Examples of molecular gyroscopes have been reported by Gladysz et al., who developed transition metal-based systems in which trans phosphorus donor atoms are bridged by three methylene chains or related linkers. For example, the system shown in Figure 36 contains either a Fe(CO)₃ or a Fe(CO)₂(NO)⁺ rotor. The latter possesses a dipole moment, which could be a possible handle for external control.⁹⁸³ A series of studies have been carried out by the same group using gyroscope-like platinum and palladium complexes with trans-spanning bis(pyridine) ligands.⁹⁸⁴

(a) Molecular structure of transition-metal-based gyroscopes 97 and 98. (b) X-ray structure of compound 97. X-ray crystal structure reprinted with permission from ref (983). Copyright 2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Molecular gyroscopes with two bulky stators such as triarylmethyl or triptycyl groups, creating space for a 1,4-phenylene, have been reported.^985−1002 Some of these wheel and axle motifs (see also section 8.6.4) showed a dielectric response as a function of external alternating electric fields.^981,1003

6. Self-Propelled Nanostructures

The mechanical self-propelled motion of microscopic objects such as bacteria and the motion of camphor or soap “boats” driven by interfacial forces have long fascinated scientists. More recently, focus has shifted to the control of nanoscale motion in synthetic systems.^1004,1005 These systems are driven not by thermal energy, but by other mechanisms more relevant on the nanoscale. Motion may be generated either autonomously when the energy required for movement is continuously supplied or nonautonomously.

6.1. Propulsion by Manipulation of Surface Tension

If surface tension is not balanced between two sides of a droplet of liquid or a bubble of gas, directional transport may occur. This is known as the Marangoni effect and is observed in several natural systems exhibiting spontaneous flow.^1006,1007 Temperature gradients have typically been used in artificial systems to generate Marangoni flows.^1008−1014 A droplet containing a species that absorbs to the surface, irreversibly modifying the surface energy thereof, has also been used to illustrate this effect in a “chemical Marangoni effect”.^1015−1018

The autonomous motion of millimeter scale objects on a liquid surface driven by the catalytic decomposition of hydrogen peroxide was reported by Whitesides et al.¹⁰¹⁹ A small area of platinum near the edge of each disc catalyzes this decomposition and releases oxygen bubbles, which drive the movement by a recoil force. Others, however, observed the motion of platinum–gold rods toward the oxygen producing platinum end.^1020−1025 The contributions of driven and Brownian motion could be distinguished at aqueous/organic interfaces,¹⁰²² and a rotor based on the same principles has also been synthesized.¹⁰²⁶ A similar system was reported by Manners and co-workers.¹⁰²⁷ Ozin et al. reported platinum–silica sphere dimers, which showed quasi-linear motion in bulk solution and rotational motion at the solution–glass interface.¹⁰²⁸ Rotors of decreased size and increased rotational rate have since been reported,¹⁰²⁹ both once more based on hydrogen peroxide decomposition.¹⁰³⁰ The catalytic domain has been scaled down to a molecular level by Feringa et al.,¹⁰³¹ who utilized a surface bound dinuclear manganese catalase analogue.

Recently, Fischer et al. reported a self-propelling nanoparticle of only 30 nm diameter, a size comparable to certain enzymes, based on a Pt–Au system.¹⁰³² Feringa and co-workers reported the use of carbon nanotube bound enzymes in autonomous propulsion.¹⁰³³ As an alternative to the ubiquitous use of hydrogen peroxide to propel nanoparticles, hydrogen evolution by a magnesium domain has been exploited to drive autonomous motion.¹⁰³⁴ Finally, Sen et al. reported the use of ring-opening metathesis polymerization using a modified Grubbs’ catalyst to propel a nanoparticle. Motion was generated by the consumption of monomer only on one side of the nanoparticle, that where the catalyst is bound. This creates a concentration gradient across the nanoparticle and thus movement.¹⁰³⁵

6.2. Mechanical Self-Propulsion

In contrast to most synthetic, surface tension driven, self-propelled systems, microorganisms almost exclusively utilize mechanical self-propulsion, akin to a swimming motion or the corkscrew motion of a boat’s motor. The low Reynolds number at the nanoscale limits the number of swimming mechanisms that are viable,¹⁰³⁶ as any useful motion must involve a nonreciprocal motion to break the time reversal symmetry.^{26,1037−1044} Various solutions have been proposed (Figure 37).^{1041,1045−1050} The key point in each is that they must possess at least two hinge points; no system with a sole hinge point can be nonreciprocal. The sequential use of each hinge point allows motion at low Reynolds number.

(a,b) Proposed designs for swimmers viable at the nanoscale. (c,d) Potential molecular solutions.¹⁴

No molecular solutions have yet been reported. However, a microscopic artificial swimmer has been reported.¹⁰⁵¹ A major difficulty in realizing any molecular design would be carrying out the driven motion rapidly and frequently enough to be observable against random Brownian motion. The repetitive, directional, rotation of a chiral molecule is also a nonreciprocal motion. The field-driven directional motion of an unconfined chiral molecular rotor would result in its propulsion via a screw-propeller type mechanism, such as the bacterial flagella system. Such a system has been theoretically studied as a means to spatially resolve a racemic mixture of propeller-like molecules.^1052,1053

7. Molecular-Level Motion Driven by Atomically Sharp Tools

The development of single molecule imaging techniques such as atomic force microscopy (AFM), scanning tunneling microscopy (STM), and optical and magnetic tweezers has significantly enhanced our understanding of the mechanical properties and working mechanisms of molecular motor proteins.^1054−1068

Instead of average statistical information obtained from an ensemble of species, these techniques allow direct measurement of molecular level forces, mechanical properties and motions such as rotation, gliding, and translation, pivoting of an individual molecule, supramolecular host–guest exchange, and coconformational changes within interlocked molecular assemblies.^{1061,1069−1089} Beside their imaging abilities, the use of such tools to drive molecular level motion has also been explored.

Molecular scale motion is driven by different forces than in the macroscopic world. Gravity is essentially irrelevant at low Reynolds number, and frictional forces differ greatly.^{606,1090−1101} The driving forces/interactions must be sufficient to overcome significant thermal fluctuations. For the desired motion to be obtained (i.e., translational motion via rotation of the wheels of a “nanocar” instead of gliding), surface–molecule interactions should be neither too strong nor too weak to balance dissociation and immobility.

STM-driven positional displacement of xenon atoms at low temperature was reported by Eigler et al.¹¹⁰² The rotation of oxygen and acetylene molecules adsorbed on Pt(111) and Cu(111) surfaces, respectively, was shown to be induced by the tunneling of electrons from an STM tip at low temperatures.^1103,1104 STM- or AFM-driven motions of aromatic molecules on surfaces have been investigated extensively.^1105−1116 The STM-driven directional diffusion of 9,10-dithioanthracene over a Cu(111) surface has been reported.¹¹¹⁷ STM-induced translational motion of porphyrins along the voids of a porphyrin monolayer on a Cu(100) surface was attributed to the rotation of a t-butyl substituent.¹¹¹³ Displacement to a region with less structural restriction led to more frequent rotation, and thus the STM probe mediated a switch between a rotating and a nonrotating porphyrin. Cyclic molecules and fluorinated C₆₀ derivatives were also shown to roll across surfaces.^1118−1120

Translational motion mediated through rolling structural units (wheels) has been reported in a number of independent publications. Initial attempts to develop a “molecular wheelbarrow” resulted in overly strong surface–-molecule interactions, and the STM tip caused fragmentation.^1121−1124 STM-driven rolling of a single molecule deposited on a Cu(111) surface was first achieved by Grill et al.¹¹²⁵ A chemically switchable metalloporphyrin pinwheel was reported by Lambert et al.¹¹²⁶ The reversible attachment of two CO₂ molecules to a diffusing anthraquinone on a Cu(111) surface was an important example of the potential of artificial molecular cargo transporters.¹¹²⁷ Chiaravalloti et al. designed the first molecular system acting as a rack and pinion device, using self-assembled hexa-tert-butyl-pyrimido-pentaphenylbenzene on Cu(111).¹¹²⁸ Interlocked arrays formed by self-assembly allowed the rotation and translocation of a single molecule along the array by manipulation with an STM tip.

In a four-wheeled “nanocar” with fullerene wheels, thermally induced translational motion on a Au(111) surface was observed (Figure 38).¹¹²⁹ Directional motion perpendicular to the axles of the molecule suggested that the observed movement was generated by rolling of the fullerene wheels rather than sliding of the entire molecule on the surface. In addition to thermal activation, an STM tip could be used to drive the motion. Pivoting also took place, clearly visible as small-angle perturbations to the path of translation in the STM images (Figure 38e,f). In a structurally related three-wheeled molecule, pivoting was observed to be the dominant motion on the surface, suggesting that the four-wheeled molecular structure was important for a rolling translational motion. Similar examples of four- and three-wheeled fluorescent molecules with different wheel sizes (adamantane and p-carboranes as wheels) have been reported, and their diffusion constants on glass surfaces were determined by fluorescence measurement.^1130,1131 The photoisomerization kinetics of a similar four-wheeled molecule functionalized with a rotary motor have also been investigated.¹¹³² When fullerene wheels were used no photoisomerization took place, whereas with carborane wheels, efficient isomerization was observed in solution.

(a) Chemical structure and (b–f) STM micrographs of translational motion of a four-wheeled “nanocar” on an Au(111) surface at 200 °C. Wheels are shown by yellow spots, and the path is highlighted with a white arrow. Reprinted with permission from ref (1129). Copyright 2005 American Chemical Society.

The rotation of dialkylthioethers adsorbed on Cu(111) surfaces has been extensively studied and electrons from an STM tip found to drive a 5% bias in rotational direction.¹¹³³ Electrical excitation of C–H stretching modes in the molecule contributed to ratcheting in the rotation. The direction and rate of rotation depended on the chiralities of both the molecule and the STM tip. In a cerium-centered double-decker molecule self-assembled on a Au(111) surface, an interesting phenomenon was detected (Figure 39).¹¹³⁴ The rotational chirality of individual molecules generated two different orientations on the gold surface, which could clearly be distinguished by STM. Upon scanning the surface with the STM tip, an irreversible, abrupt change in the chirality of some of the molecules was observed. The switch resulted from the rotation of the upper porphyrins, and the irreversibility was attributed to damage caused to the molecules by the high applied voltage.

(a) Structure of a cerium-centered double-decker molecule. (b) STM micrographs of the molecules assembled on Au(111) surface. The two distinct isomers, due rotational chirality, are shown in white and blue crosses. (c) Space-filling model of the two chiral species. Reprinted with permission from ref (1134). Copyright 2011 American Chemical Society.

Directional rotary motors undergoing well-defined structural and/or chemical changes on the application of an external stimuli were discussed in section 5. Feringa et al. developed a system utilizing paddle-wheel type directional motion over a Cu(111) surface upon sequential electronic and vibrational excitation (Figure 40).¹¹³⁵ Electron tunneling induced by a STM tip stimulated double bond isomerization, which was followed by helicity inversion. These sequential configurational and conformational changes in the molecule propelled it across the surface. For the molecule to move on the surface linearly, the four rotary wheels had to rotate in the same direction upon application of the voltage. This is only possible when the molecule was attached to the surface as the meso-(R,S–R,S) isomer. In other isomers, a lack of coherent rotation prevented translational motion or induced spinning.

(a) Chemical structure of a rotary motor with the groups responsible for double-bond isomerization (red) and helix inversion (blue) highlighted. (b) Schematic representation of a full 360° rotation with sequential double-bond isomerization and helix inversion (hexyl substituents are omitted for clarity). (c) Schematic representation of electron tunneling exciting the molecule and inducing translational motion on the surface. (d) Cartoon representation of the motion. Reprinted with permission from ref (1135). Copyright 2011 Nature Publishing Group.

Hao et al. monitored the strength of metal–ligand complexation with an AFM tip.¹¹³⁶ One terpyridine ligand was attached to a gold surface while another was tethered to a gold-coated AFM tip, and the bonding forces between osmium and the ligands were analyzed. The use of atomic tools to induce relative motion in an interlocked molecular system is of particular interest in the development of molecular machines, because each component can be designed to function like the mechanical components of a macroscopic machine.^1137,1138 In a polyrotaxane architecture adsorbed on MoS₂, cyclodextrin ring was translocated by a STM tip along a polyethylene glycol thread.¹¹³⁹ Such shuttling was thought to be responsible for the conductance switch observed upon the application of a voltage via a STM tip in a bistable [2]rotaxane.¹¹⁴⁰ The potential use of interlocked molecular constructs in information storage was highlighted by Leigh et al., who showed that regular patterns of deformations could be successfully generated on a rotaxane monolayer with the aid of a STM tip.¹¹⁴¹ These arrays formed due to the relative ease of intercomponent mobility in these molecular constructs. The effect of electrostatic and steric forces on the shuttling of a bistable [2]rotaxane tethered to an AFM tip has been investigated both experimentally and theoretically.¹¹⁴² A molecular shuttle made up of fumaramide and succinamide stations has been attached to a gold surface by thiol linkers (Figure 41).¹¹⁴³ The macrocycle was tethered to an AFM probe using poly(ethylene oxide) (PEO). Strong hydrogen-bonding interactions with the fumaramide station resulted in a 95:5 distribution of macrocycle in favor of this station. As the stretching of the PEO tether continued, and the force exerted by the PEO linker exceeded the hydrogen-bonding forces between the macrocycle and the fumaramide station, the ring moved away from the fumaramide station. Tension in the tether decreased as a result of the shuttling. Further movement of the cantilever resulted in the detachment of the PEO linker from the probe.

(a) Chemical structure of a rotaxane with fumaramide and succinamide stations depicted in green and orange, respectively. (b) Schematic representation of macrocycle movement on a thread attached to a gold surface as a result of the force exerted by an AFM probe. Application of force by cantilever movement (I,II) was followed by repositioning of the macrocycle (III) or detachment of the PEO tether (IV) depending on the strength of the force. Reprinted with permission from ref (1143). Copyright 2011 Nature Publishing Group.

In addition to molecular level motion generated by atomic tools, modulation of conductivity by molecular switches attached to nanojunctions is of great interest.^1144−1152 A STM tip could cause the rotation of selected moieties in the structure of a polyaromatic scaffold, in the hope of developing switchable nanowires.^{1110,1153−1160} Although most examples are still far from practical application, significant progress has been made in this area.^1161−1182

8. Toward Applications of Molecular Machines

8.1. Current Challenges: Constraining, Communicating, Correlating

Extracting useful work at the molecular scale requires the restriction of the thermal movement of submolecular components or the exploitation of thermal motion with additional ratcheting. Shuttling, switching, and rotation processes in solution can be modulated externally, and the directionality of each motion can be controlled in single molecules. Considering an ensemble of such molecules in solution, however, the biased motions average to give no net directionality. For various applications, the integrity of the molecular system must be conveyed to the macroscopic world. Although there are possible applications of molecular machines/devices in solution, such as their use in molecular logic gate construction or molecular sensing, they are not compatible with typical solid-state technology. For this reason, molecular machines on solid supports are needed. This challenge is being addressed with molecular devices and machines being built on surfaces, interfaces, and polymer matrixes with a variety of electronic, mechanical, or biological applications.^1183−1209 Controlled drug release through nanovalves,^1210−1226 molecular electronics,^1227−1234 artificial molecular muscles,^{18,1224,1235−1242} information storage,^{1141,1243,1244} and modulation of surface properties¹²⁴⁵ are topics of active research in this area.

Communication between molecular machines is another pertinent challenge in this area. In biological systems, the work done by one machine can be harvested by another and the second can then operate. Raymo and Credi have developed a system that addresses this challenge.^1246,1247 They used a merocyanine-type photoacid to release protons as the molecule transforms from its open form to the closed form. The acid protonated a terpyridine osmium complex and decreased the efficiency of singlet oxygen generation.¹²⁴⁷ These photogenerated protons were also used to reversibly complex and decomplex a 1-alkyl-4,4′-bipyridin-1-ium (103⁺) in a calix[6]arene wheel (104) (Figure 42).¹²⁴⁶ Thus, the control of one moiety caused a change in another via the transfer of a proton. Recently, Aprahamian and co-workers successfully coupled a hydrazone switch (section 2.2) with a merocyanine unit and used the photogeneration of acid to drive the switch reversibly with high efficiency.¹²⁴⁸

Communication between molecular devices. Acid generated upon conversion of merocyanine (MEH⁺) to spiropyran (SP) protonates a pyridine, and leads to subsequent complexation of the pyridinium ion (**103**⁺) by a calix[6]arene (**104**).¹²⁴⁶

8.2. Reporting Controlled Motion in Solution

Submolecular movement can be designed to give a detectable output. The output can be used as a measure of stimulant concentration (sensing) or it can be used for information storage. In theory, any detectable nondestructive output that provides a reliable distinction between states of the system is acceptable (NMR, CD response, etc.). However, for most useful applications, more practical and easily readable optical, electronic, or mechanical outputs are preferred. The response rate can be crucial in certain applications such as memory devices and molecular sensors. In these systems, fast-responding reporters are preferred. For a molecular system to be used repeatedly, stability and fatigue resistance are important.

8.2.1. Conformational Switches in Solution

The restriction of molecular motion or switching between bistable conformations can be achieved by external stimuli such as ion or organic molecule binding, pH change, or by photoisomerization of the molecule. Conformational perturbations in polymers or carbon chains with interesting properties have been reported.^1249−1261 Fluorescence readouts have been widely used to detect such submolecular motions in part due to their high signal-to-noise ratios.^{16,1262−1266} One way to obtain a fluorescence response is by changing the electron transfer efficiency between a fluorescent component and other moieties in the system by inducing an electronic change in the acceptor or donor units. Ligand binding or protonation can effectively change the HOMO and/or LUMO levels of molecules, which in turn affects electron transfer to or from the fluorescent moiety. The change in relative energy levels upon reduction or oxidization determines the ease of detection of the fluorescence response. A greater response can be obtained by decreasing rotational degrees of freedom or by energy transfer. Because energy transfer processes are highly distance dependent, variations in distance between the donor and acceptor units in different conformational isomers can determine the efficiency of energy transfer. Emission from dimers of certain chromophores is also widely used as a reporter of molecular processes. This emission requires the close proximity of similar (excimer) or different (exciplex) chromophores.

Mirkin et al. developed an allosterically regulated supramolecular catalyst based on ligand-dependent contraction or expansion to reveal or conceal a catalytic unit (Scheme 37). They were able to measure the conformational change indirectly using the reaction byproduct, acetic acid.¹²⁶⁷ The tetrametallic species was made of two catalytic cofacially aligned Zn(II) centers attached via two Rh(I) centers. The rate of catalysis of the acyl transfer reaction by the core Zn(II) ions was enhanced when the cavity between the two units was larger. Exchange of Rh(I) ligands from labile thioethers to chloride and carbon monoxide led to an expansion and thus an enhancement of catalytic activity. As the acetic acid byproduct protonated the amine of diethylaminomethylanthracene, an increase in fluorescence was observed caused by blocking photoinduced electron transfer from the amine moiety.

Scheme 37 — The Zn(II) center acts as a catalytic unit, and diethylaminomethylanthracene is used as the reporter.¹²⁶⁷

Lee et al. developed a conformational switch based on a cyclic hydrogen-bonding network in a tris(N-salicylideneaniline) derivative (Figure 43).^1268−1271 Structural distortion induced by folding and unfolding processes resulted in a significant change in the electronic properties of the system. BODIPY chromophores were tethered to the molecule as fluorescent energy acceptors. In the folded form, the molecule adopted a highly ordered hydrogen-bonding array, and energy transfer took place from the core tris(N-salicylideneaniline)moiety to the BODIPYs. When a hydrogen-bond acceptor such as fluoride was added, the molecule unfolded, and a substantial decrease in the fluorescence of the BODIPY dyes was detected. Because each mobile element cooperated in the folding process via hydrogen bonding, conformational change was highly cooperative. The initial fluorescence intensity could be recovered when the fluoride anions were captured by trimethylsilyl chloride.

(a) Chemical structure of the t-butylphenyl and BODIPY-substituted foldamers, and (b) X-ray structure of the t-butylphenyl functionalized foldamer. Carbon atoms of the t-butyl groups and all hydrogen atoms except OH and NH have been omitted for clarity. (c) Schematic representation of conformational switching. D and A represent energy donor and acceptor modules, respectively.^1268−1270 Parts (a) and (c) are adapted with permission from ref (1268). Copyright 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Part (b) is reprinted with permission from ref (1269). Copyright 2006 American Chemical Society.

A number of different fluorescent sensors reporting conformational changes have been synthesized on the basis of energy transfer,^1272−1274 excimer formation,^1275−1282 or charge transfer mechanisms.^1283−1286 Optical responses have been obtained by simple stimuli-dependent conformational change,^{796,1262,1273,1275,1287−1289} folding processes,^{1276−1278,1290} shuttling,^{799,1272,1283−1285,1291−1294} switching,¹²⁷³ and transitions between coiled and helical structures.¹²⁹⁵ Optical outputs have been used to develop molecular logic gates.^{1291,1292,1296} Recently, Tian et al. used both phosphorescence and an induced circular dichroism output to develop an INHIBIT molecular logic gate by taking advantage of the photoisomerization-dependent inclusion of an azobenzene and a bromonaphthalene in the β-CD cavity.¹²⁹⁷

Techniques other than optical responses have been used to measure conformational change. Flood et al. used a change in conductance to directly measure a folding process because unfolding released a bound chloride anion and changed the conductance (Figure 22 in section 3.1).⁵⁹⁵ A change in CD response can be a useful indicator of molecular motion and helicity inversion.^1298−1308 Many shape changes can be easily analyzed by NMR spectroscopy. Recently, Clayden et al. showed, by ¹¹B, ¹H, and ¹³C NMR, that the equal distribution of left-handed (M) and right-handed (P) conformers of a helical foldamer could be perturbed by the addition of a chiral ligand (Figure 44).¹²⁹⁸ Upon ligand complexation to the boronic ester, chiral information was transferred along the helix, and the isochronous NMR signals of the diastereotopic nuclei were transformed into anisochronous signals, indicating a bias in the distribution of helical conformers. When the meso diastereoisomer of the diol was used to complex the boronic ester, no splitting of the ¹H NMR signals was observed due to the symmetry of the ligand.

(a) Ligand-induced variation of the chemical shifts (¹¹B (160 MHz) and ¹H NMR (500 MHz)) of the helix in CD₃OD at 298 K. (b) Schematic representation of fast exchange between two degenerate helical conformers with a single NMR signal and (c) induced bias of helicity upon ligand binding (yellow), and the anisochronous NMR signal generated. Adapted with permission from ref (1298). Copyright 2013 Nature Publishing Group.

8.2.2. Rotaxane Switches in Solution

Fluorescence spectroscopy has been widely used to detect shuttling processes in interlocked systems, particularly in rotaxanes. The strong distance dependence of fluorescence quenching by electron transfer has frequently been exploited to measure the relative position of molecular subcomponents. Photoisomerization-dependent shuttling of a pyridinium bearing macrocycle along a two station thread was monitored by changes in the fluorescence of an anthracene group tethered near one station.¹²⁸⁵ When the distribution of macrocycle was biased to this station, charge transfer from the anthracene to the pyridinium moiety quenched the fluorescence, thus providing a detectable fluorescence response due to macrocyclic position. The location of a macrocycle along an alkyl chain in a rotaxane structure has also been probed using similar techniques.¹²⁷²

Greater rotational and vibrational freedom leads to a greater probability of nonradiative processes and hence a lower fluorescence quantum yield. Any interaction affecting rotation or vibration can influence emission intensity. Tian et al. used this effect with a 4-aminonaphthalimide fluorophore in a stilbene bearing rotaxane where the steric hindrance generated by photoisomerization of the stilbene unit resulted in the relocation of the α-cyclodextrin macrocycle along the thread.⁷⁹⁶ As a result of this movement, fluorescence increased by 46%, which was attributed to the restriction of molecular motion of the nearby linker moieties. The same group utilized an azobenzene as an additional photoisomerizable moiety to develop a molecular half adder logic gate (Scheme 38).¹²⁹¹ This logic gate performs binary addition using two inputs and two outputs to provide both XOR and AND gates. When either the azobenzene or the stilbene moiety was isomerized, fluorescence emission of the naphthalimide close to photoisomerized species increased ((Z,E)-112 or (E,Z)-112). However, if none or both of them were isomerized ((E,E)-112 or (Z,Z)-112), fluorescence intensity decreased due to rapid shuttling of the ring between the stations in the nonisomerized form or because the ring was trapped in the center of the thread when both functional moieties were isomerized. These fluorescence outputs collectively result in a XOR gate (output 1 in the truth table). The photoisomerization-dependent decrease in absorbance at 350 nm and increase at 270 nm were used as an additional output for the construction of the AND gate of the half adder. The change in absorbance at the isosbestic point (301 nm) was followed and only breached a predetermined threshold when both units were isomerized. As such, an interlocked molecular system was successfully used as an all-photonic logic gate in solution where the inputs induce submolecular motion and outputs are reporters of their motion. Acid–base and redox switchable bistable rotaxanes with crown ether macrocycles have been used to create an INHIBIT logic gate.¹²⁹² Room-temperature phosphorescence and CD responses have been used in a pseudo[1]rotaxane to create a primitive logic gate.¹²⁹⁷

Scheme 38 — The percentage of the major isomer in the photostationary state is shown over the reaction arrows. The truth table for a half-adder logic gate is shown, with the inputs being 380 nm (I1) and 313 nm (I2) irradiation, and outputs being the change in absorbance (O2) and fluorescence (O1) values.¹²⁹¹

Indicator displacement assays involving supramolecular complexes and interlocked molecules are widely used for molecular sensing applications.¹³⁰⁹ In these systems, a fluorescent molecule with complexation-dependent fluorescence properties is usually used as a guest. The optical change generated upon exchange of the fluorescent guest with the analyte is used as the reporting function. Smith et al. used a similar idea to develop a chloride anion sensor based on a rotaxane (Figure 45).^1310,1311 A [2]rotaxane (113) was synthesized using a tetralactam macrocycle and a squaraine dye as building blocks. Tetralactam macrocycles are known to bind to and quench the emission of red light from squaraines.¹³¹² The exposure of this dye, upon chloride-induced displacement of the macrocycle, restored fluorescence. The process could be reversed by chloride precipitation as the NaCl salt. When the same rotaxane was adsorbed on a C-18 coated reverse-phase silica gel plate and dipped into different concentrations of aqueous solutions of chloride, the change in fluorescence was large enough to be visually observable. Later, a ratiometric chloride sensor based on the same squaraine rotaxane was reported.⁷⁸⁶ Interlocked systems are useful in such dye-displacement assays, as the displaced dye typically diffuses away preventing reversibility, whereas the stable rotaxane structure allows reversibility and reusability. In a similar example, the sodium ion-dependent shuttling of a [2.2.2]cryptand away from a squaraine station enhanced squaraine emission.¹³¹² Interlocked architectures have been mounted on metal nanoparticles and shown to keep their switching ability.¹³¹³

(a) Chloride-dependent shuttling of tetralactam macrocycle, and (b) subsequent fluorescence enhancement in CHCl₃ upon titration with tetrabutylammonium chloride. (c) Rotaxane solution in the absence (left) or presence (right) of chloride. Adapted with permission from ref (1310). Copyright 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Liu et al. have developed a [2]pseudorotaxane with a dual stimulus luminescent lanthanide switch using a diarylperfluorocyclopentene as the photochromic component (Figure 46).¹³¹⁴ The diarylperfluorocyclopentene (114) bears a benzyl ammonium recognition unit and reacts reversibly to generate its closed form upon absorption of UV irradiation (365 nm). The open form can be obtained via irradiation at 614 nm. The Eu³⁺ complex of terpyridinyldibenzo-24-crown-8 (115) was used to reversibly complex the ammonium moiety of 114. This Eu³⁺ center fluoresces at 619 nm through intramolecular energy transfer from an excited terpyridine ligand. Upon complexation of the two compounds through crown ether–ammonium interactions, a small amount of quenching of the lanthanide fluorescence at 619 nm was observed (ca. 10%) due to the poor spectral overlap between the donor emission and acceptor absorbance (which is required for resonant energy transfer (RET)). Upon UV irradiation to form the closed form of compound 114, spectral overlap increased and fluorescence was quenched by 80%, with an accompanying 3-fold decrease in excited-state lifetime. The pseudorotaxane could be reversibly disassembled by the addition of potassium cations and regenerated by the addition of 18-crown-6.

(a) Chemical structures of **115**, and the open and closed forms of **114**. (b) Schematic representation of light modulated switch and K⁺/18-crown-6-mediated complexation. (c) Fluorescence quenching of the Eu³⁺ complex upon UV irradiation in 1:1 CH₃CN/CHCl₃. Fluorescence before (I) and after (II) excitation at 390 nm (c inset). Reprinted with permission from ref (1314). Copyright 2013 American Chemical Society.

The responsive nature of induced circular dichroism makes it an interesting phenomenon to study with the CD response of one species changing upon its interaction with another.^{387,1315−1319} The transformation of an achiral carbon center to a chiral one upon hydrogen-bonding-dependent symmetry breaking provided an early example of the influence of supramolecular interactions on chirality.¹³²⁰ A number of chiral supramolecular assemblies,^{1315,1316,1321} chiral spaces (dissymmetric cavities),¹³²² and helices^1323−1325 have been reported. The solvent-dependent rearrangement of a macrocycle along a thread has been shown to alter the CD response of a rotaxane (section 4.3.1).⁷¹⁵ The position of a macrocycle has been used to control the reactivity of a secondary alcohol toward esterification in the presence of a chiral catalyst in a chemical information ratchet (section 4.4.1).^809,810 Similarly, a chiraloptic switch has been reported based on a benzylic amide macrocycle and fumaramide/peptide stations (Figure 47).^1285,1326 Photoisomerization-dependent relocation of the macrocycle to the peptide station altered the CD response due to proximity-dependent macrocycle–leucine residue interactions. A large reversible difference in elliptical polarization response (>1500 deg cm² dmol^–1) was obtained upon isomerization of the fumaramide station from E to Z.

(a) Chiraloptical switching upon photoinduced shuttling of the macrocycle between fumaramide (green) and peptide (orange) stations; the chiral center of the peptide station is highlighted by a black circle. (b) Percentage of E isomer calculated using ¹H NMR (left y axis) and induced CD absorption at 246 nm after alternating irradiation between 254 nm (half integer) and 312 nm (integers) (right y axis). Reprinted with permission from ref (1326). Copyright 2003 American Chemical Society.

Li et al. synthesized rotaxane 117 bearing a tetracyanobutadiene (TCBD) stopper, which tends to form aggregates via intermolecular dipole–dipole interactions, to attempt to control this clustering behavior (Figure 48).¹³²⁷ The position of macrocycle relative to the TCBD group determined the strength of intermolecular interactions and hence the structure of the assemblies formed. In a hexane:chloroform mixture (1/1, v/v), the macrocycle rested on the peptidic station, and the TCBD units were free to interact to generate nanofibers (Figure 48b). In methanol:chloroform (1/1, v/v), the amphiphilic nature of the molecules generated perforated nanocapsules (Figure 48c). Finally, when DMSO was used as the solvent, the macrocycle relocated closer to the TCBD group, interfering with aggregation and generating a worm-like nanostructure (Figure 48d). A similar phenomenon was reported in which a fumaramide bearing rotaxane displayed different nanostructures when the macrocycle bound Zn²⁺ metal in the presence or absence of irradiation.¹³²⁸ Anion and acid/base-dependent control over the formation of an organogel has been achieved using a [2]rotaxane architecture.¹³²⁹ In this system, stimuli-induced shuttling of the macrocycle between urea and ammonium stations led to sol–gel phase transitions. Polyrotaxane structures have been formed in a concentration-dependent manner in solution using the interaction of an electron-deficient macrocycle with a monoanionic species.¹³³⁰ Recently, light and acid/base-dependent threading and dethreading of pseudorotaxane structures embedded in nanofibers was reported to induce a macroscopic change (more than 1.5-fold enhancement of Young’s modulus upon dethreading).¹³³¹

(a) Solvent-induced shuttling on a tetracyanobutadiene bearing rotaxane **117**. (b) Proposed assembly of rotaxane and SEM images in CHCl₃/n-C₆H₁₄ (1/1, v/v), (c) in CHCl₃/MeOH (1/1, v/v), and (d) in DMSO. Reprinted with permission from ref (1327). Copyright 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The concept of a “molecular muscle”, created from doubly threaded rotaxanes or interlocked daisy chain molecular structures, was developed by Sauvage et al.¹³³² In these systems, submolecular movement drives a relative motion that either contracts or expands the entire molecule upon metal exchange,¹³³² solvent exchange,^1333,1334 redox reaction,^{1236,1238,1335} or acid/base exchange.^{18,1336−1339} Photoinduced contraction/expansion has also been reported.¹³⁴⁰ The concept has been used to cause the macroscopic bending of a microcantilever by means of redox-driven shuttling of the surface-adsorbed macrocycle along a thread (section 8.6.4).^1238,1341

The design of enzyme-responsive molecular machines is an emerging area and could find applications in biotechnology. Biodegradable polyrotaxanes have been studied as selective drug and gene delivery systems.^1342−1349 Leigh and co-workers published two generations of [2]rotaxane-based propeptides (118, 119) where the peptide axle is protected from degradation from general peptidases by the macrocycle.^1350,1351 The introduced glycosidase-cleavable stopper allows the release of the free peptide in a controlled fashion through treatment with a specific glycosidase. The sequence of reactions triggered by the β-galactosidase leading to the decomposition of the stopper is shown in Scheme 39. This approach offers a promising alternative delivery system for peptide-based therapies, because many bioactive peptides suffer from in vivo instability and poor bioavailability. Similar principles have been used to deliver a deactivated cancer drug (acting as a stoppering moiety in a rotaxane) via the blood before the macrocycle immolates inside a cell. This releases the thread, and enzyme-mediated hydrolysis furnishes the active drug molecule. The rate of hydrolysis in cancerous cells versus benign cells was somewhat enhanced due to their overexpression of the hydrolyzing enzyme.¹³⁵²

8.3. Synthetic Molecular Walkers

8.3.1. Introduction

Biological motor proteins have evolved a plethora of functionalities. DNA, RNA, and protein synthesis machineries (DNA polymerases, RNA polymerases, the ribosome) work cooperatively with helper proteins to “unzip” molecules (helicases,¹³⁵³ poly(ADP-ribose) polymerases),¹³⁵⁴ release strain in a substrate (gyrase,^1355,1356 topoisomerase),^1357,1358 slide over the substrate, and processively synthesize a product (DNA polymerases, RNA polymerases, the ribosome).⁶⁸⁻⁷⁰ The ATPase rotary motor is the energy factory of the cell producing ATP via complex mechanical processes.¹³⁵⁹ Pumps¹³⁶⁰ and pores¹³⁶¹ are essential to maintain communication and transportation across the membranes of different compartments (functioning at organelle, cell–environment, or cell–cell boundaries). Among these machines, molecular walkers are attracting increasing attention as their mechanism of action has been revealed. Dynein, myosin, and kinesin are walker proteins of the ATPase family and differ in their structure, function, and use of energy.^1362−1365 Proteins such as collagenase and exonucleases, which are not traditionally viewed as walker proteins, migrate along their substrate tracks by destroying the track via a “burnt-bridges” mechanism.^1366−1368

Biological walkers have some important characteristics.¹³⁶⁹ First, they must be supplied with energy to do work against random Brownian fluctuations. ATP hydrolysis normally provides this energy. Second, attachment to a track results in a restriction of their degrees of freedom facilitating directional 1-D or 2-D walking in solution. Inertia and momentum under conditions of low Reynold’s number are irrelevant, and work is performed under the influence of viscous and thermal motions. Third, to drive the walker away from equilibrium, that is, to generate directional motion, a ratcheting process (either an energy or an information ratchet) must take place. In addition to the requirements of a Brownian motor, certain additional characteristics are necessary for a motor to be defined as a walker.

(i)
Processivity is a measure of the integrity of walker–track interactions during its operation. A walker should remain attached over multiple operations to extract useful work.
(ii)
Directionality is the exclusive or preferential movement of the walker in one direction along the track.
(iii)
Repetitive operation means the motor should be able to carry out similar mechanical cycles repetitively.
(iv)
Progressive operation is the ability of the motor to culmulatively perform work with each operating cycle.
(v)
Autonomous operation allows the motor to function continuously without external intervention, as long as an energy source (fuel) is available.

Conventional kinesin (kinesin I) meets all of these criteria and was first isolated by Vale et al. in 1985.¹³⁷⁰ It is a homodimeric protein with two identical heads that interact with a microtubule track. Through cyclical binding, hydrolysis, and then release of ATP, it can walk along the track by an asymmetric hand-over-hand mechanism.^1371−1373 Because at any time one of the heads remains attached to the track during the walking process, processivity is high. On average, this walker takes 100 steps before detaching from the track.^1374−1377 Although walkers with two attachment points or more are common, this is not a requirement for processivity. The KIF1A kinesin protein processively walks along microtubules using a single leg.¹³⁷⁸ In contrast, some 2-legged biological walkers such as myosin-II are nonprocessive.¹³⁶⁵ Even without being processive, myosin-II can still move directionally, and in a large ensemble it can generate macroscopic motions such as muscle contraction.

DNA has the notable ability to form predictable hydrogen bonds with a complementary strand and can be synthesized using machine-assisted technologies. Strand displacement provides a versatile design for walking processes, and the ability to make complex 3-D structures can be exploited to perform complex physical tasks. The first artificial walkers were made of DNA. Directional walkers,¹³⁷⁹ autonomous walkers,¹³⁸⁰ walkers using the burnt-bridges mechanism,¹³⁸⁰ cargo-carrying walkers,¹³⁸¹ and a light-driven walker^1382,1383 based on DNA have been reported, and will be examined in section 9.4. Aside from DNA-based walkers, the preferential diffusion of molecules along the higher symmetry axis of a metal surface has also been observed.^1117,1127 Huskens et al. reported the gradient-driven diffusion of molecules bearing two adamantane legs across α-cyclodextrin-functionalized surfaces.¹³⁸⁴ Processive crown ether migration on an oligoglycine chain¹³⁸⁵ and migration of metal atoms on aromatic scaffolds^{615,1386,1387} have also been explored. Rearrangement reactions enable the migration of a fragment along a molecule (such as the Claisen^1388,1389 and Cope^1390−1393 rearrangements). However, progressive and repetitive operation using sigmatropic rearrangement reactions is generally challenging.

For the design of processive small molecule synthetic molecular walkers, mechanically interlocked architectures are good candidates, because the walker (macrocycle) is mechanically bonded to the track (thread). However, their interlocked-structure prevents resetting because each resetting process undoes the walking process, by relocating the walker to its original position.¹³⁶⁹ Moreover, the macrocycle cannot choose a new path without bond breaking, which would result in detachment from the thread. A two-leg system operating under orthogonal conditions could provide a viable synthetic molecular walker. Orthogonal dynamic covalent exchange reactions can provide a suitable balance of reversibility and kinetic stability. A rigid track can decrease the possibility of overstepping.

8.3.2. Spontaneous Walking of Small Synthetic Molecular Walkers

Reversible and processive migration of a Michael acceptor along a protein was reported in 1979 by Lawton et al.¹³⁹⁴ More recently, Lehn et al. used dynamic imine exchange to transport a salicylidene walker 125 along an amine bearing track (Figure 49).¹³⁹⁵ Deprotection of the amine at one side of the track using methoxyamine initiated the dynamic exchange reactions. The speed of exchange was shown to be modulated when substitution, composition of the solvent, or temperature was altered. ¹H NMR analysis in CDCl₃ proved that the relative intensity of a characteristic signal corresponding to the transported walker (H₆) increased gradually and in 2 days the transported walker was the dominant product in solution. Recently, the same group reported a modified version of their walker with thermodynamic sinks at each end of the track. These trap the stochastic walker at one end in acid as an imine, or as a lactone at the other end under basic conditions.¹³⁹⁶

(a) The structure and operation of walker **125**, which uses dynamic imine exchange chemistry. Amine footholds are highlighted in blue and red. Each molecule is labeled with one or two numbers in parentheses indicating the amine footholds to which the walker is attached (foothold amines are assigned with numbers starting from the left). (b) ¹H NMR spectra of indicated protons in CDCl₃. H₇ corresponds to a side product in which the walker is detached from the track. Reprinted with permission from ref (1395). Copyright 2012 American Chemical Society.

Leigh et al. reported a spontaneous walking process using a Michael addition reaction between an α-methylene-4-nitrostyrene walker and a polyamine track (Figure 50).¹³⁹⁷ It was shown that the walker translocated preferentially through successive 1,4-N,N-migration rather than by overstepping. After 48 h, no out of sequence N,N-migration was observed with a model walker (Figure 50a,b). ¹H NMR analysis showed that the walking was highly solvent dependent and accelerated in polar solvents such as dimethylformamide and dimethyl sulfoxide. In d₆-DMSO, the walker reached an equilibrium distribution in 15 h. A ratio of 1:0.9 between the occupancy of initial position and the central amine of the track was achieved over this time period. Intermolecular exchange of less than 6% took place when the model walker was mixed with a longer free track for 3 days. This indicates a high processivity (on average 530 steps taken before detachment). Using a longer track modified with an anthracene at the far end, it was possible to monitor walking via an observed decrease in fluorescence as the walker approached the anthracene. As the nitrostyrene walker approached the edge of the track, it quenched the fluorophore (Figure 50d). Leigh et al. have since reported an extended system with a naphthalene moiety at one end of the track (Figure 51 a).¹³⁹⁸ In the presence of excess base (iPr₂NEt), the walker was “trapped” by the naphthylmethylamine, which was the thermodynamic sink. ¹H NMR analysis showed that the steady-state distribution of the walker was biased and 46% of walker molecules had reached the final benzylic foothold in 48 h (Figure 51b,c). When a longer track (with 9 footholds) was used, the percentage at the final station dropped to 19%.

(a) The chemical structure of the model walker **127**, and (b) gradual change in ¹H NMR of the model walker in d₆-DMSO upon formation of new positional isomer on the track. Ratio of (1):(2) isomers reaches 1:0.9 after 15 h of operation. (c) Chemical structure of the walker on a larger track bearing an anthracene moiety, **128**. (d) Fluorescence quenching of anthracene after 6.5 h of walking. Reprinted with permission from ref (1397). Copyright 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

(a) Chemical structure of walker **129**, with each positional isomer labeled in a different color, and amines numbered. (b) Change in the partial ¹H NMR spectra over 48 h of operation. (c) Occupancy of each foothold over time. Reprinted with permission from ref (1398). Copyright 2013 American Chemical Society.

A walker with two chemically different legs that labilize under orthogonal conditions has been reported by Leigh et al. (130, Scheme 40).¹³⁹⁹ The walker unit was attached to the thread by hydrazone and disulfide linkages. Hydrazone exchange took place under acidic conditions, while under these conditions the disulfide bond was stable. Disulfide exchange required basic conditions, which did not affect the hydrazone bond. Successive acid–base cycles led to a 39:36:19 (1,2:2,3:3,4) distribution of walker, with only 6% forming the overstepped (1,4) isomer. Changing the length of the walker alkyl chain from 6 carbons to 5 and using oxidation instead of base exchange at the final step, the distribution could be biased in favor of the (3,4) isomer, which was attributed to strain in the (2,3) isomer.¹⁴⁰⁰

Recently, Bayley et al. monitored an organoarsenic molecule walking along a cysteine bearing track in a protein pore, by measuring changes in ionic current. The walker “stepped” by thiol exchange reactions and displayed a limited degree of processivity and directionality (the latter due to the thermodynamic sink at the track terminus).¹⁴⁰¹ An inchworm walker able to walk on a copper surface has been reported. It could be constrained to one dimension of motion by the use of oligomeric “fences”.¹⁴⁰²

8.3.3. Directional Synthetic Small Molecule Walkers

The biased migration of molecules along a track requires either a preference for one isomer over others under the operating conditions or that strain should be released upon stepping. An efficient ratcheting step is needed. Recently, the use of metal complexes in a molecular biped was explored by Leigh et al. (Figure 52).¹⁴⁰³ The track contained three different pyridine derivatives: 2,6-dialkyl-4-N,N-dimethylaminopyridine (foothold 1, green), 3,5-dialkylpyridine (foothold 2, red), and 2,6-dialkylpyridine (foothold 3, blue). The walker consisted of pincer ligands able to complex the pyridine foothold via Pd(II) or Pt(II) centers. Initially, the walker was attached to the track by complexation of Pd(II) with foothold 1, and Pt(II) with foothold 2. Upon protonation of the free 2,6-dialkylpyridine foothold (foothold 3) and heating, exchange of the Pd(II) complex between foothold 1 and foothold 3 took place. A distribution of 15:85 in favor of foothold 3 was observed. The proton on foothold 3 was captured by the more strongly basic foothold 1 in this process. Migration could be reversed when the first foothold was deprotonated and the solution was heated. A ratio of 95:5 in favor of the initial position was obtained. Even though this example is not truly a walker, the significant directional bias in the stepping process of the metal-based biped could be used to inform more advanced designs.

Toward directional molecular walkers. (a) Chemical structure and schematic representation of the walker attached to the track, and (b) operation of walking through successive acid–base addition and heating cycles. Reprinted with permission from ref (1403). Copyright 2014 American Chemical Society.

Finally, a small molecule walker displaying all of the desired properties of an artificial walker, save autonomy, has been reported by Leigh et al. (Scheme 41).¹⁴⁰⁴ The walker was based on the previously published 130 (Scheme 40), but a stilbene moiety now linked footholds 2 and 3 (Scheme 41). The walker operated by the same hydrazone and disulfide exchange reactions, but with photoisomerization of the stilbene moiety driving directionality. Isomerization led to greater proximity between footholds 2 and 3 (over 1 and 2) in the cis form of the stilbene, resulted in a steady-state distribution of 40:60 in favor of the (2,3) positional isomer. During the second hydrazone exchange step, reisomerization to trans stilbene moved footholds 2 and 3 apart, which led to almost exclusive (5:95) formation of the (3,4) isomer.

Scheme 41 — Footholds are shown in blue and green; the walker unit is depicted in red. Each molecule is labeled with two numbers in parentheses indicating the two footholds to which the walker is attached. (a) (i) hν (365 nm), CD₂Cl₂, (ii) DBU, DTT, CHCl₃; (b) (i) I₂, hν (500 nm), CD₂Cl₂, (ii) TFA, CHCl₃.¹⁴⁰⁴

8.3.4. Challenges Yet To Be Overcome

Significant progress has been achieved in the synthesis of synthetic molecular walkers with highly processive, progressive, and in some cases directional walkers being reported. The exploration of additional, reversible, walker–track interactions may lead to greater control over the directionality of motion. Autonomous walking remains a challenge to be addressed. Polymeric tracks could be designed for cargo transport over large distances. The ability to immobilize walkers on surfaces could lead to future technological applications.

8.4. Switchable Catalysts

In the living cell, many processes and reactions occur in parallel. To make sure that these reactions and their products do not interfere with each other, these operations must be rigorously controlled and switched on or off when necessary. In nature, enzymes control the outcome and rate of the large majority of reactions taking place in a cell. Recently, a number of biologically inspired systems have been published using molecular machines to control the outcome of reactions by switching on and off catalytic units or by controlling the enantioselectivity of the process.^1405−1412 In this section, switchable catalysts controlled by stimuli such as light, pH change, ion influx, and redox chemistry will be explored.

8.4.1. Photoswitchable Catalysts

Several examples of photoswitchable catalytic systems have been reported.^{1407,1413−1415} The reactivity of the catalytic unit is typically controlled through alteration of the steric shielding of the active site or by bringing the catalytic units into closer proximity. In these examples, switching between the cis and trans forms of a photochromic group such as an azobenzene or a stilbene, or the electrocyclization of a diarylethene, provides the requisite control. An early example of a photoswitchable catalyst was published by Rebek Jr. and co-workers.¹⁴¹⁶ Two adenine receptors capable of forming complexes with purine bases were linked through a trans azobenzene moiety. When the system was isomerized to its cis conformation, the rate of reaction between an amine and p-nitrophenyl ester was markedly increased due to greater proximity between the reactive groups, which increased the effective molarity of these groups and thus increased the rate of reaction. A switchable catalyst based on a light-responsive cavitand was published by the same group. The cavitand was functionalized with an azobenzene switch and the cavity of the trans state accessible to a guest molecule, while the cis conformation could not bind guests. Piperidinium acetate was used as the guest, and it could be shown that the host–guest complex significantly accelerated a Knoevenagel condensation between malononitrile and an aromatic aldehyde.¹⁴¹⁷ Hecht and co-workers described the photoswitchable tertiary piperidine derivative 133, which could function as a general base catalyst in a Henry reaction between p-nitrobenzaldehyde and nitroethane (Figure 53). Catalysis was regulated through the shielding/deshielding of the catalytic site upon irradiation of an azobenzene unit.¹⁴¹⁸ The reversible shielding and deshielding of a catalytic site by photoisomerization has also been used to control the organocatalytic activity of a thiourea and a guanidine catalyst.^1419,1420

(a) Molecular structure of the photoswitchable piperidine base **133**, and (b) X-ray structure of the photoswitchable piperidine base **133**. X-ray crystal structure reprinted with permission from ref (1418). Copyright 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The photoswitchable organocatalyst 134 consisting of a photochromic diarylethene (DAE) unit and an imidazolium salt was reported by Bielawski and co-workers.^1421,1422 Under ambient light and in the presence of base, the imidazolium species catalyzed transesterification and amidation. These reactions were considerably slowed upon photoinduced formation of the ring-closed isomer (Scheme 42).¹⁴²¹

Exploiting the ability of dithienylethene to switch between ring-closed and ring-opened isomers upon irradiation, Branda et al. designed a photo responsive system mimicking enzyme cofactor pyridoxal 5′-phosphate 135 (PLP) (Scheme 43). PLP is responsible for amino acid metabolism and participates in a diverse range of enzymatic reactions such as transamination, racemization, decarboxylation, and various elimination processes. The structural features responsible for the action of PLP are the conjugated aldehyde and pyridinium functional groups. Branda and co-workers replaced the core ring of PLP with a dithienylethene where, in the ring-open form, the pyridinium and aldehyde units were electronically isolated from each other preventing catalytic activity (138-inactive). However, photoirradiation to form the ring-closed (138-active) isomer resulted in a fully conjugated structure, which restored the connectivity between the pyridinium and the aldehyde groups and therefore led to catalytic activity.¹⁴²³

Feringa et al. used one of their rotary molecular motors based on a chiral overcrowded alkene, which can perform a directional 360° rotary cycle fueled by light and heat to create a photoswitchable catalyst. During this rotation, the helicity of the motor changes, which changes the overall chirality of the system. A DMAP (dimethylaminopyridine) Brønsted base (Figure 54) and a thiourea hydrogen-bonding donor group, which together comprise a bifunctional organocatalyst, perform Michael additions when in close proximity. As a consequence, the catalytic activity as well the stereoselectivity can be controlled. Michael addition of 2-methoxy thiophenol to cyclohexanone was used as a test system. The (P,P)-trans-140 isomer resulted in a racemic (R,S)-thiol adduct in low yield (7%) after a lengthy reaction. When the (M,M)-cis-140 isomer was used, the Michael addition proceeded significantly faster furnishing a 50% yield of product, with an er of 75/25 (S/R). Finally, the (P,P)-cis-140 isomer led an 83% yield with an inversion in enantioselectivity providing an er of 23/77 (S/R).¹⁴²⁴ Recently, the same group reported a bisphosphine derivative of the same photoswitchable rotary motor. Both product enantiomers of a palladium-catalyzed desymmetrization reaction could be formed, although in situ switching experiments were complicated by the photosensitivity of the active palladium complex.¹⁴²⁵

Schematic representation and molecular structure of a bifunctional organocatalyst integrated in a directional light-driven molecular motor. A, DMAP; B, thiourea hydrogen-bonding donor group. (a) A and B are remote. (b) A and B are in close proximity with M helicity in the (M,M)-*cis*-**140** isomer, preferentially providing the (S) enantiomer of the reaction product. (c) A and B are in close proximity with P helicity in the (P,P)-*cis*-**140** isomer, generating (R) enriched product. Step 1: irradiation at 312 nm at 20 °C. Step 2: heating at 70 °C. Step 3: irradiation at 312 nm at −60 °C. Step 4: temperature −10 °C.¹⁴²⁴

8.4.2. pH-Dependent Switchable Catalysts

Several rotaxanes containing a catalytic unit have been reported. However, these cannot typically be switched on/off.^{1318,1426−1430} Leigh et al. described the rotaxane-based switchable organocatalyst 141, in which catalytic activity could be controlled by pH-dependent macrocycle shuttling (Scheme 44). The design consisted of a dibenzo[24]crown-8 macrocycle and an axle containing both triazolium rings and a dibenzylamine/ammonium moiety. The secondary amine/ammonium group was able to carry out iminium catalysis. However, when the rotaxane was protonated, the ammonium group was a better binding site for the macrocycle than the triazolium ring, and so the macrocycle blocked the catalytic center, preventing the reaction. When the secondary amine of the rotaxane was not protonated, the triazolium ring provided a better binding site for the macrocycle and the dibenzylamine group was exposed, and could therefore participate in catalysis. As a model reaction, the Michael addition of an aliphatic thiol to trans-cinnamaldehyde was performed. The free thread was found to efficiently catalyze the reaction in both its protonated and its deprotonated states.¹⁴³¹ Recently, Leigh and co-workers explored the activation modes of rotaxane catalyst 141 and published a chiral version of this design, with a chiral center next to the secondary amine.^1432,1433 This chiral organocatalyst was able to perform an asymmetric Michael addition with good stereoselectivity.¹⁴³³ The pH-driven shuttling of a pyridyl-2,6-dicarboxyamide macrocycle between squaramide (hydrogen bond catalyst) and ammonium (iminium catalyst) stations has been reported.¹⁴³⁴ The macrocycle blocks the site it is bound to, allowing the selective exposure of catalytic sites and the generation of different products.

8.4.3. Allosteric Regulation of Switchable Catalysts through Ion Addition

A different approach to the regulation of catalytic activity is via the addition of small molecules such as ions, which can change the supramolecular structure of the catalyst, as is observed in many enzymatic processes. Mirkin and co-workers reported the synthesis of triple-layer complex 142 composed of two transition metal hinges, two chemically inert blocking exterior layers, and a single catalytically active interior Al (III)-salen complex, which can act as a ring-opening polymerization catalyst for ε-caprolactone (Figure 55). Polymer growth and molecular weight could be controlled by the addition of Cl^– (catalytic layer exposed) or of the Cl^– abstracting agent NaB(ArF)₄, which results in the fully closed complex 142.^1435−1437 Recently, the same research group reported an allosterically regulated photoredox catalyst based on a similar switching mechanism.¹⁴³⁸

(a) Allosteric supramolecular triple-layer complex **142**, which regulates the catalytic living polymerization of ε-caprolactone. (b) Molecular structures of the components.¹⁴³⁵

Another ion triggered switch was the self-locking system published by Schmittel and co-workers (Scheme 45).^1439−1441 Their design consisted of a zinc porphyrin and a 4-aza-2,2′-bipyridine tether, which either coordinated to the zinc porphyrin or formed a complex with copper and a shielded phenanthroline. In the presence of copper, the tether was removed from the zinc porphyrin center, and piperidine was bound at the coordination site. When copper was removed, piperidine was liberated and able to catalyze Knoevenagel reactions.¹⁴³⁹

8.4.4. Redox-Driven Switchable Catalysts

Canary and co-workers have reported a redox-switchable chiral catalyst capable of delivering either enantiomer of a nitro-Michael addition product depending on the oxidation state of a single copper atom. The design, inspired by previous work carried out in their group and by others,^1442−1444 is based on complexes derived from methionine, which were shown to undergo inner sphere ligand rearrangement upon one-electron oxidation or reduction of copper. The rearrangement is coupled to the orientation of quinolone rings to afford enantiomeric configurations. Urea catalysis produced the (S) enantiomer in 72% ee and 55% yield, and the in situ reduced complex produced the (R) enantiomer in 71% ee and 43% yield.¹⁴⁴⁵

8.5. Synthesis Using Artificial Molecular Machines

Nature provides us with many examples of biological molecular machines that engage in sequence-specific chemical synthesis. For example, the ribosome utilizes sequence information stored in mRNA to synthesize proteins with excellent fidelity.⁶⁸⁻⁷⁰ The various DNA polymerases provide further examples of sequence-specific polymer synthesis by biological molecular machines.⁷¹ The inherently programmable nature of DNA has been used by synthetic chemists to accomplish sequential oligomer synthesis. A common strategy is exemplified by the seminal work of Liu et al.,¹⁴⁴⁶ where complementary sequences of DNA capped with different, mutually reactive end groups are annealed to create an extremely high local concentration of the two reactive species ensuring intracomplex bond formation predominates. After the first reaction is complete, a biotin tag on one strand allows its selective removal, after which a new reactive partner can be annealed to the existing strand and a second reaction conducted. Peptide,^1446−1448 carbon–carbon,^1449−1452 carbon–heteroatom bond forming reactions,¹⁴⁵³ and even cycloaddition reactions have all been reported on the basis of this type of methodology.¹⁴⁵⁴ More elaborate DNA systems have been used by Seeman and co-workers to create a “molecular assembly line” where three gold nanoparticles could be combined to form eight differently composed products, illustrating the complexity that can be achieved with DNA-based molecular machines.¹⁴⁵⁵

In a seminal example of a synthetic system mimicking some of the properties of an enzyme, Nolte, Rowan et al. reported a rotaxane-based catalytic system.¹⁴⁵⁶ A glycoluril clip-based macrocycle containing a manganese porphyrin catalyst catalyzed the epoxidation of a butadiene polymer, which formed the thread of the rotaxane. A greatly enhanced proportion of cis-epoxide was observed in the product, consistent with previous work showing that when the reaction occurred in the macrocyclic cavity steric constraints favored the cis product.¹⁴⁵⁷ This system has been further optimized by substitution of the porphyrin macrocycle with protective ligand groups, which increase turnover number (TON) and provide even greater cis selectivity by preventing reaction on the exterior face of the macrocycle (Figure 56).¹⁴⁵⁸ The rate of threading of their macrocycle onto polymeric materials was also studied and found to be highly dependent on interactions between the thread and the outside of the macrocycle preassociating the two moieties.¹⁴⁵⁹

Porphyrin-catalyzed epoxidation of a butadiene polymer by **144**, utilizing a rotaxane architecture. Reprinted with permission from ref (1456). Copyright 2003 Nature Publishing Group.

A cyclodextrin dimer has been used as both a catalyst (for the polymerization of δ-valerolactone) and a molecular “clamp”, which guides the output of the polymer.¹⁴⁶⁰ In this system, an α-cyclodextrin acts as the active site while a β-cyclodextrin acts as the clamp guiding the growing chain away from the active site (Scheme 46). An additional example was provided by Takata et al.,¹⁴³⁰ where the cyclization of propargyl or allyl urethane groups in the rotaxane backbone to oxazolidinones was catalyzed by a palladium center, bound to the macrocycle.

Scheme 46 — Reprinted with permission from ref (1460). Copyright 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recently, Leigh et al. reported the first small molecule artificial molecular machine (146) capable of sequence-specific peptide synthesis.⁶⁶⁶ The machine is based on a rotaxane architecture, which is used to ensure processivity in a manner reminiscent of both the ribosome-mRNA structure and the DNA clamp of DNA polymerases.⁶⁸⁻⁷¹ Sequence information contained in the track is directly converted into the sequence of the peptide synthesized, and thus the track plays some aspects of the role of mRNA in the ribosomal system. Reactive phenolic ester groups take the place of tRNA-bound amino acids and are sequentially “picked up” by the catalytic arm of the macrocycle. The catalytic arm bears a cysteine group and operates by native chemical ligation (NCL) chemistry where the thiolate of the cysteine unit reacts first with the ester group before transferring the activated amino acid to the end of the growing chain.¹⁴⁶¹ The steric bulk of the loaded amino acid prevents the macrocycle passing over the barrier unit before this reaction has taken place but allows free passage of the macrocycle after being cleaved. This prevents the peptide sequence from being scrambled and allows sequential reaction. Rigid spacing units between each loaded amino acid minimize the likelihood of the catalytic arm encountering an out of sequence amino acid. The catalytic unit consists of a cysteine-glycine-glycine motif with the second two amino acids present to prevent an unfavorable 1,8-S,N-acyl shift transition state during the second ligation (Figure 57).

Leigh’s small molecule peptide synthesizer, **146**.⁶⁶⁶

After the third and final amino acid has been cleaved from the thread, the macrocycle can dethread and be isolated. The fidelity of sequence transfer in this process was demonstrated by tandem mass spectrometry of the macrocyclic product, identical to an authentic sample synthesized by conventional methods. No out of sequence or abbreviated products were observed by HPLC–MS underlining the extremely high level of control afforded by this system. This molecular machine showed processivity, sequence specificity, and autonomy and an exceptional level of control at the molecular level. However, several problems remain with this design. The rate of reaction is vastly slower than that of the ribosome; one peptide bond takes an average of 12 h to form, whereas the ribosome makes approximately 20 amide bonds every second.⁶⁸ Additionally, information is read in a destructive manner; once the macrocycle has cleaved the ester bonds, there is no way to reload the machine for a second run. Finally, the NCL reaction used to catalyze peptide formation limits the scope of amino acids that can be incorporated into the growing peptide chain.

Recently, Leigh et al. reported an extension to this system, creating a four barrier machine whose final product is a macrocycle-bound heptapeptide.⁶⁶¹ The sequence specificity of the product was again confirmed by tandem mass spectrometry and compared to an authentic sample. Although no problems were encountered in this system, whose final bond formation involves a 20-membered ring S,N-acyl transfer, the ever-expanding size of the required cyclic transition state will at some point limit the length of potential peptide products formed by the current design (Scheme 47).

Scheme 47 — Reprinted with permission from ref (666). Copyright 2013 American Association for the Advancement of Science (AAAS).

8.6. Controlled Motion on Surfaces, in Solids, and Other Condensed Phases

8.6.1. Controlled Motion in Solids and Condensed Phases

A major challenge is to use molecular machines for practical applications by utilizing molecular scale changes to create macroscopic effects. Using molecular machines in the solid state or other condensed-phase matter could lead to new materials with a higher level of complexity with controlled cooperative molecular motion leading to changes in the properties and function of the material on a macroscopic scale. In recent years, several examples of molecular motion in condensed-phase matter have been described, some of which show promise for applications in the fields of electronics and optoelectronics.

Garcia-Garibay and co-workers have investigated the rotational dynamics and photophysical properties of the crystalline, linearly conjugated, phenyleneethynylene molecular dirotor 147 (Figure 58). A pentiptycene unit was incorporated as a central stator about which the two flanking ethynylphenylene rotators could adopt various torsion angles. X-ray diffraction studies showed that in the solid-state structure of molecular dirotor 147 all of the phenyleneethynylene chromophors are arranged parallel to one another and therefore shared the same rotation axis. The chromophore displayed significant fluorescence changes as a function of interphenylene torsion angles. The authors suggest that with this system external control of the rotation could be achieved by the application of an electric field, which would allow a rapid shift of solid-state fluorescence emission and optical properties upon the application of appropriate stimuli.^1462−1470

(a) Molecular structure of linear conjugated phenylethynylene molecular dirotor **147**. Rotation of the phenylene rotor (shown with an arrow) creates rotamers with varying degrees of π-conjugation and so wavelengths of emission. (b) X-ray structure of the dirotor **147**. X-ray crystal structure reprinted with permission from ref (1462). Copyright 2013 American Chemical Society.

Sozzani and co-workers have published several examples of molecular rotors in crystals with open porosity, as well as molecular rotors embedded in porous frameworks such as aromatic or organosilica frameworks. In some of these systems, the rotational motion can be actively regulated in response to guest molecules such as CO₂, I₂, tetraethylammonium chloride, and water. These responsive materials may find applications spanning from sensors to actuators, which could capture and release chemicals on command.^1471−1474 Recently, Schurko and Loeb published a metal–organic framework (MOF) material containing dynamically interlocked components.¹⁴⁷⁵ They used [2]rotaxane 148 as the organic linker and binuclear Cu(II) units as the nodes (Figure 59). Void spaces inside the rigid framework allowed the macrocyclic ring of the rotaxane to rotate rapidly. Initially the macrocycle is locked in place through hydrogen bonding from an ether oxygen atom of the macrocycle to a copper-bound H₂O. Dynamic motion occurs upon removal of the water molecules by heating to 150 °C under vacuum, destroying hydrogen-bond interactions and allowing rapid circumrotation about the rotaxane axle. Rotation can be quenched by the addition of water. This type of material could be useful for the creation of solid-state molecular switches and machines.¹⁴⁷⁵ A rotaxane-based molecular shuttle incorporated into the structure of a MOF has recently been reported.¹⁴⁷⁶

(a) Structure of [2]rotaxane **148**. (b) Schematic representation of the structural design components used to create the metal–organic framework. (c) X-ray structure of the tetra-ester precursor to [2]rotaxane **148**. (d) X-ray structure of a single unit of the mechanically interlocked molecule, coordinated to four Cu(II) paddlewheel clusters. X-ray crystal structure reprinted with permission from ref (1475). Copyright 2012 Nature Publishing Group.

8.6.2. Solid-State Molecular Electronic Devices

In a series of ground-breaking but controversial experiments interfacing switchable rotaxanes and catenanes with silicon-based electronics, molecular shuttles have been employed in solid-state molecular electronic devices.^{1146,1477−1485} Bistable [2]rotaxanes and [2]catenanes have been the subject of numerous experimental investigations in the course of the development of such molecular electronic devices.^{1233,1478,1486−1495} Here, the bistable [2]catenanes and [2]rotaxanes feature a cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺) macrocycle and two stations, often a tetrathiafulvalene (TTF) site and a dioxynaphtalene site (DNP). Initially the macrocycle preferentially resides over the TTF site due to strong aromatic charge-transfer interactions between the components; this is referred to as the ground-state coconformation (GSCC). Electrochemical oxidation of the TTF station to form TTF²⁺ generates Coulombic repulsion between CBPQT⁴⁺ and TTF²⁺, and drives the translation of the macrocycle to the DNP station, to give the metastable state coconformation (MSCC). The process can be reversed on reduction of TTF²⁺ to TTF followed by either thermal relaxation of the macrocycle to the TTF station, or reduction of the bipyridinium units in the cyclophane ring to the corresponding radical cations, which reduces the activation barrier to shuttling, restoring the system to the GSCC. These two mechanically distinguishable states exhibit different characteristic tunneling currents. On the basis of quantum mechanical computational studies, the MSCC state is predicted to be the more highly conducting state. The switching cycle can be detected by a number of experimental techniques including time- and temperature-dependent electrochemistry and spectroscopy. Studies have shown that current levels on switching are influenced by temperature, the structure of the rotaxane/catenane, and the environment in which the molecular machines are embedded.^1496−1498 Different environments, including Langmuir–Blodgett (LB) films,^1499−1501 self-assembled monolayers (SAMs),^1502−1506 and solid-state molecular-switch tunnel junctions (MSTJs), have been extensively studied.^{1150,1151,1488,1489,1507−1512} In one particular MSTJ, a monolayer of switchable rotaxane 149 was embedded between two conducting electrodes (Figure 60). This MSTJ acts as a gate, which can be opened or closed in response to an applied voltage by changes in conductivity and resistance and could be used in molecular logic gate designs. The reported design showed stable switching voltages of −2 and +2 V, with reasonable on/off ratios and low switch-closed currents. Nanometer-scale devices have been built using this approach and connected to form 2-D crossbar circuit architectures.¹¹⁴⁴ As a next step, the authors published the design of a 160-kilobit molecular electronic memory circuit consisting of 400 silicon-nanowire electrodes (16 nm wide) and crossed by 400 Ti electrodes sandwiching a monolayer of bistable [2]rotaxanes.¹⁵¹³ Despite the interesting findings, many remain skeptical about the utility of rotaxanes in electronics, and an array of scientific and engineering challenges remain to be addressed such as device robustness, improved etching tools, and improved switching speed.^1514−1516

(a) Rotaxane **149**-based molecular switch tunnel junctions and proposed mechanism for the operation. (i) In the ground state, the tetracationic cyclophane (dark blue) mainly encircles the TTF station (green) and the junction exhibits low conductance. (ii) Application of a positive bias results in one- or two-electron oxidation of the TTF units (green → pink), and increases electrostatic repulsion causing (iii) shuttling of the macrocycle to the DNP station (red). (iv) Returning the bias to near −0 V provides a high conductance state, in which the TTF units have been regenerated, but translocation of the cyclophane has not yet occurred due to a significant activation barrier to movement. Thermally activated decay of this metastable state may occur slowly ((iv) → (i), in a temperature-dependent manner) or can be triggered by the application of a negative voltage (v), which temporarily reduces the cyclophane to its diradical dication form (dark blue → orange), allowing facile recovery of the thermodynamically favored coconformation (vi). (b) Example of one design of a molecular switch. The coloring of the functional units corresponds to that used for the structural diagrams.^{1479,1482,1483} Reprinted with permission from ref (14). Copyright 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

8.6.3. Using Mechanical Switches To Affect the Optical Properties of Materials

Molecular machines can influence the optical properties of materials in the solid state as well as in solution (section 8.2.2). Numerous molecular-machine-functionalized materials where changes can be visually monitored have been reported. Some pertinent examples are discussed below.

Liquid crystals have become widespread in numerous technological applications.^1517−1520 The photoalignment of liquid crystals has considerable potential for display and other optoelectronic applications. The reorienting effect of light on nematic liquid crystals is well-known.^1521−1525 However, the effect can be greatly enhanced by the presence of a dopant dichroic dye. Studies have suggested that the mechanism of this effect involves the photoexcited dye molecules acting as Brownian rotors in the nematic liquid crystal.^1526,1527 The change in orientation was attributed to a ratchet mechanism operating via the generation of torque. Feringa and co-workers reported a chiral nematic liquid crystal film doped with a previously reported chiral light-driven molecular motor. Irradiation of the film resulted in directional motion of the molecular motor, which induced a rotation of the rod-like liquid crystal molecules. This rotation led to the alteration of the color of the film over a large part of the visible spectrum (Figure 61).^1528,1529

Color changes in a liquid-crystal film doped with a light-driven rotor. Reprinted with permission from ref (1528). Copyright 2002 American National Academy of Sciences.

Yamaguchi et al. reported crystalline molecular gyrotop, which showed temperature-dependent changes in optical properties as a result of structural expansion upon rotor acceleration (Figure 62).^1530−1532 Utilizing a phenylene moiety as the rotor, they observed that the orientation of the rotor in the crystal was ordered below 270 K, but became disordered above this temperature generating a slight deformation of the crystal lattice. Using the temperature-dependent features of the crystal, the birefringence (Δn) of the crystal could be controlled. At 280 K, the phenylene moiety undergoes a 180° flipping between two equilibrium states, which provides an almost constant Δn. Above this temperature, Δn decreases as the phenylene moiety rapidly rotates, and the cage expands. The dynamic and optical properties are reversible.¹⁵³⁰

(a) Molecular structure of gyrotops **150** and **151**. The bulkier **151** does not exhibit rotation. (b) X-ray structure of **150**. (c) Single crystal of **150** irradiated with polarized white light. (d) X-ray structure of **151**. (e) Single crystal irradiated with polarized white light. For **150**, a continuous change in color was observed, due to thermal expansion. Reprinted with permission from ref (1530). Copyright 2012 American National Academy of Sciences.

A pseudorotaxane that acts as a thermally driven molecular switch in a crystalline state was recently published by Horie and co-workers.^1533−1535 Crystals of the pseudorotaxane underwent phase transitions upon heating with accompanying changes in optical properties.

Leigh et al. used [2]rotaxanes to control fluorescence by distance-dependent intercomponent electron transfer both in solution and on a polymer film. The thread of these rotaxanes included an anthracene fluorophore as a stopper attached to a glycylglycine hydrogen-bonding station and a C₁₁ alkyl chain that could act as a second station. The macrocycles in 152 and 153·2H²⁺ contained nitrophenyl and pyridinium moieties, respectively, which are known to quench the fluorescence by distance-dependent electron transfer. Macrocyclic shuttling could be induced by changes in solvent with strongly hydrogen-bonding solvents displacing the macrocycle from the glycylglycine station to the alkyl thread. In non-hydrogen-bonding solvents (e.g., benzene, CH₂Cl₂, CH₃CN), the macrocycle was located on the glycylglycine station and fluorescence was completely quenched. In strongly hydrogen-bonding solvents (e.g., DMSO and NH₂CHO), the macrocycle encapsulated the alkyl chain and fluorescence was restored. Polymer/rotaxane hybrids were used to prepare transparent films on quartz slides. Initially, no fluorescence was detected when the slides coated with a 154 containing film were illuminated with UV light (254–350 nm). However, after the slides were exposed to DMSO vapor, prior to illumination, a characteristic blue fluorescence was observed showing that similar shuttling processes were occurring on the polymer film as were observed in solution. Masking regions of the film from the DMSO vapor allowed the transitory etching of patterns on the polymeric films (Figure 63).¹⁵³⁶

(a) Chemical structures of rotaxane initiators **152** and **153** and the corresponding PMMA-based polymers **154**, **155**, and **155**·2H²⁺. (b) Images obtained by casting films of polymer **154** on quartz slides, then covering the films with aluminum masks and exposing the unmasked area to DMSO vapor for 5 min. The photographs were taken while illuminating the slides with an 8-W UV lamp (254–350 nm). Reprinted with permission from ref (1536). Copyright 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polymeric 155·2H²⁺ films responded to two different stimuli. Protonation of the macrocycle by CF₃CO₂H vapor caused quenching of fluorescence, while DMSO vapor induced shuttling of the macrocycle and subsequently restored fluorescence emission. The response of 155·2H²⁺ to the different combinations of two stimuli (DMSO and protons) corresponds to an INHIBIT Boolean logic gate (Figure 64).¹⁵³⁶

(a) Aluminum grid used in the experiment. (b) Pattern generated when films of **155** were exposed to trifluoroacetic acid vapor for 5 min through the aluminum-grid mask. (c) Mesh pattern obtained by rotation of the aluminum grid by 90° and exposure of the film shown in (b) to DMSO vapor for a further 5 min; only regions exposed to trifluoroacetic acid but not to DMSO were quenched as shown in the magnified view. Inset: Truth table for an INHIBIT logic gate. The photographs were taken while illuminating the slides with an 8-W UV lamp (254–350 nm). Reprinted with permission from ref (1536). Copyright 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrosol–gel systems represent another example of a nonsolution media. The effect of doping these systems with rotaxanes has been studied by various groups.^{1208,1537−1541} Light-driven rotaxanes based on α-cyclodextrin and cucurbit[7]uril have been dispersed in thermoreversible hydrogel systems by Tian and co-workers. They observed that when the rotaxanes were embedded in the hydrogel, their optical performance (fluorescence and induced circular dichroism) improved. They attributed this observation to the restriction of movement in the hydrogel system.^1539,1542

8.6.4. Using Mechanical Switches To Affect the Mechanical Properties of Materials

Piezoelectric materials provide the most common example of an external stimulus being converted into a mechanical change in the material. Materials incorporating molecular machines could provide a far greater level of control over macroscopic properties than is currently possible, and their development has been the focus of great interest.^1543,1544 Conformational changes in polymers leading to macroscopic mechanical changes have been extensively studied. Hydrogels, consisting of water-swollen cross-linked networks of neutral or ionic amphiphilic polymers, have been shown to undergo reversible phase transitions in response to changes in temperature, solvent, pH, electric field, or irradiation with an up to 100-fold expansion on phase change.^1545−1558 Katchalsky et al. first exploited these properties to develop devices that converted chemical potential energy into macroscopic mechanical work.^1559,1560 A large variety of devices based on the characteristics of these materials have been proposed^1561−1581 including guest binding and release,¹⁵⁸² control of enzyme activity,¹⁵⁸³ and the macroscopic motion of a polymer gel by selective contraction of alternate sides of a gel.¹⁵⁷¹ Finally, guest binding by built-in recognition sites can lead to large-scale changes in the volume of the host gel.^1584−1598

Shape memory materials have also been designed that utilize control at a molecular level.^1599,1600 While most of these systems rely on a temperature variation-induced shape change, a system utilizing a photoinitiated radical reaction to rearrange covalent cross-links and recover the “memorized” shape has been reported.¹⁶⁰¹ A reversible cross-linking [2 + 2] cycloaddition has also been used to achieve this control.¹⁶⁰²

Conducting polymers have been used to create stimuli responsive mechanical changes.^1603−1605 Electrochemical oxidation can induce counterion expulsion or inclusion and thus volume change, although these changes tend to be slow in aqueous solution.^1606−1609 Solid state,¹⁶¹⁰ gel,¹⁶¹¹ and ionic liquid electrolytes have been shown to accelerate this process.¹⁶¹² Conformationally flexible calix[4]arenes have been used as “hinges” to form conducting oligothiophenes where the cone (but not the kite) form of the calix[4]arene maximizes the desired π–π interactions and switching could be utilized to provide macroscopic mechanical motion.^1613,1614

In the previous examples, a macroscopic change was induced by the sum of multiple, relatively uncontrolled conformational changes in a polymeric network; that is, the observed change is not an inbuilt feature of the molecular components. The use of particular submolecular conformational/configurational switches to directly trigger macroscopic changes has numerous benefits such as overcoming problems caused by slow diffusion of guests or solvents and ensuring a uniform response in the material. The use of configurational switches to control long-range order in liquid crystalline phases has been discussed elsewhere (section 8.6.3), but a similar application in synthetic polymers often furnishes a useful result.

Azobenzenes are often used to control reversible contraction in polymers, a process that has been observed at a molecular level using AFM,¹⁶¹⁵ as well as properties such as viscosity and solubility.^1616,1617 In the aforementioned AFM experiment, the application of a “load” to the AFM tip and subsequent isomerization toward the cis isomer provided the first direct measurement of the conversion of light to mechanical energy. Chiral azobenzene side chains can allow control over the screw sense of artificial helical polymers with isomerization leading to interconversion of the P and M forms.^1618−1620 Several liquid crystal polymeric systems have been reported.^{209,1621−1635} Macroscopic motion was induced in liquid crystal polymer springs devised by Fletcher, Katsonis et al.¹⁶³⁶ Here, a chiral dopant, a polymerizable liquid crystal, and a polymerizable azobenzene switch were used to generate a liquid crystal polymeric spring. Irradiation with UV light caused cis–trans isomerization of the azobenzene switch, which in turn led to coiling/uncoiling or helical inversion of the spring. More complex behavior such as side to side bending could be induced by careful manipulation of the initial helical state and directed illumination.¹⁶³⁶

Light-driven directional rotor 156 has been used to drive the macroscopic motion of a glass rod.^1637,1638 When doped at 1 wt % into a liquid crystal, the helicity of the rotor induced a helical arrangement in the liquid crystal, giving rise to a characteristic “fingerprint” texture in the liquid crystal’s surface. Irradiation altered the distribution of isomers of the rotor and thus caused the liquid crystal’s helical nature to rearrange. This process could be observed by the clockwise rotation it caused of a glass rod laid on the surface and of the “fingerprint” pattern. Eventually, however, rotation stopped as the system reached a photostationary state with the distribution of molecules between isomers reaching equilibrium. When the light source was removed, the isomer distribution decayed back to its initial state, with concomitant reverse rotation. The use of the opposite isomer of the rotor led to inversion of the direction of rotation (Figure 65).

(a) Rotor **156**. (b) Rotation of micrometer scale glass rod on doped liquid crystal film. Photos taken at 15 s intervals. Reprinted with permission from ref (1637). Copyright 2001 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Shuttling in [3]rotaxane 157 has been used to generate a macroscopic mechanical response, deformation of a microcantilever beam, which had been coated with a monolayer of ca. 6 billion rotaxanes.^1238,1341 Oxidation of the tetrathiafulvalene (TTF, green) station decreased the affinity of the macrocycle for this station, and induced shuttling to the naphthalene (red) station. A deformation of 550 nm was recorded, and the process could be reversed and repeated (with diminishing amplitude) over several cycles (Scheme 48).^1238,1341 Microcantilever deformation by guest recognition at the surface has been used by several groups as a “read-out” from molecular detectors.^1639−1646 A polymer has been reported that contracts upon illumination based on a directional light-driven rotor (Scheme 48).¹⁶⁴⁷ A photodriven rotary motor has also been used to induce the disassembly of self-assembled nanotubes.¹⁶⁴⁸

Scheme 48 — Reprinted with permission from ref (1647). Copyright 2015 Nature Publishing Group.

8.6.5. Using Mechanical Switches To Affect Interfacial Properties

The ability to easily modify the properties of surfaces in a reversible manner would be extremely valuable in the design and synthesis of technologically useful devices. Stimuli-responsive polymer modification of surfaces can lead to control over wettability, adhesive ability, porosity, patterning, and interfacial interactions; this topic has been reviewed elsewhere.^1649−1663

Interlocked architectures such as bistable rotaxane 158 have been used to restrict or allow access to the pores in materials such as mesoporous silica particles.¹⁶⁶⁴ The positively charged macrocyclic ring initially prefers the TTF station, and in this conformation, diffusion into and out of the nanopores of the silica is allowed. Oxidation of the TTF moiety causes shuttling of the ring to the dioxynaphthalene station, and closure of the nanopores, trapping a portion of the solvent/solute mixture. Solvent exchange and reduction of the oxidized TTF station leads to guest release (Figure 66). The aggregation and deaggregation of a polymeric material has been caused by the formation of pseudorotaxanes between strands. This has been used to transiently trap nanoparticles in the pores formed upon aggregation.¹⁶⁶⁵

(a) Structure of nanopore gate, and (b) controlled release of guest from nanopores.¹⁶⁶⁴ Reprinted with permission from ref (14). Copyright 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The translation of the macrocyclic ring of 159 has been converted into an electric signal.^1666−1668 A gold electrode was used in place of one stopper of the rotaxane, and a cyclodextrin ring with an attached ferrocene was used as the macrocycle. On photoactivated shuttling, the change in rate of distance-dependent oxidation of the ferrocene moiety allowed detection of the shuttling motion.¹⁶⁶⁹ When a glucose oxidase enzyme was attached via a rotaxane architecture to a gold electrode, the CBPQT⁴⁺ macrocycle of the rotaxane acted as a two-electron shuttle and allowed enzyme operation, which was prevented when the enzyme was attached solely by the thread.¹⁶⁷⁰ A similar effect was seen in a system involving a CdS nanoparticle in place of the enzyme in which the observed photocurrent was amplified 8-fold in the rotaxane over the thread.¹⁶⁷¹ In a simpler analogue of these systems involving a CBPQT⁴⁺ macrocycle and a diiminobenzene station (159), electrode-induced shuttling could be directly observed.¹⁶⁷² The reduction in macrocycle charge on shuttling was shown to decrease the hydrophilicity of the surface, and thus increased the contact angle of a drop of water on the surface (Scheme 49).

This control of wettability has been exploited by many groups to form a wide range of interesting systems, especially in the development of “self-cleaning” surfaces.^1673−1679 Surface wettability has been controlled by surface mounted photochromic switches.¹⁶⁸⁰ Self-assembled monolayers of carboxylate-terminated alkanethiols on gold have been switched between hydrophilic (carboxylate exposed, gold electrode at a negative potential) and hydrophobic (carboxylate surface bound, gold electrode at a positive potential) states by varying the electric potential.¹⁶⁸¹ Bipyridinium groups have been used in place of carboxylates to similar effect.¹⁶⁸²

Several methods for the photoswitchable change of surface wettability have been developed. Systems based on the reversible exposure of hydrophobic groups upon shuttling of a cyclodextrin ring,¹⁶⁸³ or the release of a hydrophilic guest,¹⁶⁸⁴ have been successfully exploited. Feringa and co-workers exploited a tripodal stator to fix a molecular directional rotor to a surface, which upon irradiation exposed or hid a hydrophobic fluorinated chain providing control over surface wettability (Figure 67).¹⁶⁸⁵

Feringa’s tripodal wettability switch **160**.¹⁶⁸⁵

Perhaps the most powerful demonstration of the usefulness of control over wettability is in the macroscopic transport of a liquid across a surface. The earliest example came from Whitesides and Chaudhury who created a hydrophilicity gradient on a silica wafer by reaction with a trichloroalkylsilane vapor and observed the motion of a droplet of water up a 15° incline.¹⁶⁷⁷ Numerous examples of droplet motion driven by surface energy gradients/steps have since been reported.^1686−1690 However, remotely controlling wettability to generate droplet motion has remained challenging.¹⁶⁹¹ This remote control would be particularly useful in “lab-on-a-chip” type applications where it could provide a gentle and cheap alternative to expensive microscopic pumps and strong electric fields.¹⁶⁹²

Azobenzene containing calix[4]resorcinarene 161, when deposited as a monolayer, provided the first example of remote control of surface energy and therefore droplet motion by irradiation.¹⁶⁹³ The monolayer initially consisted of all cis isomers. However, a droplet of olive oil has more favorable interactions with the extended trans form, where interactions with the alkyl chain of the calix[4]arene can be maximized. As such, when an asymmetric light source irradiated the droplet, forming more trans-calix[4]arene on one side of the droplet than the other, a surface energy gradient was created and the droplet moved away from the trans enriched area. This movement could be continued if the light source followed the rear edge of the droplet (Figure 68).

Calix[4]arene **161**, used to control surface wettability.¹⁶⁹³

Photoresponsive control of droplet motion has also been achieved using a system based on bistable rotaxane 162, adsorbed onto a gold surface using a thiol linker.¹²⁴⁵ Diiodomethane drops could be transported on a millimeter scale across a surface using the macrocycle of 162 to either hide or expose the fluoroalkane region of the rotaxane and thus modify surface energy. Using this strategy, a microliter droplet could be moved up a 12° incline. Roughly 50% of the absorbed photon energy was converted into gravitational potential energy of the drop (Figure 69).

Light switchable rotaxane **162**, and transport of a microliter drop of CH₂I₂ across a flat surface (a–d) and up a 12° incline (e–h). Reprinted with permission from ref (1245). Copyright 2005 Nature Publishing Group.

The above examples of macroscopic control utilizing molecular motion underscore the potential importance of this concept for technological applications. Similar control of motion has been achieved with surfaces microscopically patterned with thermoresponsive polymers^1694−1696 and by amplifying the effect of the photochemical switching of a spiropyran-functionalized surface.¹⁶⁹⁷

9. Artificial Biomolecular Machines

9.1. Hybrid Biomolecular Systems

Biological systems make extensive use of motor proteins such as ATPase, kinesin, myosin, and dynein. These biological motors provide both examples of machines viable at the nanoscale and useful building blocks for the creation of hybrid systems. The availability of preformed nanoscale machines has greatly expedited the creation of complex nanotechnological systems. Although a thorough exploration of this topic is beyond the purview of this Review and has been covered elsewhere,^{15,47,1364,1698−1702} a brief overview is useful. The initial purpose of these biohybrid experiments was to further probe the complex mechanisms by which biological machines operate. An early example was provided by Kinosita et al., who reported a series of experiments exploring the F₁-ATPase rotary motor.^1703−1707 They were able to observe the 360° rotation of the motor, powered by the hydrolysis of ATP, directly, via microscopy, for individual motors mounted on glass. Mechanical rotation has also been observed in an F₀F₁-ATPase, where the rotor domain is coupled to a proton transporting domain.¹⁷⁰⁸ Even more remarkably, ATP synthesis has been driven by rotating a magnetic bead attached to an F₁-ATPase with electromagnets.¹⁷⁰⁹ This is a stunning example of chemical synthesis driven by an external mechanical force. ATPase systems have been less exploited in recent years due to the difficulties in using them in synthetic systems.¹⁷¹⁰ However, a recent example showed the insertion of ATP synthases into an artificial lipid microcapsule and their subsequent use to generate ATP inside the capsule.¹⁷¹¹

Kinesin, myosin, and dynein systems have been much more extensively utilized.^1712−1722 They have been shown to transport cargos in artificial systems, although cargos must typically be large to outcompete diffusive forces.^{1375,1723−1727} These biological walkers have been controlled by the design of appropriate tracks,^1728−1730 or by the application of external forces. Kinesin has been used to stretch a length of DNA,¹⁷¹⁵ and to enable the detection of nanomolar concentrations of a targeted protein.¹⁷³¹ Cross-linked actin and myosin gels were found to move over each other in the presence of ATP.¹⁷³² Microtubule containing gels combined with kinesin and ATP have been shown to spontaneously generate autonomous motility.^1733,1734 As a further benefit to using biological motors, ATPase motors have been shown to operate at a near 100% efficiency,^{1707,1735−1737} and kinesin at >50%,¹⁷³⁸ whereas in a typically used polymeric system where phase transitions are used to generate molecular level forces, an efficiency of 0.0001% was observed. The field of biomolecular electronics often uses molecular motion as a switching mechanism, particularly in systems utilizing photoactive proteins (be they native or engineered).^1739−1750

9.2. Hybrid Membrane-Bound Machines

Ionophores and ion channels, both synthetic^1751−1755 and biological,^1756−1766 have been extensively explored and exploited. Biological ion channels have been inserted into artificial membranes and used to sequence single strands of DNA,¹⁷⁵⁶ to open the pore of a nonselective efflux channel,^{406,1767,1768} and to effect the light-driven production of ATP by F₀F₁-ATPase.¹⁷⁶⁹ Feringa et al. reported the switching of the “mechanosensitive channel of large conductance’ (MscL) of E. coli, which can be opened in response to the introduction of charged entities at a certain location in the protein channel.⁴⁰⁶ Initially, a light-cleavable group was used to release acetate anions and thus open the channel, with a reversible version, utilizing a spiropyran switch, also reported (Scheme 50). Ion channel proteins modified postsynthetically to be light switchable have been inserted into living cells, and successfully opened and closed.^1770−1777 Unnatural, light switchable amino acids have also been incorporated into ion channel proteins.^{400,1778−1780}

Scheme 50 — MscL = mechanosensitive channel.⁴⁰⁶

Active transport between aqueous phases across an organic phase,^1781−1783 and lipid bilayers,¹⁷⁸⁴ has been observed, driven by differing redox potentials in each aqueous phase. An electron donor–acceptor molecule has been directionally inserted into a lipid bilayer, which on irradiation created a redox potential gradient and ferried protons across the bilayer establishing a pH gradient. However, the quantum yield for the process was only 0.004.¹⁷⁸⁵ Calcium ions have been transported across a membrane in a similar system.¹⁷⁸⁶ Work to establish longer lived photoinduced charge separated states, which might lead to greater quantum yields and further applications, has continued.^{627,1787−1807} Alternating currents have been induced in a protein-based photoelectrochemical cell by irradiation with intermittent light.¹⁸⁰⁸ An interesting recent example utilized the light-induced ring-opening of spiropyrans under ultraviolet light and their ring closure under visible light illumination. When a membrane doped with spiropyran 165 was illuminated with ultraviolet light on one side and visible light on the other, the differing proton affinities of ring-opened and ring-closed spiropyran led to proton shuttling across the membrane and the generation of an electric potential of ca. 210 mV and pH gradient of ca. 3.6 pH units (Figure 70).¹⁸⁰⁹

Proton gradient established by spiropyran (**165**) shuttling upon differential illumination of the two sides of a membrane. Reprinted with permission from ref (1809). Copyright 2014 Nature Publishing Group.

9.3. DNA-Based Motors and Switches

Biological building blocks have been used to design and create molecular machines by many research groups.^1810−1828 A large number of DNA-based molecular motors,^1829−1832 walkers,^{1382,1833−1838} tweezers,¹⁸³⁹ gears,¹⁸⁴⁰ springs,¹⁸⁴¹ robots,^1842,1843 transporters,¹⁸⁴⁴ and interlocked structures such as DNA rotaxanes and catenanes can be found in the literature.^1845−1850 All are built by self-assembly, exploiting the sequence-specific interactions that bind complementary oligonucleotides together to form double helix or triplex structures.^1851−1870 Beside base-pairing, other structural motifs can be formed and used in the design of molecular machines such as the pH-induced self-assembly of C-rich sequences into i-motif configurations,^1871,1872 the ion-induced self-organization of G-rich sequences into G-quadruplexes,^1873−1876 and the metal–ion bridging of duplex DNA by T–Hg²⁺–T or C–Ag⁺–C complexes.^1877,1878 Various fuels such as single-stranded oligonucleotide fragments, pH variation, metal ions, and light have been used to trigger these DNA devices.^1879−1884 These systems have been used in molecular sensing, drug delivery and other medical applications, the construction of logic gates, the control of chemical transformations, and for many other purposes.^{1874,1885−1911}

DNA tweezers represent a simple class of DNA machines.^1884,1912 They are two-armed constructs bridged by a DNA linker that can undergo transitions between open and closed states in response to external triggers such as the addition of single-stranded DNA or metal ions, or a change in pH. Willner et al. reported a biomolecular logic gate based on three different DNA tweezers A, B, and C. These were activated by different inputs: protons, Hg²⁺ ions, and nucleic acid strands (Figure 71). The output delivered by this machine depends both on the inputs provided and its initial internal state. Depending on the input, there are eight possible configurations of the three tweezers (open or closed for each). The output could be studied by measuring the Förster resonance energy transfer (FRET) between different pairs of fluorophore and quenching molecules attached to the arms of each of the three tweezers. The linker unit is common to all three tweezers, meaning that tweezers A and B can also be opened by the complementary antilinker. Thus, for any pair of tweezers, there are two different inputs that cause a change in the state of the device. In total, the device can adopt 16 different states and can furthermore be used as a memory storage system because each state and output is dependent not only on the most recent input but also on past states and inputs.^1913,1914

(a) Tweezer A: in the closed form the arms are bound to the linker unit (blue) by Hg²⁺ ions through T–Hg²⁺–T bonds. To open the molecular tweezer, Hg²⁺ is sequestered by the addition of cysteine. (b) Tweezer B: in acid the arms form an i-motif, thus releasing the linker unit, whereas at pH = 7.2, the i-motif is destroyed resulting in the stabilization of the closed structure. (c) Tweezer C: the linker unit can be released by a complementary strand, the antilinker that opens the tweezers. Reprinted with permission from ref (1914). Copyright 2010 American National Academy of Sciences.

DNA machines have been used to regulate enzyme cascade reactions.^1890,1891 Liu and co-workers reported a machine containing DNA double crossover (DX) motifs, which formed two rigid arms, joined by an immobile four-way junction (Figure 72).¹⁹¹⁵ A DNA motor that could switch between stem-loop and double-helix structures, driven by a strand displacement reaction, was incorporated at the center of the machine to cycle between open and closed states. This design amplifies the small motion generated by the DNA motor into a much greater change in separation between the ends of the two arms where glucose oxidase (GOx) and horseradish peroxidase (HRP) were attached. In this biochemical cascade system, GOx first catalyzed the oxidation of glucose to generate gluconic acid and hydrogen peroxide. Hydrogen peroxide is catalytically reduced by HRP into H₂O. At the same time, HRP turns ABTS^2– into ABTS^–, which allowed the kinetics of the peroxidase to be monitored. HRP has a much higher turnover rate then GOx, so the distance hydrogen peroxide must diffuse has a crucial influence on the rate of reaction. Therefore, when the two enzymes are attached to the two arms, the diffusion distance of hydrogen peroxide can be changed from 6 to 18 nm by operation of the DNA motor, regulating the rate of enzymatic reaction. Sequential addition of fuel and antifuel strands showed that this regulation was reversible.

DNA machine reported by Liu and co-workers, which could be used to regulate an enzyme cascade reaction. Reprinted with permission from ref (1915). Copyright 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Willner and co-workers have used catenated DNA machines as carriers of Au nanoparticles.¹⁹¹⁶ Ordered assemblies of nanoparticles with defined geometries have recently attracted a great deal of interest as these engineered nanoparticle systems are anticipated to show unique plasmonic properties.^1917,1918 The synthesis and structural characterization of DNA catenanes has been reported previously,^{1847,1849,1919,1920} as has a three-station directional DNA catenane rotary motor.¹⁹²¹ A three-ring catenated nanostructure has been used to program the assembly of two Au nanoparticles (of 5 and 10 nm diameter, Figure 73). One of the nanoparticles was attached to ring α and the other to ring γ (L₁). Ring α included two equivalent domains, I and II, which are complementary to domain III on ring γ. While the initial duplex between rings β and γ in region III is energetically favored, treatment of the linear catenated system L₁ with a fuel strand (Fu) displaces ring γ, which then translocates through hybridization to either site I or II of ring α (structures M₁ or M₂). In the presence of the appropriate blocker units (B), the directional translocation of ring γ proceeds below or above the central ring β to yield the configurations M₃ or M₄, respectively. The changes in proximity of the nanoparticles led to changes in plasmonic coupling, which was theoretically modeled. Such systems could have uses in nanomedicine and intracellular diagnostics.¹⁹¹⁶

(a) Programmed migration of two Au nanoparticles. (b) STEM images corresponding to the different structures; the bar corresponds to 20 nm. Reprinted with permission from ref (1916). Copyright 2013 Nature Publishing Group.

9.4. DNA Walkers

The controlled and predictable strand displacement of DNA and RNA has been used to construct complex devices.^{1369,1869,1922−1932} Among them, walkers represent a major subclass. The basic principle behind 1-D walking is illustrated in Figure 74. A relatively rigid and stable DNA track functionalized with protruding single-stranded anchorage points (footholds) is typically used.^1369,1933 Unlike the direct interactions of biological walker proteins with polymeric tracks, the footholds are attached to the track and bind the walker unit by base paring. The walker unit consists of regions with different nucleotide sequences (feet), which are attached to the track via another DNA fragment (the anchor strand), that can hybridize with both the walker and one of the footholds leaving a “toehold region” unpaired. Addition of the fuel strand results in base-pairing with an anchor strand, starting from the protruding toehold, and forms a more thermodynamically favored waste duplex. The removal of the anchor strand liberates the foothold and one foot of the walker. Walking is processive because the other foot is still attached to the track by a holding strand, which provides additional stabilization. The walker can be reattached to the track via the addition of another anchor strand.

Schematic representation of a DNA-based walker and track system. Footholds protrude from the track as single-stranded DNA fragments. Anchor and holding strands enable the walker unit to bind to the footholds by hybridization. Areas with functional importance are labeled, and complementary strands are depicted in the same color for clarity.

Stimuli-dependent positional DNA switches^1934,1935 and DNA-based devices performing multistep organic synthesis while migrating along a track have been reported.¹⁴⁴⁷ An in silico “tumbleweed” walker design has also been proposed.¹⁹³⁶ The first DNA-based walker was nonautonomous and bipedal and was reported by Sherman and Seeman.¹⁸³⁴ High dilution conditions were used to prevent the walker from scrambling betwen different tracks. Sequential addition of two different anchor and fuel strands in an aqueous buffer at 16 °C led to the desired walking motion being obtained. The products were characterized by polyacrylamide gel electrophoresis (PAGE). The energy required for directional walking was provided by the additional base-pairing in the waste duplex (red toehold region, Figure 74). Mechanistically, this walker is an inchworm walker because the leading foot remains the same throughout the operation. A hand-over-hand DNA walker (the mechanism of operation of kinesin) has been published by Shin and Pierce who used a similar design.¹⁸³³ Transport of a cargo over a DNA origami tile and the synthesis of nanoparticle sequences have been reported. It used a DNA origami walker unit with four “feet” for controlled movement, and three “arms” for picking up cargo, each consisting of single strands of DNA (Figures 75 and 76).^{1455,1937,1938} Fuel strands (F_i) were used to drive the motion and to remove the anchor strands (A_i). Each station was loaded with a distinct gold nanoparticle cargo and could be switched between states where cargo delivery was possible and where it was not. By manipulating the selective release of each foot from complementary strands of DNA on the DNA tile, the movement of the walker could be controlled. When coupled to the ability of the stations to be switched “on” or “off”, this allowed the formation of eight, differently composed, noncovalently bound products from the full operational sequence. This remarkable level of control on the nanoscale shows that the forces of Brownian motion can be exploited to great effect in the synthesis of complex supramolecular products. Transportation of a DNA cargo on a DNA origami tile over 16 consecutive steps has also been reported.¹⁹³⁹

(a) Structure of the DNA walker with four “feet” (F1–4) and three “hands” (H1–3). (b) Movement of walker across the DNA origami tile driven by sequentially added DNA “fuel” strands labeled FA. (c) Loading of cargo onto DNA walker. Reprinted with permission from ref (1455). Copyright 2010 Nature Publishing Group.

(a) Operation of DNA-based walker. (b) AFM images of walker. Reprinted with permission from ref (1455). Copyright 2010 Nature Publishing Group.

Turberfield, Reif, and Yan have reported autonomous walking in a DNA-based system.¹³⁷⁹ Three enzymes, the PfIM I and BstAP I restriction enzymes, and T4 ligase, were required for autonomous operation. Successive cleavage and ligation of the walker-foothold duplex resulted in directional walking along the track. Two autonomous burnt-bridges walkers have been reported using either a restriction endonuclease as an additive¹⁹⁴⁰ or a walker unit with intrinsic DNAzyme activity.^{1380,1941,1942} An autonomous DNA motor whose propulsion was driven by random polymerization has been synthesized.¹⁸²⁹ DNA strands were propeled at the growing end of the polymer by the energy gained from hybridization. A number of enzyme-free autonomous DNA walkers have since been published.^{1836,1943−1945} Autonomous multipedal walkers^1842,1946 and walkers performing autonomous and progressive acylation reactions have been disclosed.¹⁴⁴⁷ Autonomous DNA walkers that are driven by pyrene-mediated photocleavage of disulfide bonds,¹⁹⁴⁷ or photoisomerization-dependent hindrance/exposure of a complementary strand,¹³⁸³ have been designed.

A vital requirement for useful cargo transport is the ability to choose the correct path at a junction point. The walker should be capable of crossing the junction, and the path choice should be programmable. Turberfield et al. were able to autonomously regulate the transport of a DNA cargo on a branched track (Figure 77).¹⁸⁴³ Successive Holliday junctions formed between the selected fuel, foothold, and the cargo as the walker migrated. These led to strand exchange (equivalent to junction migration), followed by loop opening, which allowed the controlled migration of the cargo from one foothold to another. The same group have since used a single nucleoside, adenosine, to control the route taken at the track junction.¹³⁸¹

Walker with a choice of path at a junction. (a) Initially cargo resides on position W, and (b) the use of different set of fuels (F) leads to transport of cargo to either position. A displacing strand (Dz) was used for the fragmentation of the molecular ensemble and subsequent analysis of the cargo position. Reprinted with permission from ref (1843). Copyright 2011 American Chemical Society.

10. Conclusion and Outlook

Perhaps the best way to appreciate the technological potential of controlled molecular-level motion is to recognize that molecular machines lie at the heart of every significant biological process. Over billions of years of evolution, nature has not repeatedly chosen this solution for achieving complex task performance without good reason. In stark contrast to biology, none of mankind’s fantastic myriad of present-day technologies exploit controlled molecular-level motion in any way at all: every catalyst, every material, every polymer, every pharmaceutical, and every reagent all function through their static or equilibrium dynamic properties. When we learn how to build artificial structures that can control and exploit molecular-level motion, and interface their effects directly with other molecular-level substructures and the outside world, it will potentially impact on every aspect of functional molecule and materials design. An improved understanding of physics and biology will surely follow.

As indicated by the many examples that appear in this Review, the future for the field of artificial molecular machines is very bright.¹⁹⁴⁸ After a somewhat difficult period in the 1990s, when chemists struggled to understand the basic differences between machines at the macroscopic and nanometer length scales, scientists now have the know-how and synthetic tools available to enable them to make suitable machine architectures (e.g., catenanes, rotaxanes, overcrowded alkenes, molecules that walk upon tracks, etc.). They can switch the position of components (often by clever manipulation of noncovalent interactions between the various parts), they understand how to use ratchet mechanisms to create motor-mechanisms, and they are learning how to introduce them into more complex molecular machine systems.

Yet there are still several basic challenges to overcome for molecular machines to be able to fulfill their potential:

(i) In contrast to motor proteins, powered by ATP hydrolysis or proton gradients, there are as yet no chemically driven synthetic small-molecule motors that can operate autonomously (i.e., move or rotate directionally as long as a chemical fuel is present), the closest counter-examples being the Feringa overcrowded alkene motors that rotate continuously under irradiation with light.^429−453

(ii) Most of the synthetic molecular machines reported to date are based on only a single functioning part that moves, stops, fluoresces, catalyzes a reaction, etc. To perform tasks that cannot be accomplished by conventional chemical means, it will be necessary to design systems with multiple integrated parts, each component performing a dedicated role within the machine ensemble. This will not be straightforward because unlike a watch where the second hand, say, does not interfere with the components in the escapement mechanism, the components of a chemical machine are not easily isolated from each other (or the environment) and interference from one reactive part of a machine with another will be a significant issue as complexity increases beyond the current rather trivial systems.

(iii) The machines we are familiar with in the macroscopic world are generally stable, operating unchanged through many cycles, and by and large they do not make “mistakes”. This contrasts with those in the biological world where the stochastic nature of molecular dynamics mean that motors stall, or step backward, or detach from tracks, or make errors in synthesis that are spotted or corrected by other machines. These are intrinsic differences that require fundamentally different philosophies in terms of the way machines carry out tasks that chemists have not yet started to tackle.

(iv) The “reading” of a sequence of functional groups on a polymer stand (mRNA or DNA) is how biological molecular machines are programmed to carry out synthesis operations in the correct sequence. Although it is possible to use biological polymers to do this, molecular machines made from DNA are obviously far more limited in terms of operating conditions, chemical stability, and functionality than wholly synthetic systems. As yet there is no small-molecule “Turing machine”,¹⁹⁴⁹ that is, a molecular machine that can read information from a symbol-encoded molecular strand. Programming of small-molecule machines with an information-rich non-DNA strand (rather than the sequential addition of chemical stimuli, say) would be a game-changing development.

There are also issues on which protagonists in the field have differing points-of-view. The debate continues over whether it will ultimately prove more productive to build molecular machines based on macroscopic objects (e.g., Stoddart’s “molecular elevator”⁷³⁰ and “molecular pistons”⁵²⁷ and Tour’s “nanocars”,^1129−1132 etc.) or based on biological machines (e.g., artificial systems that seek to reproduce aspects of the behavior of kinesin^1398−1400 or the ribosome⁶⁶⁶). Certainly mimicking biology is not the only way to achieve complex functionality: computer chips are manufactured from silicon wafers rather than being wet and carbon-based like our brains. Yet equally machines have to be designed according to the environment they are intended to operate in, and there may be reasons why biology uses motors and not switches, and tracks and not wheels, to transport molecular cargoes. Or it may be that evolution just did not discover these solutions to such problems and that mankind, with the whole of the periodic table and known synthetic chemistry to work with, can. Perhaps the most productive approach will ultimately be found by following neither of these lines of investigation too closely, for example, by using chemical principles for “molecular robotics” in which ratcheted motions of molecular components (i.e., biologically inspired mechanisms) are used to perform tasks that have their origins in innovations introduced to advance developments in macroscopic technology (e.g., factory assembly lines).

The environments that molecular machines can most productively operate in also remain an open question. Efforts to incorporate molecular machines into regular arrays within crystalline solids (e.g., MOFs) are progressing apace and should allow tethered molecular machines to interact effectively with solution- or gas-phase substrates. It will be interesting to see what applications such systems are being tailored for. Molecular machines mounted on surfaces should allow for surface properties to be changed in a facile and effective manner using a minimal amount of the high-cost molecular structures. However, whether monolayers of molecular machines can be sufficiently robust will no doubt be an issue for practical applications. Most biological molecular machines operate while dissolved in solution, a situation that has no equivalent for macroscopic mechanical machines, and so chemists will have to consider carefully how to effectively address and utilize such machines in that environment. Molecular machines have the potential to act productively under each of these conditions; what is important is that the application is appropriate for which to use synthetic molecular machines. In most cases, the cost of synthesis will mean that this will only be the case if there is no way to carry out the task without using a molecular machine. So rotaxane-based “molecular muscles” have to compete with shape-memory polymers (or even stilbene-containing polymers) to be effective, and rotaxane-based switches, which work through the physical displacement of submolecular components, will have to compete with electron movements in silicon for applications. Chemical synthesis is one area where artificial molecular machines may one day be able to perform tasks that are not possible to achieve using conventional chemical methods, a potential “killer app”!

A quarter-of-a-century after chemists made the first fledging molecular protomachines, the tantalizing prospect of artificial molecular machines that can perform useful tasks is moving ever closer to becoming a reality. Molecular machines with multiple integrated parts are in design terms a fusion of the familiar with the strange. Examples of mechanical engineering from the world around us provide a conceptual framework for what we want tiny machines to achieve. Biology shows us how machines cope with the nature of the environment in performing tasks at nanometer length scales, and physics explains the often counterintuitive ways that such small objects must behave. Yet ultimately, while drawing on all of these disciplines for ideas, guidance, and inspiration, such machines have to be designed, built, and operated through chemistry, the central science.

Acknowledgments

We thank the ERC and EPSRC for financial support and the European Union Seventh Framework Marie Curie Intra-European Fellowship Program and the Swiss National Science Foundation for Postdoctoral Fellowships (to S.E.-C. and A.L.N., respectively).

Glossary

Abbreviations

AB: azobenzene
ABTS: 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid)
AFM: atomic force microscope
ATP: adenosine triphosphate
BODIPY: boron-dipyrromethene
Bpy: bipyridine
CB: cucurbituril
CBPQT: cyclobis(paraquat-p-phenylene)
CBS: Corey–Bakshi–Shibata
CD: circular dichroism or cyclodextrin
CuAAC: copper-catalyzed azide–alkyne cycloaddition
Cys: cysteine
D: displacing strand
DAE: diarylethene
DBU: 1,8-diazabicycloundec-7-ene
DMAP: 4-dimethylaminopyridine
DMF: dimethylformamide
DMSO: dimethyl sulfoxide
DNA: DNA
DNP: dioxynaphtalene
DTT: dithiothreitol
ee: enantiomeric excess
ESIPT: excited-state intramolecular proton transfer
EXSY: exchange spectroscopy
F: fuel strand
FRET: Förster resonance energy transfer
GOx: glucose oxidase
GSCC: ground-state coconformation
HBT: 2-(2-hydroxyphenyl)-benzothiazole
HOMO: highest occupied molecular orbital
HPLC: high-performance liquid chromatography
HRP: horseradish peroxidase
iPr₂NEt: N,N-diisopropylethylamine
IR: infrared
LB: Langmuir–Blodgett
LUMO: lowest unoccupied molecular orbital
MOF: metal organic framework
Mc: merocyanine
MS: mass spectrometry
MSCC: metastable state coconformation
MscL: large-conductance mechanosensitive channel
MSTJ: molecular switch tunnel junction
MV: methyl viologen
NCL: native chemical ligation
NMR: nuclear magnetic resonance
XPS: X-ray photoelectron spectroscopy
PAGE: polyacrylamide gel electrophoresis
PEO: poly(ethylene oxide)
PLP: pyridoxal 5′-phosphate
PMB: p-methoxybenzyl
PMMA: poly(methyl methacrylate)
R: Reynolds number
RET: resonance energy transfer
RNA: ribonucleic acid
SAM: self-assembled monolayer
SEM: scanning electron microscope
Sp: spiropyran
STM: scanning tunneling microscope
T: temperature
TBDMSCl: tert-butyldimethylsilyl chloride
TCBD: tetracyanobutadiene
TFA: trifluoroacetic acid
TNF: 2,4,7-trinitro-9-fluorenone
TON: turnover number
TTF: tetrathiafulvalene
UV: ultraviolet

Biographies

graphic file with name cr-2015-001465_0128.jpg

Sündüs Erbaş Çakmak obtained her B.Sc. degree in Molecular Biology and Genetics in 2007 from Boğaziçi University in Istanbul, Turkey. She carried out her Ph.D. degree (2013) in Materials Science and Nanotechnology at the National Nanotechnology Institute, Bilkent University, under the supervision of Prof. Engin U. Akkaya, investigating concatenation and the use of molecular logic gates for the activity modulation of photodynamic therapy agents. She worked under the supervision of Amar H. Flood in Indiana University for 6 months during her Ph.D. working on the development of fluorescent anion sensors. In 2013 she joined Prof. David A. Leigh’s group as a Marie-Curie Intra-European Post-Doctoral Fellow. Her research interests include artificial molecular machines, supramolecular catalysis, and molecular computing.

graphic file with name cr-2015-001465_0129.jpg

David Leigh was born in Birmingham (UK) and obtained his B.Sc. and Ph.D. degrees from the University of Sheffield. After postdoctoral research in Ottawa (1987–1989), he was appointed to a Lectureship at the University of Manchester Institute of Science and Technology (UK). After spells at the Universities of Warwick and Edinburgh, he returned to Manchester in 2012, where he currently holds the Sir Samuel Hall Chair of Chemistry. Prizes and awards for his group’s research contributions include the 2007 International Izatt-Christensen Award for Macrocyclic Chemistry, 2007 Feynman Prize for Nanotechnology, 2007 EU Descartes Prize for Research, 2009 RSC Merck Award, 2010 RSC Tilden Prize, 2013 Royal Society Bakerian Lecture and Prize, and the 2014 RSC Pedler Prize. In 2009 he was elected to the Fellowship of the Royal Society (London). His research interests include the design, synthesis, and operation of artificial molecular-level motors and machines.

graphic file with name cr-2015-001465_0130.jpg

Charlie Thomas McTernan was born in London and obtained his M.Chem. from the University of Oxford. His Part II project was conducted under the supervison of Prof. Tim Donohoe, investigating the synthesis of isoquinoline motifs using palladium-catalyzed α-arylation. He joined David Leigh’s group in 2013, funded by a University of Manchester Dean’s Faculty Award. His research interests include the synthesis of artificial molecular machines, switchable catalysts, and rotaxanes.

graphic file with name cr-2015-001465_0131.jpg

Alina Laura Nussbaumer was born in Bern (Switzerland) and obtained her B.Sc. and M.Sc. degrees from the University of Bern. She completed her Ph.D. under the supervision of Prof. Robert Häner at the same University, investigating DNA as a scaffold for chromophore assembly toward the development of novel DNA-based materials and the production of supramolecular polymers based on DNA-conjugates that show strong amplification of chirality. In 2012, she joined David Leigh’s group as a Swiss National Science Foundation Post-Doctoral Fellow. Her research interests include controlled molecular motion and the development of new synthetic tactics toward topologically complex molecules.

Special Issue

This paper is an additional review for Chem. Rev. 2015, 115, 15, “Supramolecular Chemistry”.

The authors declare no competing financial interest.

References

Brown R. A Brief Account of Microscopical Observations Made on the Particles Contained in the Pollen of Plants. Philos. Mag. 1828, 4, 171–173 10.1080/14786442808674769. [DOI] [Google Scholar]
Brown R. On the Particles Contained in the Pollen of Plants; and on the General Existence of Active Molecules in Organic and Inorganic Bodies. Edinb. New Philos. J. 1828, 5, 358–371. [Google Scholar]
Perrin J. In Atoms (English Translation), 2nd ed.; Hammick D. L., Ed.; Constable and Co.: London, 1923. [Google Scholar]
Einstein A. Über die von der Molekularkinetischen Theorie der Wärme Geforderte Bewegung von in Ruhenden Flüssigkeiten Suspendierten Teilchen. Ann. Phys. 1905, 17, 549–560 10.1002/andp.19053220806. [DOI] [Google Scholar]
Feynman R. P.; Leighton R. B.; Sands M.. The Feynman Lectures on Physics; Addison-Wesley: Reading, MA, 1963; Vol. 1, Chapter 46. [Google Scholar]
Smalley R. E.; Drexler K. E. Nanotechnology. Chem. Eng. News 2003, 81, 37–42. [Google Scholar]
Balzani V.; Credi A.; Raymo F. M.; Stoddart J. F. Artificial Molecular Machines. Angew. Chem., Int. Ed. 2000, 39, 3348–3391. [DOI] [PubMed] [Google Scholar]
Credi A. Artificial Molecular Motors Powered by Light. Aust. J. Chem. 2006, 59, 157–169 10.1071/CH06025. [DOI] [Google Scholar]
Paxton W. F.; Sundararajan S.; Mallouk T. E.; Sen A. Chemical Locomotion. Angew. Chem., Int. Ed. 2006, 45, 5420–5429 10.1002/anie.200600060. [DOI] [PubMed] [Google Scholar]
Tian H.; Wang Q.-C. Recent Progress on Switchable Rotaxanes. Chem. Soc. Rev. 2006, 35, 361–374 10.1039/b512178g. [DOI] [PubMed] [Google Scholar]
Leigh D.; Pérez E.. Dynamic Chirality: Molecular Shuttles and Motors. In Supramolecular Chirality; Crego-Calama M., Reinhoudt D., Eds.; Springer: Berlin, Heidelberg, 2006; Vol. 265, pp 185–208. [Google Scholar]
Hess H. Self-assembly Driven by Molecular Motors. Soft Matter 2006, 2, 669–677 10.1039/b518281f. [DOI] [PubMed] [Google Scholar]
Browne W. R.; Feringa B. L. Making Molecular Machines Work. Nat. Nanotechnol. 2006, 1, 25–35 10.1038/nnano.2006.45. [DOI] [PubMed] [Google Scholar]
Kay E. R.; Leigh D. A.; Zerbetto F. Synthetic Molecular Motors and Mechanical Machines. Angew. Chem., Int. Ed. 2007, 46, 72–191 10.1002/anie.200504313. [DOI] [PubMed] [Google Scholar]
Balzani V.; Credi A.; Venturi M. Molecular Machines Working on Surfaces and at Interfaces. ChemPhysChem 2008, 9, 202–220 10.1002/cphc.200700528. [DOI] [PubMed] [Google Scholar]
Ma X.; Tian H. Bright Functional Rotaxanes. Chem. Soc. Rev. 2010, 39, 70–80 10.1039/B901710K. [DOI] [PubMed] [Google Scholar]
Wang J.; Manesh K. M. Motion Control at the Nanoscale. Small 2010, 6, 338–345 10.1002/smll.200901746. [DOI] [PubMed] [Google Scholar]
Coskun A.; Banaszak M.; Astumian R. D.; Stoddart J. F.; Grzybowski B. A. Great Expectations: Can Artificial Molecular Machines Deliver on Their Promise?. Chem. Soc. Rev. 2012, 41, 19–30 10.1039/C1CS15262A. [DOI] [PubMed] [Google Scholar]
Yang W.; Li Y.; Liu H.; Chi L.; Li Y. Design and Assembly of Rotaxane-Based Molecular Switches and Machines. Small 2012, 8, 504–516 10.1002/smll.201101738. [DOI] [PubMed] [Google Scholar]
Neal E. A.; Goldup S. M. Chemical Consequences of Mechanical Bonding in Catenanes and Rotaxanes: Isomerism, Modification, Catalysis and Molecular Machines for Synthesis. Chem. Commun. 2014, 50, 5128–5142 10.1039/c3cc47842d. [DOI] [PubMed] [Google Scholar]
van Dongen S. F. M.; Cantekin S.; Elemans J. A. A. W.; Rowan A. E.; Nolte R. J. M. Functional Interlocked Systems. Chem. Soc. Rev. 2014, 43, 99–122 10.1039/C3CS60178A. [DOI] [PubMed] [Google Scholar]
Zhang M. M.; Yan X. Z.; Huang F. H.; Niu Z. B.; Gibson H. W. Stimuli-Responsive Host-Guest Systems Based on the Recognition of Cryptands by Organic Guests. Acc. Chem. Res. 2014, 47, 1995–2005 10.1021/ar500046r. [DOI] [PubMed] [Google Scholar]
Xue M.; Yang Y.; Chi X. D.; Zhang Z. B.; Huang F. H. New Class of Macrocycles for Supramolecular Chemistry. Acc. Chem. Res. 2012, 45, 1294–1308 10.1021/ar2003418. [DOI] [PubMed] [Google Scholar]
Gil-Ramirez G.; Leigh D. A.; Stephens A. J. Catenanes Fifty Years of Molecular Links. Angew. Chem., Int. Ed. 2015, 54, 6110–6150 10.1002/anie.201411619. [DOI] [PMC free article] [PubMed] [Google Scholar]
Colinvaux P. Life at Low Reynolds-Number. Nature 1979, 277, 353–354 10.1038/277353a0. [DOI] [Google Scholar]
Purcell E. M. Life at Low Reynolds-Number. Am. J. Phys. 1977, 45, 3–11 10.1119/1.10903. [DOI] [Google Scholar]
Shenker O. R. Maxwell’s Demon 2: Entropy, Classical and Quantum Information, Computing. Stud. Hist. Philos. M. P. 2004, 35B, 537–540 10.1016/j.shpsb.2004.04.001. [DOI] [Google Scholar]
Maxwell J. C.Theory of Heat; Longmans, Green and Co.: London, 1871; Chapter 22. [Google Scholar]
Smoluchowski M. S. On Opalescence of Gases in the Critical State. Philos. Mag. 1912, 23, 165–173 10.1080/14786440108637209. [DOI] [Google Scholar]
Feynman R. P.; Vernon F. L. The Theory of a General Quantum System Interacting with a Linear Dissipative System. Ann. Phys. 1963, 24, 118–173 10.1016/0003-4916(63)90068-X. [DOI] [Google Scholar]
Ehrenberg W. Maxwell’s Demon. Sci. Am. 1967, 217, 103–110 10.1038/scientificamerican1167-103. [DOI] [Google Scholar]
For the first private written discussion of the “temperature demon”, see:; Maxwell J. C.Letter to P. G. Tait, 11 December 1867; quoted in C. G. Knott, Life and Scientific Work of Peter Guthrie Tait; Cambridge University Press: London, 1911; p 213; [Google Scholar]; and reproduced in: The Scientific Letters and Papers of James Clerk Maxwell 1862; Harman P. M., Ed.; Cambridge University Press: Cambridge, 1995; Vol. II, p 331. [Google Scholar]
Szilard L. On the Minimization of Entropy in a Thermodynamic System with Interferences of Intelligent Beings. Eur. Phys. J. A 1929, 53, 840–856 10.1007/BF01341281. [DOI] [Google Scholar]
Bennett C. The Thermodynamics of Computation—A Review. Int. J. Theor. Phys. 1982, 21, 905–940 10.1007/BF02084158. [DOI] [Google Scholar]
Landauer R. Irreversibility and Heat Generation in the Computing Process. IBM J. Res. Dev. 1961, 5, 183–191 10.1147/rd.53.0183. [DOI] [Google Scholar]
Berut A.; Arakelyan A.; Petrosyan A.; Ciliberto S.; Dillenschneider R.; Lutz E. Experimental Verification of Landauer’s Principle Linking Information and Thermodynamics. Nature 2012, 483, 187–189 10.1038/nature10872. [DOI] [PubMed] [Google Scholar]
The idea of a “pressure demon” was introduced by Maxwell in a later letter to Tait (believed to date from early 1875); quoted in: Knott C. G.Life and Scientific Work of Peter Guthrie Tait; Cambridge University Press: London, Cambridge, 1911; p 214; and reproduced in: The Scientific Letters and Papers of James Clerk Maxwell 1874; Harman P. M., Ed.; Cambridge University Press: London, Cambridge, 2002; Vol. III, p 185. [Google Scholar]
Zheng J. Z.; Zheng X.; Zhao Y.; Xie Y.; Yam C. Y.; Chen G. H.; Jiang Q.; Chwang A. T. Maxwell’s Demon and Smoluchowski’s Trap Door (vol 75, art no 041109, 2007). Phys. Rev. E 2007, 75, 041109. 10.1103/PhysRevE.75.041109. [DOI] [PubMed] [Google Scholar]
Skordos P. A.; Zurek W. H. Maxwell’s Demon, Rectifiers, and the Second Law: Computer Simulation of Smoluchowski’s Trapdoor. Am. J. Phys. 1992, 60, 876–882 10.1119/1.17007. [DOI] [Google Scholar]
Parrondo J. M. R.; Espanol P. Criticism of Feynman’s Analysis of the Ratchet as an Engine. Am. J. Phys. 1996, 64, 1125–1130 10.1119/1.18393. [DOI] [Google Scholar]
Sakaguchi H. A Langevin Simulation for the Feynman Ratchet Model. J. Phys. Soc. Jpn. 1998, 67, 709–712 10.1143/JPSJ.67.709. [DOI] [Google Scholar]
Hondou T.; Takagi F. Irreversible Operation in a Stalled State of Feynman’s Ratchet. J. Phys. Soc. Jpn. 1998, 67, 2974–2976 10.1143/JPSJ.67.2974. [DOI] [Google Scholar]
Magnasco M. O.; Stolovitzky G. Feynman’s Ratchet and Pawl. J. Stat. Phys. 1998, 93, 615–632 10.1023/B:JOSS.0000033245.43421.14. [DOI] [Google Scholar]
Jarzynski C.; Mazonka O. Feynman’s Ratchet and Pawl: An Exactly Solvable Model. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1999, 59, 6448–6459 10.1103/PhysRevE.59.6448. [DOI] [PubMed] [Google Scholar]
Jahn R.; Fasshauer D. Molecular Machines Governing Exocytosis of Synaptic Vesicles. Nature 2012, 490, 201–207 10.1038/nature11320. [DOI] [PMC free article] [PubMed] [Google Scholar]
Piccolino M. Biological Machines: From Mills to Molecules. Nat. Rev. Mol. Cell Biol. 2000, 1, 149–153 10.1038/35040097. [DOI] [PubMed] [Google Scholar]
Kinbara K.; Aida T. Toward Intelligent Molecular Machines: Directed Motions of Biological and Artificial Molecules and Assemblies. Chem. Rev. 2005, 105, 1377–1400 10.1021/cr030071r. [DOI] [PubMed] [Google Scholar]
Pomorski T.; Hrafnsdóttir S.; Devaux P. F.; Meer G. V. Lipid Distribution and Transport Across Cellular Membranes. Semin. Cell Dev. Biol. 2001, 12, 139–148 10.1006/scdb.2000.0231. [DOI] [PubMed] [Google Scholar]
Haydon D. A.; Hladky S. B. Ion Transport Across Thin Lipid Membranes: A Critical Discussion of Mechanisms in Selected Systems. Q. Rev. Biophys. 1972, 5, 187–282 10.1017/S0033583500000883. [DOI] [PubMed] [Google Scholar]
Whittam R.; Wheeler K. P. Transport Across Cell Membranes. Annu. Rev. Physiol. 1970, 32, 21–60 10.1146/annurev.ph.32.030170.000321. [DOI] [PubMed] [Google Scholar]
Gouaux E.; MacKinnon R. Principles of Selective Ion Transport in Channels and Pumps. Science 2005, 310, 1461–1465 10.1126/science.1113666. [DOI] [PubMed] [Google Scholar]
Jorgensen P. L.; Hakansson K. O.; Karlish S. J. D. Structure and Mechanism of Na,K-ATPase: Functional Sites and Their Interactions. Annu. Rev. Physiol. 2003, 65, 817–849 10.1146/annurev.physiol.65.092101.142558. [DOI] [PubMed] [Google Scholar]
Hayashi S.; Ueno H.; Shaikh A. R.; Umemura M.; Kamiya M.; Ito Y.; Ikeguchi M.; Komoriya Y.; Iino R.; Noji H. Molecular Mechanism of ATP Hydrolysis in F₁-ATPase Revealed by Molecular Simulations and Single-Molecule Observations. J. Am. Chem. Soc. 2012, 134, 8447–8454 10.1021/ja211027m. [DOI] [PubMed] [Google Scholar]
Nakanishi-Matsui M.; Sekiya M.; Nakamoto R. K.; Futai M. The Mechanism of Rotating Proton Pumping ATPases. Biochim. Biophys. Acta, Bioenerg. 2010, 1797, 1343–1352 10.1016/j.bbabio.2010.02.014. [DOI] [PubMed] [Google Scholar]
von Ballmoos C.; Wiedenmann A.; Dimroth P. Essentials for ATP Synthesis by F₁F₀ ATP Synthases. Annu. Rev. Biochem. 2009, 78, 649–672 10.1146/annurev.biochem.78.081307.104803. [DOI] [PubMed] [Google Scholar]
Nyblom M.; Poulsen H.; Gourdon P.; Reinhard L.; Andersson M.; Lindahl E.; Fedosova N.; Nissen P. Crystal Structure of Na⁺, K⁺-ATPase in the Na⁺-Bound State. Science 2013, 342, 123–127 10.1126/science.1243352. [DOI] [PubMed] [Google Scholar]
Nakamoto R. K.; Scanlon J. A. B.; Al-Shawi M. K. The Rotary Mechanism of the ATP Synthase. Arch. Biochem. Biophys. 2008, 476, 43–50 10.1016/j.abb.2008.05.004. [DOI] [PMC free article] [PubMed] [Google Scholar]
Toyoshima C.; Inesi G. Structural Basis of Ion Pumping by Ca²⁺-ATPase of the Sarcoplasmic Reticulum. Annu. Rev. Biochem. 2004, 73, 269–292 10.1146/annurev.biochem.73.011303.073700. [DOI] [PubMed] [Google Scholar]
Kastritis P. L.; Bonvin A. M. J. J. On the Binding of Macromolecular Interactions: Daring to Ask Why Proteins Interact. J. R. Soc., Interface 2012, 10, 20120835. 10.1098/rsif.2012.0835. [DOI] [PMC free article] [PubMed] [Google Scholar]
Maloney P. C.; Kashket E. R.; Wilson T. H. A Protonmotive Force Drives ATP Synthesis in Bacteria. Proc. Natl. Acad. Sci. U. S. A. 1974, 71, 3896–3900 10.1073/pnas.71.10.3896. [DOI] [PMC free article] [PubMed] [Google Scholar]
Møller J. V.; Nissen P.; Sørensen T. L. M.; Maire M. l. Transport Mechanism of the Sarcoplasmic Reticulum Ca²⁺-ATPase Pump. Curr. Opin. Struct. Biol. 2005, 15, 387–393 10.1016/j.sbi.2005.06.005. [DOI] [PubMed] [Google Scholar]
Birge R. R. Nature of the Primary Photochemical Events in Rhodopsin and Bacteriorhodopsin. Biochim. Biophys. Acta, Bioenerg. 1990, 1016, 293–327 10.1016/0005-2728(90)90163-X. [DOI] [PubMed] [Google Scholar]
Neutze R.; Pebay-Peyroula E.; Edman K.; Royant A.; Navarro J.; Landau E. M. Bacteriorhodopsin: A High-resolution Structural View of Vectorial Proton Transport. Biochim. Biophys. Acta, Biomembr. 2002, 1565, 144–167 10.1016/S0005-2736(02)00566-7. [DOI] [PubMed] [Google Scholar]
Lanyi J. K.; Luecke H. Bacteriorhodopsin. Curr. Opin. Struct. Biol. 2001, 11, 415–419 10.1016/S0959-440X(00)00226-8. [DOI] [PubMed] [Google Scholar]
Shibata M.; Yamashita H.; Uchihashi T.; Kandori H.; Ando T. High-speed Atomic Force Microscopy Shows Dynamic Molecular Processes in Photoactivated Bacteriorhodopsin. Nat. Nanotechnol. 2010, 5, 208–212 10.1038/nnano.2010.7. [DOI] [PubMed] [Google Scholar]
Hirai T.; Subramaniam S. Protein Conformational Changes in the Bacteriorhodopsin Photocycle: Comparison of Findings from Electron and X-Ray Crystallographic Analyses. PLoS One 2009, 4, e5769. 10.1371/journal.pone.0005769. [DOI] [PMC free article] [PubMed] [Google Scholar]
Haupts U.; Tittor J.; Oesterhelt D. Closing in on Bactereorhodopsin: Progress in Understanding the Molecule. Annu. Rev. Biophys. Biomol. Struct. 1999, 28, 367–399 10.1146/annurev.biophys.28.1.367. [DOI] [PubMed] [Google Scholar]
Yonath A. Hibernating Bears, Antibiotics, and the Evolving Ribosome (Nobel Lecture). Angew. Chem., Int. Ed. 2010, 49, 4340–4354 10.1002/anie.201001297. [DOI] [PubMed] [Google Scholar]
Ramakrishnan V. Unraveling the Structure of the Ribosome (Nobel Lecture). Angew. Chem., Int. Ed. 2010, 49, 4355–4380 10.1002/anie.201001436. [DOI] [PubMed] [Google Scholar]
Steitz T. A. From the Structure and Function of the Ribosome to New Antibiotics (Nobel Lecture). Angew. Chem., Int. Ed. 2010, 49, 4381–4398 10.1002/anie.201000708. [DOI] [PubMed] [Google Scholar]
Bruck I.; O’Donnell M. The Ring-type Polymerase Sliding Clamp Family. Genome Biol. 2001, 2, reviews3001.1–reviews3001.3 10.1186/gb-2001-2-1-reviews3001. [DOI] [PMC free article] [PubMed] [Google Scholar]
Astumian R. D. Comment: Detailed Balance Revisited. Phys. Chem. Chem. Phys. 2009, 11, 9592–9594 10.1039/b911608g. [DOI] [PubMed] [Google Scholar]
Astumian R. D. Adiabatic Operation of a Molecular Machine. Proc. Natl. Acad. Sci. U. S. A. 2007, 104, 19715–19718 10.1073/pnas.0708040104. [DOI] [Google Scholar]
Mattia E.; Otto S. Supramolecular Systems Chemistry. Nat. Nanotechnol. 2015, 10, 111–119 10.1038/nnano.2014.337. [DOI] [PubMed] [Google Scholar]
Chatterjee M. N.; Kay E. R.; Leigh D. A. Beyond Switches: Ratcheting a Particle Energetically Uphill with a Compartmentalized Molecular Machine. J. Am. Chem. Soc. 2006, 128, 4058–4073 10.1021/ja057664z. [DOI] [PubMed] [Google Scholar]
Astumian R. D. Stochastic Conformational Pumping: A Mechanism for Free-energy Transduction by Molecules. Annu. Rev. Biophys. 2011, 40, 289–313 10.1146/annurev-biophys-042910-155355. [DOI] [PubMed] [Google Scholar]
Astumian R. D. Microscopic Reversibility as the Organizing Principle of Molecular Machines. Nat. Nanotechnol. 2012, 7, 684–688 10.1038/nnano.2012.188. [DOI] [PubMed] [Google Scholar]
Simon M. S.; Peskin C. S.; Oster G. F. What Drives the Translocation of Proteins?. Proc. Natl. Acad. Sci. U. S. A. 1992, 89, 3770–3774 10.1073/pnas.89.9.3770. [DOI] [PMC free article] [PubMed] [Google Scholar]
Astumian R. D. Thermodynamics and Kinetics of a Brownian Motor. Science 1997, 276, 917–922 10.1126/science.276.5314.917. [DOI] [PubMed] [Google Scholar]
Bier M. Brownian Ratchets in Physics and Biology. Contemp. Phys. 1997, 38, 371–379 10.1080/001075197182180. [DOI] [Google Scholar]
Juelicher F.; Ajdari A.; Prost J. Modeling Molecular Motors. Rev. Mod. Phys. 1997, 69, 1269–1281 10.1103/RevModPhys.69.1269. [DOI] [Google Scholar]
Astumian R. D. Making Molecules into Motors. Sci. Am. 2001, 285, 56–64 10.1038/scientificamerican0701-56. [DOI] [PubMed] [Google Scholar]
Lipowsky R.; Jaster N. Molecular Motor Cycles: From Ratchets to Networks. J. Stat. Phys. 2003, 110, 1141–1167 10.1023/A:1022101011650. [DOI] [Google Scholar]
Parrondo J. M. R.; Dinís L. Brownian Motion and Gambling: From Ratchets to Paradoxical Games. Contemp. Phys. 2004, 45, 147–157 10.1080/00107510310001644836. [DOI] [Google Scholar]
Astumian R. D. Design Principles for Brownian Molecular Machines: How to Swim in Molasses and Walk in a Hurricane. Phys. Chem. Chem. Phys. 2007, 9, 5067–5083 10.1039/b708995c. [DOI] [PubMed] [Google Scholar]
Parrondo J. M. R.; de Cisneros B. J. Energetics of Brownian Motors: A Review. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 179–191 10.1007/s003390201332. [DOI] [Google Scholar]
Reimann P.; Hänggi P. Introduction to the Physics of Brownian Motors. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 169–178 10.1007/s003390201331. [DOI] [Google Scholar]
Landauer R. Inadequacy of Entropy and Entropy Derivatives in Characterizing the Steady State. Phys. Rev. A: At., Mol., Opt. Phys. 1975, 12, 636–638 10.1103/PhysRevA.12.636. [DOI] [Google Scholar]
Büttiker M. Transport as a Consequence of State-dependent Diffusion. Z. Phys. B: Condens. Matter 1987, 68, 161–167 10.1007/BF01304221. [DOI] [Google Scholar]
Landauer R. Motion out of Noisy States. J. Stat. Phys. 1988, 53, 233–248 10.1007/BF01011555. [DOI] [Google Scholar]
Van Kampen N. G. Relative Stability in Nonuniform Temperature. IBM J. Res. Dev. 1988, 32, 107–111 10.1147/rd.321.0107. [DOI] [Google Scholar]
Sinha K.; Moss F. Analog Simulation of a Simple System with State-dependent Diffusion. J. Stat. Phys. 1989, 54, 1411–1423 10.1007/BF01044724. [DOI] [Google Scholar]
Rousselet J.; Salome L.; Ajdari A.; Prostt J. Directional Motion of Brownian Particles Induced by a Periodic Asymmetric Potential. Nature 1994, 370, 446–447 10.1038/370446a0. [DOI] [PubMed] [Google Scholar]
Faucheux L. P.; Bourdieu L. S.; Kaplan P. D.; Libchaber A. J. Optical Thermal Ratchet. Phys. Rev. Lett. 1995, 74, 1504–1507 10.1103/PhysRevLett.74.1504. [DOI] [PubMed] [Google Scholar]
Faucheux L. P.; Libchaber A. Selection of Brownian Particles. J. Chem. Soc., Faraday Trans. 1995, 91, 3163–3166 10.1039/ft9959103163. [DOI] [Google Scholar]
Faucheux L. P.; Stolovitzky G.; Libchaber A. Periodic Forcing of a Brownian Particle. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1995, 51, 5239–5250 10.1103/PhysRevE.51.5239. [DOI] [PubMed] [Google Scholar]
Astumian R. D.; Bier M. Mechanochemical Coupling of the Motion of Molecular Motors to ATP Hydrolysis. Biophys. J. 1996, 70, 637–653 10.1016/S0006-3495(96)79605-4. [DOI] [PMC free article] [PubMed] [Google Scholar]
Gorre L.; Ioannidis E.; Silberzan P. Rectified Motion of a Mercury Drop in an Asymmetric Structure. Europhys. Lett. 1996, 33, 267–272 10.1209/epl/i1996-00331-2. [DOI] [Google Scholar]
Zhou H.-X.; Chen Y.-D. Chemically Driven Motility of Brownian Particles. Phys. Rev. Lett. 1996, 77, 194–197 10.1103/PhysRevLett.77.194. [DOI] [PubMed] [Google Scholar]
Gorre-Talini L.; Jeanjean S.; Silberzan P. Sorting of Brownian Particles by the Pulsed Application of an Asymmetric Potential. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1997, 56, 2025–2034 10.1103/PhysRevE.56.2025. [DOI] [Google Scholar]
Gorre-Talini L.; Silberzan P. Force-Free Motion of a Mercury Drop Alternatively Submitted to Shifted Asymmetric Potentials. J. Phys. I (France) 1997, 7, 1475–1485. [Google Scholar]
Astumian R. D.; Derényi I. Fluctuation Driven Transport and Models of Molecular Motors and Pumps. Eur. Biophys. J. 1998, 27, 474–489 10.1007/s002490050158. [DOI] [PubMed] [Google Scholar]
Gorre-Talini L.; Spatz J. P.; Silberzan P. Dielectrophoretic Ratchets. Chaos 1998, 8, 650–656 10.1063/1.166347. [DOI] [PubMed] [Google Scholar]
Linke H.; Sheng W.; Löfgren A.; Hongqi X.; Omling P.; Lindelof P. E. A Quantum Dot Ratchet: Experiment and Theory. Europhys. Lett. 1998, 44, 341–347 10.1209/epl/i1998-00562-1. [DOI] [Google Scholar]
Lorke A.; Wimmer S.; Jager B.; Kotthaus J. P.; Wegscheider W.; Bichler M. Far-infrared and Transport Properties of Antidot Arrays with Broken Symmetry. Phys. B 1998, 249–251, 312–316 10.1016/S0921-4526(98)00121-5. [DOI] [Google Scholar]
Bekele M.; Rajesh S.; Ananthakrishna G.; Kumar N. Effect of Landauer’s Blow Torch on the Equilibration Rate in a Bistable Potential. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1999, 59, 143–149 10.1103/PhysRevE.59.143. [DOI] [Google Scholar]
Derényi I.; Bier M.; Astumian R. D. Generalized Efficiency and its Application to Microscopic Engines. Phys. Rev. Lett. 1999, 83, 903–906 10.1103/PhysRevLett.83.903. [DOI] [Google Scholar]
Linke H.; Humphrey T. E.; Löfgren A.; Sushkov A. O.; Newbury R.; Taylor R. P.; Omling P. Experimental Tunneling Ratchets. Science 1999, 286, 2314–2317 10.1126/science.286.5448.2314. [DOI] [PubMed] [Google Scholar]
Mennerat-Robilliard C.; Lucas D.; Guibal S.; Tabosa J.; Jurczak C.; Courtois J. Y.; Grynberg G. Ratchet for Cold Rubidium Atoms: The Asymmetric Optical Lattice. Phys. Rev. Lett. 1999, 82, 851–854 10.1103/PhysRevLett.82.851. [DOI] [Google Scholar]
Parmeggiani A.; Jülicher F.; Ajdari A.; Prost J. Energy Transduction of Isothermal Ratchets: Generic Aspects and Specific Examples Close to and Far from Equilibrium. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1999, 60, 2127–2140 10.1103/PhysRevE.60.2127. [DOI] [PubMed] [Google Scholar]
Switkes M.; Marcus C. M.; Campman K.; Gossard A. C. An Adiabatic Quantum Electron Pump. Science 1999, 283, 1905–1908 10.1126/science.283.5409.1905. [DOI] [PubMed] [Google Scholar]
van Oudenaarden A.; Boxer S. G. Brownian Ratchets: Molecular Separations in Lipid Bilayers Supported on Patterned Arrays. Science 1999, 285, 1046–1048 10.1126/science.285.5430.1046. [DOI] [PubMed] [Google Scholar]
Linke H.; Sheng W. D.; Svensson A.; Löfgren A.; Christensson L.; Xu H. Q.; Omling P.; Lindelof P. E. Asymmetric Nonlinear Conductance of Quantum Dots with Broken Inversion Symmetry. Phys. Rev. B: Condens. Matter Mater. Phys. 2000, 61, 15914–15926 10.1103/PhysRevB.61.15914. [DOI] [Google Scholar]
Lipowsky R.Molecular Motors and Stochastic Models. In Stochastic Processes in Physics, Chemistry, and Biology; Freund J., Pöschel T., Eds.; Springer: Berlin Heidelberg, 2000; Vol. 557, pp 21–31. [Google Scholar]
Mahadevan L.; Matsudaira P. Motility Powered by Supramolecular Springs and Ratchets. Science 2000, 288, 95–99 10.1126/science.288.5463.95. [DOI] [PubMed] [Google Scholar]
Bustamante C.; Keller D.; Oster G. The Physics of Molecular Motors. Acc. Chem. Res. 2001, 34, 412–420 10.1021/ar0001719. [DOI] [PubMed] [Google Scholar]
Höhberger E. M.; Lorke A.; Wegscheider W.; Bichler M. Adiabatic Pumping of Two-dimensional Electrons in a Ratchet-type Lateral Superlattice. Appl. Phys. Lett. 2001, 78, 2905–2907 10.1063/1.1355672. [DOI] [Google Scholar]
Astumian R. D. Protein Conformational Fluctuations and Free-energy Transduction. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 193–206 10.1007/s003390201406. [DOI] [Google Scholar]
Linke H.; Humphrey T. E.; Lindelof P. E.; Löfgren A.; Newbury R.; Omling P.; Sushkov A. O.; Taylor R. P.; Xu H. Quantum Ratchets and Quantum Heat Pumps. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 237–246 10.1007/s003390201335. [DOI] [Google Scholar]
Marquet C.; Buguin A.; Talini L.; Silberzan P. Rectified Motion of Colloids in Asymmetrically Structured Channels. Phys. Rev. Lett. 2002, 88, 168301. 10.1103/PhysRevLett.88.168301. [DOI] [PubMed] [Google Scholar]
Huang L. R.; Cox E. C.; Austin R. H.; Sturm J. C. Tilted Brownian Ratchet for DNA Analysis. Anal. Chem. 2003, 75, 6963–6967 10.1021/ac0348524. [DOI] [PubMed] [Google Scholar]
Matthias S.; Muller F. Asymmetric Pores in a Silicon Membrane Acting as Massively Parallel Brownian Ratchets. Nature 2003, 424, 53–57 10.1038/nature01736. [DOI] [PubMed] [Google Scholar]
Mogilner A.; Oster G. Polymer Motors: Pushing out the Front and Pulling up the Back. Curr. Biol. 2003, 13, R721–R733 10.1016/j.cub.2003.08.050. [DOI] [PubMed] [Google Scholar]
Oster G.; Wang H. Rotary Protein Motors. Trends Cell Biol. 2003, 13, 114–121 10.1016/S0962-8924(03)00004-7. [DOI] [PubMed] [Google Scholar]
Kurzyński M.; Chełminiak P. Stochastic Action of Actomyosin Motor. Phys. A 2004, 336, 123–132 10.1016/j.physa.2004.01.017. [DOI] [Google Scholar]
de Souza Silva C. C.; Van de Vondel J.; Morelle M.; Moshchalkov V. V. Controlled Multiple Reversals of a Ratchet Effect. Nature 2006, 440, 651–654 10.1038/nature04595. [DOI] [PubMed] [Google Scholar]
Linke H.; Downton M. T.; Zuckermann M. J. Performance Characteristics of Brownian Motors. Chaos 2005, 15, 26111. 10.1063/1.1871432. [DOI] [PubMed] [Google Scholar]
Reimann P. Brownian Motors: Noisy Transport Far from Equilibrium. Phys. Rep. 2002, 361, 57–265 10.1016/S0370-1573(01)00081-3. [DOI] [Google Scholar]
Gabryś B. J.; Pesz K.; Bartkiewicz S. J. Brownian Motion, Molecular Motors and Ratchets. Phys. A 2004, 336, 112–122 10.1016/j.physa.2004.01.016. [DOI] [Google Scholar]
Mislow K. Stereochemical Consequences of Correlated Rotation in Molecular Propellers. Acc. Chem. Res. 1976, 9, 26–33 10.1021/ar50097a005. [DOI] [Google Scholar]
Rappoport Z.; Biali S. E. Sterically Crowded Stable Simple Enols. Acc. Chem. Res. 1988, 21, 442–449 10.1021/ar00156a002. [DOI] [Google Scholar]
Rappoport Z.; Biali S. E. Threshold Rotational Mechanisms and Enantiomerization Barriers of Polyarylvinyl Propellers. Acc. Chem. Res. 1997, 30, 307–314 10.1021/ar960216z. [DOI] [Google Scholar]
Wolf C.Dynamic Stereochemistry of Chiral Compounds; RSC Publishing: UK, 2008; Chapter 8, pp 399–443. [Google Scholar]
Gust D.; Mislow K. Analysis of Isomerization in Compounds Displaying Restricted Rotation of Aryl Groups. J. Am. Chem. Soc. 1973, 95, 1535–1547 10.1021/ja00786a031. [DOI] [Google Scholar]
Mislow K.; Gust D.; Finocchiaro P.; Boettcher R.. Stereochemical Correspondence Among Molecular Propellers. Stereochemistry I; Springer: Berlin, Heidelberg, 1974; Vol. 47, pp 1–28. [Google Scholar]
Katoono R.; Kawai H.; Fujiwara K.; Suzuki T. Dynamic Molecular Propeller: Supramolecular Chirality Sensing by Enhanced Chiroptical Response through the Transmission of Point Chirality to Mobile Helicity. J. Am. Chem. Soc. 2009, 131, 16896–16904 10.1021/ja906810b. [DOI] [PubMed] [Google Scholar]
Driesschaert B.; Robiette R.; Le Duff C. S.; Collard L.; Robeyns K.; Gallez B.; Marchand-Brynaert J. Configurationally Stable Tris(tetrathioaryl)methyl Molecular Propellers. Eur. J. Org. Chem. 2012, 6517–6525 10.1002/ejoc.201200801. [DOI] [Google Scholar]
Katoono R.; Kawai H.; Ohkita M.; Fujiwara K.; Suzuki T. A C(3)-symmetric Chiroptical Molecular Propeller Based on Hexakis(phenylethynyl)benzene with a Threefold Terephthalamide: Stereospecific Propeller Generation Through the Cooperative Transmission of Point Chiralities on the Host and Guest upon Complexation. Chem. Commun. 2013, 49, 10352–10354 10.1039/c3cc43571g. [DOI] [PubMed] [Google Scholar]
Finocchiaro P.; Gust D.; Mislow K. Structure and Dynamic Stereochemistry of Trimesitylmethane. I. Synthesis and Nuclear Magnetic Resonance Studies. J. Am. Chem. Soc. 1974, 96, 2165–2167 10.1021/ja00814a028. [DOI] [Google Scholar]
O̅ki M. Unusually High Barriers to Rotation Involving the Tetrahedral Carbon Atom. Angew. Chem., Int. Ed. Engl. 1976, 15, 87–93 10.1002/anie.197600871. [DOI] [Google Scholar]
Yamamoto G.; O̅ki M. Dual Mechanisms of the Aryl Group Rotation in 9-(3,5-dimethylbenzyl) Triptycene Derivatives. Chem. Lett. 1979, 1251–1254 10.1246/cl.1979.1251. [DOI] [Google Scholar]
Yamamoto G.; O̅ki M. Two Consecutive Gear Motions in Conformational Interconversion in 9-(2-methylbenzyl)triptycene Derivatives. Chem. Lett. 1979, 1255–1258 10.1246/cl.1979.1255. [DOI] [Google Scholar]
Yamaoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. XXXV. Stereodynamics of 9-(3,5-Dimethylbenzyl)triptycene Derivatives. Bull. Chem. Soc. Jpn. 1981, 54, 473–480 10.1246/bcsj.54.473. [DOI] [Google Scholar]
Yamamoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. XXXVI. Stereodynamics of 9-(2-MethylbenzyI)triptycene Derivatives. Bull. Chem. Soc. Jpn. 1981, 54, 481–487 10.1246/bcsj.54.481. [DOI] [Google Scholar]
Yamamoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. Part 46. Correlated Rotation in 9-(2,4,6-trimethylbenzyl)triptycenes. Direct and Roundabout Enantiomerization-diastereomerization Processes. J. Org. Chem. 1983, 48, 1233–1236 10.1021/jo00156a017. [DOI] [Google Scholar]
Yamamoto G. Molecular Gears with Two-toothed and Three-toothed Wheels. J. Mol. Struct. 1985, 126, 413–420 10.1016/0022-2860(85)80130-7. [DOI] [Google Scholar]
Yamamoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. LVII. Stereodynamics of 9-(2-Alkylphenoxy)-1,4-dimethyltriptycenes. Bull. Chem. Soc. Jpn. 1985, 58, 1953–1961 10.1246/bcsj.58.1953. [DOI] [Google Scholar]
Yamamoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. LIX. Stereodynamics of Singly peri-Substituted 9-(3,5-Dimethylphenoxy)triptycene Derivatives. Bull. Chem. Soc. Jpn. 1986, 59, 3597–3603 10.1246/bcsj.59.3597. [DOI] [Google Scholar]
Yamamoto G. Detailed Dynamic NMR Study of a Molecular Gear, 1-Methoxy-9-(3,5-dimethylbenzyl)triptycene. Bull. Chem. Soc. Jpn. 1989, 62, 4058–4060 10.1246/bcsj.62.4058. [DOI] [Google Scholar]
Hiizu Iwamura K. M. Stereochemical Consequences of Dynamic Gearing. Acc. Chem. Res. 1988, 21, 175–182 10.1021/ar00148a007. [DOI] [Google Scholar]
Kawada Y.; Iwamura H. Unconventional Synthesis and Conformational Flexibility of Bis(1-triptycyl) ether. J. Org. Chem. 1980, 45, 2548–2550 10.1021/jo01300a069. [DOI] [Google Scholar]
Kawada Y.; Iwamura H. Bis(4-chloro-1-triptycyl) ether. Separation of a Pair of Phase Isomers of Labeled Bevel Gears. J. Am. Chem. Soc. 1981, 103, 958–960 10.1021/ja00394a049. [DOI] [Google Scholar]
Kawada Y.; Iwamura H. Bis(4-chloro-1-triptycyl) ether. Separation of a Pair of Phase Isomers of Labeled Bevel Gears. Tetrahedron Lett. 1981, 22, 1533–1536 10.1016/S0040-4039(01)90370-3. [DOI] [Google Scholar]
Kawada Y.; Iwamura H. Correlated Rotation in Bis(9-triptycyl)methanes and Bis(9-triptycyl) Ethers. Separation and Interconversion of the Phase Isomers of Labeled Bevel Gears. J. Am. Chem. Soc. 1983, 105, 1449–1459 10.1021/ja00344a006. [DOI] [Google Scholar]
Kawada Y.; Okamoto Y.; Iwamura H. Correlated Internal Rotation in Bis(2,6-dichloro-9-triptycyl)methane. To what Extent can Phase Isomers be Separated and Identified?. Tetrahedron Lett. 1983, 24, 5359–5362 10.1016/S0040-4039(00)87868-5. [DOI] [Google Scholar]
Iwamura H.; Ito T.; Ito H.; Toriumi K.; Kawada Y.; Osawa E.; Fujiyoshi T.; Jaime C. Crystal and Molecular Structure of Bis(9-triptycyl) Ether. J. Am. Chem. Soc. 1984, 106, 4712–4717 10.1021/ja00329a013. [DOI] [Google Scholar]
Iwamura H. Molecular Design of Correlated Internal Rotation. J. Mol. Struct. 1985, 126, 401–412 10.1016/0022-2860(85)80129-0. [DOI] [Google Scholar]
Koga N.; Iwamura H. Barrier to Coupled Internal Rotation in Bis(9-triptycyl) Ether. Kinetics of Intramolecular Exciplex Formation in Racemic 2,3-Benzo-9-triptycyl 2-(N,N-dimethylaminomethyl)-9-triptycyl ether. J. Am. Chem. Soc. 1985, 107, 1426–1427 10.1021/ja00291a061. [DOI] [Google Scholar]
Koga N.; Iwamura H. A Kinetic Study of Coupled Internal Rotation in Racemic 2,3-Benzo-9-triptycyl 2-(dimethylaminomethyl)-9-triptycyl ether by Means of Exciplex Fluorescence Dynamics. Chem. Lett. 1986, 247–250 10.1246/cl.1986.247. [DOI] [Google Scholar]
Kawada Y.; Yamazaki H.; Koga G.; Murata S.; Iwamura H. Bis(9-triptycyl)amines, A Missing Link Between the Corresponding Methanes and Ethers. An Unconventional Synthesis and Influence of Nitrogen Configurational Inversion on the Coupled Disrotatory Trajectory. J. Org. Chem. 1986, 51, 1472–1477 10.1021/jo00359a016. [DOI] [Google Scholar]
Kawada Y.; Ishikawa J.; Yamazaki H.; Koga G.; Murata S.; Iwamura H. Bis(9-triptycyl)amines, A Missing Link Between the Corresponding Methanes and Ethers. An Unconventional Synthesis and Influence of Nitrogen Configurational Inversion on the Coupled Disrotatory Trajectory. Tetrahedron Lett. 1987, 28, 445–448 10.1016/S0040-4039(00)95752-6. [DOI] [Google Scholar]
Hounshell W. D.; Johnson C. A.; Guenzi A.; Cozzi F.; Mislow K. Sterochemical Consequences of Dynamic Gearing in Substituted bis (9-triptycyl) Methanes and Related Molecules. Proc. Natl. Acad. Sci. U. S. A. 1980, 77, 6961–6964 10.1073/pnas.77.12.6961. [DOI] [PMC free article] [PubMed] [Google Scholar]
Cozzi F.; Guenzi A.; Johnson C. A.; Mislow K. Stereoisomerism and Correlated Rotation in Molecular Gear Systems. Residual Diastereomers of Bis(2,3-dimethyl-9-triptycyl)methane. J. Am. Chem. Soc. 1981, 103, 957–958 10.1021/ja00394a048. [DOI] [Google Scholar]
Johnson C. A.; Guenzi A.; Mislow K. Restricted Gearing and Residual Stereoisomerism in Bis(1,4-dimethyl-9-triptycyl)methane. J. Am. Chem. Soc. 1981, 103, 6240–6242 10.1021/ja00410a054. [DOI] [Google Scholar]
Johnson C. A.; Guenzi A.; Nachbar R. B. Jr.; Blount J. F.; Wennerstroem O.; Mislow K. Crystal and Molecular Structure of Bis(9-triptycyl) ketone and Bis(9-triptycyl)methane. J. Am. Chem. Soc. 1982, 104, 5163–5168 10.1021/ja00383a028. [DOI] [Google Scholar]
Buergi H. B.; Hounshell W. D.; Nachbar J. R. B.; Mislow K. Conformational Dynamics of Propane, di-tert-Butylmethane, and Bis(9-triptycyl)methane. An Analysis of the Symmetry of Two Threefold Rotors on a Rigid Frame in Terms of Nonrigid Molecular Structure and Energy Hypersurfaces. J. Am. Chem. Soc. 1983, 105, 1427–1438 10.1021/ja00344a004. [DOI] [Google Scholar]
Guenzi A.; Johnson C. A.; Cozzi F.; Mislow K. Dynamic Gearing and Residual Stereoisomerism in Labeled Bis(9-triptycyl)methane and Related Molecules. Synthesis and Stereochemistry of Bis(2,3-dimethyl-9-triptycyl)methane, Bis(2,3-dimethyl-9-triptycyl)carbinol, and Bis(1,4-dimethyl-9-triptycyl) Methane. J. Am. Chem. Soc. 1983, 105, 1438–1448 10.1021/ja00344a005. [DOI] [Google Scholar]
Koga N.; Kawada Y.; Iwamura H. Recognition of the Phase Relationship between Remote Substituents in 9,10-Bis(3-chloro-9-triptycycloxy)triptycene Molecules Undergoing Rapid Internal Rotation Cooperatively. J. Am. Chem. Soc. 1983, 105, 5498–5499 10.1021/ja00354a063. [DOI] [Google Scholar]
Yamamoto G. Molecular Gears with Two-toothed and Three-thoothed Wheels. J. Mol. Struct. 1985, 126, 413–420 10.1016/0022-2860(85)80130-7. [DOI] [Google Scholar]
Yamamoto G. Dynamic Stereochemistry of Molecular Geras, 9-Benzyltriptycene and 9-Phenoxytriptycene, Studied by ¹³C Dynamic NMR Spectroscopy and Molecular Mechanics Calculations. Tetrahedron 1990, 46, 2761–2772 10.1016/S0040-4020(01)88370-8. [DOI] [Google Scholar]
Chance J. M.; Geiger J. H.; Okamoto Y.; Aburatani R.; Mislow K. Stereochemical Consequences of a Parity Restriction on Dynamic Gearing in Tris(9-triptycyl)germanium Chloride and Tris(9-triptycyl)cyclopropenium Perchlorate. J. Am. Chem. Soc. 1990, 112, 3540–3547 10.1021/ja00165a044. [DOI] [Google Scholar]
Kawada Y.; Sakai H.; Oguri M.; Koga G. Preparation of an Dynamic Gearing in cis-1,2-Bis(9-triptycyl)ethylene. Tetrahedron Lett. 1994, 35, 139–142 10.1016/0040-4039(94)88184-7. [DOI] [Google Scholar]
Nikitin K.; Müller-Bunz H.; Ortin Y.; Risse W.; McGlinchey M. J. Twin Triptycyl Spinning Tops: A Simple Case of Molecular Gearing with Dynamic C₂ Symmetry. Eur. J. Org. Chem. 2008, 2008, 3079–3084 10.1002/ejoc.200800202. [DOI] [Google Scholar]
Frantz D. K.; Linden A.; Baldridge K. K.; Siegel J. S. Molecular Spur Gears Comprising Triptycene Rotators and Bibenzimidazole-based Stators. J. Am. Chem. Soc. 2012, 134, 1528–1535 10.1021/ja2063346. [DOI] [PubMed] [Google Scholar]
Stevens A. M.; Richards C. J. A Metallocene Molecular Gear. Tetrahedron Lett. 1997, 38, 7805–7808 10.1016/S0040-4039(97)10042-9. [DOI] [Google Scholar]
Brydges S.; Harrington L. E.; McGlinchey M. J. Sterically Hindered Organometallics: Multi-n-rotor (n = 5, 6 and 7) Molecular Propellers and the Search for Correlated Rotations. Coord. Chem. Rev. 2002, 233, 75–105 10.1016/S0010-8545(02)00098-X. [DOI] [Google Scholar]
Kuttenberger M.; Frieser M.; Hofweber M.; Mannschreck A. Axially Chiral Thioamides of Acrylic Acid: Correlated and Uncorrelated Internal Rotations. Tetrahedron: Asymmetry 1998, 9, 3629–3645 10.1016/S0957-4166(98)00373-5. [DOI] [Google Scholar]
Clayden J.; Pink J. H. Concerted Rotation in a Tertiary Aromatic Amide: Towards a Simple Molecular Gear. Angew. Chem., Int. Ed. 1998, 37, 1937–1939. [DOI] [Google Scholar]
Johnston E. R.; Fortt R.; Barborak J. C. Correlated Rotation in a Conformationally Restricted Amide. Magn. Reson. Chem. 2000, 38, 932–936. [DOI] [Google Scholar]
Bragg R. A.; Clayden J. Using Symmetry to Monitor Geared Bond Rotation in Aromatic Amides by Dynamic NMR. Org. Lett. 2000, 2, 3351–3354 10.1021/ol0064462. [DOI] [PubMed] [Google Scholar]
Bragg R. A.; Clayden J.; Morris G. A.; Pink J. H. Stereodynamics of Bond Rotation in Tertiary Aromatic Amides. Chem. - Eur. J. 2002, 8, 1279–1289. [DOI] [PubMed] [Google Scholar]
Hellwinkel D.; Melan M.; Degel C. R. Die Stereochemie ortho-Substituierter Triphenylamin-derivate. Tetrahedron 1973, 29, 1895–1907 10.1016/S0040-4020(01)83217-8. [DOI] [Google Scholar]
Hummel J. P.; Gust D.; Mislow K. Mechanism of Stereoisomerization in Triarylboranes. J. Am. Chem. Soc. 1974, 96, 3679–3681 10.1021/ja00818a068. [DOI] [Google Scholar]
Wille E. E.; Stephenson D. S.; Capriel P.; Binsch G. Iterative Analysis of Exchange-Broadened NMR Band Shapes. The Mechanism of Correlated Rotations in Triaryl Derivatives of Phosphorus and Arsenic. J. Am. Chem. Soc. 1982, 104, 405–415 10.1021/ja00366a006. [DOI] [Google Scholar]
Clegg W.; Lockhart J. C.; McDonnell M. B. Comparison of the Steric Barriers in Three- and Two-bladed Propeller Crowns. J. Chem. Soc., Perkin Trans. 1 1985, 1019–1023 10.1039/p19850001019. [DOI] [Google Scholar]
Berg U.; Liljefors T.; Roussel C.; Sandstroem J. Steric Interplay Between Alkyl Groups Bonded to Planar Frameworks. Acc. Chem. Res. 1985, 18, 80–86 10.1021/ar00111a003. [DOI] [Google Scholar]
Biali S. E.; Rappoport Z. Stable Simple Enols. 8.′ Synthesis and Keto Enol Equilibria of the Elusive 2,2-Dimesitylethanal and 1,2,2-Trimesitylethanone. Conformations of 1,2,2-Trimesitylethanone and 1,2,2-Trimesitylethanol. J. Am. Chem. Soc. 1985, 107, 1007–1015 10.1021/ja00290a043. [DOI] [Google Scholar]
Hansen P. E.; Spanget-Lansen J.; Laali K. K. Conformational Studies of Phenyl and (1-Pyrenyl) Triarylmethylcarbenium Ions: Semiempirical Calculations and NMR Investigations under Stable Ion Conditions. J. Org. Chem. 1998, 63, 1827–1835 10.1021/jo9715480. [DOI] [Google Scholar]
Yamaguchi S.; Akiyama S.; Tamao K. Synthesis, Structures, Photophysical Properties, and Dynamic Stereochemistry of Tri(9-anthryl)silane Derivatives. Organometallics 1998, 17, 4347–4352 10.1021/om9804778. [DOI] [Google Scholar]
Sedo J.; Ventosa N.; Molins M. A.; Pons M.; Rovira C.; Veciana J. Stereoisomerism of Molecular Multipropellers. 2. Dynamic Stereochemistry of Bis- and Tris-Triaryl Systems. J. Org. Chem. 2001, 66, 1579–1589 10.1021/jo000474g. [DOI] [PubMed] [Google Scholar]
Grilli S.; Lunazzi L.; Mazzanti A. Conformational Studies by Dynamic NMR. 83.1 Correlated Enantiomerization Pathways for the Stereolabile Propeller Antipodes of Dimesityl Substituted Ethanol and Ethers. J. Org. Chem. 2001, 66, 5853–5858 10.1021/jo010420m. [DOI] [PubMed] [Google Scholar]
Benincori T.; Celentano G.; Pilati T.; Ponti A.; Rizzo S.; Sannicolò F. Configurationally Stable Molecular Propellers: First Resolution of Residual Enantiomers. Angew. Chem., Int. Ed. 2006, 45, 6193–6196 10.1002/anie.200601869. [DOI] [PubMed] [Google Scholar]
Bulo R. E.; Allaart F.; Ehlers A. W.; de Kanter F. J. J.; Schakel M.; Lutz M.; Spek A. L.; Lammertsma K. Circumambulatory Rearrangement with Characteristics of a 2:1 Covalent Molecular Bevel Gear. J. Am. Chem. Soc. 2006, 128, 12169–12173 10.1021/ja0627895. [DOI] [PubMed] [Google Scholar]
Romeo R.; Carnabuci S.; Fenech L.; Plutino M. R.; Albinati A. Overcrowded Organometallic Platinum(II) Complexes That Behave as Molecular Gears. Angew. Chem., Int. Ed. 2006, 45, 4494–4498 10.1002/anie.200600827. [DOI] [PubMed] [Google Scholar]
Peck T.-G.; Lai Y.-H. Conformational Isomerism in 1,2-Di-o-tolylnaphthalenes: Selective Rotation of the 2-Aryl Ring. Tetrahedron 2009, 65, 3664–3667 10.1016/j.tet.2009.02.068. [DOI] [Google Scholar]
Mati I. K.; Cockroft S. L. Molecular Balances for Quantifying Non-covalent Interactions. Chem. Soc. Rev. 2010, 39, 4195–4205 10.1039/b822665m. [DOI] [PubMed] [Google Scholar]
Hiraoka S.; Harano K.; Tanaka T.; Shiro M.; Shionoya M. Quantitative Formation of Sandwich-shaped Trinuclear Silver(I) Complexes and Dynamic Nature of Their P ≤ > M Flip Motion in Solution. Angew. Chem., Int. Ed. 2003, 42, 5182–5185 10.1002/anie.200351068. [DOI] [PubMed] [Google Scholar]
Hiraoka S.; Shiro M.; Shionoya M. Heterotopic Assemblage of Two Different Disk-Shaped Ligands through Trinuclear Silver (I) Complexation: Ligand Exchange-Driven Molecular Motion. J. Am. Chem. Soc. 2004, 126, 1214–1218 10.1021/ja036388q. [DOI] [PubMed] [Google Scholar]
Hiraoka S.; Okuno E.; Tanaka T.; Shiro M.; Shionoya M. Ranging Correlated Motion (1.5 nm) of Two Coaxially Arranged Rotors Mediated by Helix Inversion of a Supramolecular Transmitter. J. Am. Chem. Soc. 2008, 130, 9089–9098 10.1021/ja8014583. [DOI] [PubMed] [Google Scholar]
Hiraoka S.; Hirata K.; Shionoya M. A Molecular Ball Bearing Mediated by Multiligand Exchange in Concert. Angew. Chem., Int. Ed. 2004, 43, 3814–3818 10.1002/anie.200453753. [DOI] [PubMed] [Google Scholar]
Okuno E.; Hiraoka S.; Shionoya M. A Synthetic Approach to a Molecular Crank Mechanism: Toward Intramolecular Motion Transformation Between Rotation and Translation. Dalton Trans. 2010, 39, 4107–4116 10.1039/b926154k. [DOI] [PubMed] [Google Scholar]
Liu S.; Kondratuk D. V.; Rousseaux S. A.; Gil-Ramirez G.; O’Sullivan M. C.; Cremers J.; Claridge T. D.; Anderson H. L. Caterpillar Track Complexes in Template-directed Synthesis and Correlated Molecular Motion. Angew. Chem., Int. Ed. 2015, 54, 5355–5359 10.1002/anie.201412293. [DOI] [PMC free article] [PubMed] [Google Scholar]
Kelly T. R.; Bowyer M. C.; Bhaskar K. V.; Bebbington D.; Garcia A.; Lang F.; Kim M. H.; Jette M. P. A Molecular Brake. J. Am. Chem. Soc. 1994, 116, 3657–3658 10.1021/ja00087a085. [DOI] [Google Scholar]
Kelly T. R. Progress Toward a Rationally Designed Molecular Motor. Acc. Chem. Res. 2001, 34, 514–522 10.1021/ar000167x. [DOI] [PubMed] [Google Scholar]
Sestelo J. P.; Kelly T. R. A Prototype of a Rationally Designed Chemically Powered Brownian Motor. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 337–343 10.1007/s003390201328. [DOI] [Google Scholar]
Jog P. V.; Brown R. E.; Bates D. K. A Redox-Mediated Molecular Brake: Dynamic NMR Study of 2-[2-(Methylthio)phenyl]isoindolin-1-one and S-Oxidized Counterparts. J. Org. Chem. 2003, 68, 8240–8243 10.1021/jo034613g. [DOI] [PubMed] [Google Scholar]
Dial B. E.; Pellechia P. J.; Smith M. D.; Shimizu K. D. Proton Grease: An Acid Accelerated Molecular Rotor. J. Am. Chem. Soc. 2012, 134, 3675–3678 10.1021/ja2120184. [DOI] [PubMed] [Google Scholar]
Dial B. E.; Rasberry R. D.; Bullock B. N.; Smith M. D.; Pellechia P. J.; Profeta S.; Shimizu K. D. Guest-Accelerated Molecular Rotor. Org. Lett. 2011, 13, 244–247 10.1021/ol102659n. [DOI] [PubMed] [Google Scholar]
Kanazawa H.; Higuchi M.; Yamamoto K. An Electric Cyclophane: Cavity Control Based on the Rotation of a Paraphenylene by Redox Switching. J. Am. Chem. Soc. 2005, 127, 16404–16405 10.1021/ja055681i. [DOI] [PubMed] [Google Scholar]
Tomohiro Y.; Satake A.; Kobuke Y. Synthesis of Bipyridylene-Bridged Bisporphyrin by Nickel-Mediated Coupling Reaction: ON–OFF Control of Cofacial Porphyrin Unit by Reversible Complexation. J. Org. Chem. 2001, 66, 8442–8446 10.1021/jo015852b. [DOI] [PubMed] [Google Scholar]
Zehm D.; Fudickar W.; Linker T. Molecular Switches Flipped by Oxygen. Angew. Chem., Int. Ed. 2007, 46, 7689–7692 10.1002/anie.200700443. [DOI] [PubMed] [Google Scholar]
Kelly T. R.; Tellitu I.; Sestelo J. P. In Search of Molecular Ratchets. Angew. Chem., Int. Ed. Engl. 1997, 36, 1866–1868 10.1002/anie.199718661. [DOI] [Google Scholar]
Kelly T. R.; Sestelo J. P.; Tellitu I. New Molecular Devices: In Search of a Molecular Ratchet. J. Org. Chem. 1998, 63, 3655–3665 10.1021/jo9723218. [DOI] [Google Scholar]
Sebastian K. L. Molecular Ratchets: Verification of the Principle of Detailed Balance and the Second Law of Dynamics. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 2000, 61, 937–939 10.1103/PhysRevE.61.937. [DOI] [PubMed] [Google Scholar]
Davis A. P. Tilting at Windmills? The Second Law Survives. Angew. Chem., Int. Ed. 1998, 37, 909–910. [DOI] [PubMed] [Google Scholar]
Kelly T. R.; De Silva H.; Silva R. A. Unidirectional Rotary Motion in a Molecular System. Nature 1999, 401, 150–152 10.1038/43639. [DOI] [PubMed] [Google Scholar]
Kelly T. R.; Silva R. A.; Silva H. D.; Jasmin S.; Zhao Y. A Rationally Designed Prototype of a Molecular Motor. J. Am. Chem. Soc. 2000, 122, 6935–6949 10.1021/ja001048f. [DOI] [PubMed] [Google Scholar]
Kelly T. R.; Cai X.; Damkaci F.; Panicker S. B.; Tu B.; Bushell S. M.; Cornella I.; Piggott M. J.; Salives R.; Cavero M. Progress Toward a Rationally Designed, Chemically Powered Rotary Molecular Motor. J. Am. Chem. Soc. 2007, 129, 376–386 10.1021/ja066044a. [DOI] [PubMed] [Google Scholar]
Mock W. L.; Ochwat K. J. Theory and Example of a Small-molecule Motor. J. Phys. Org. Chem. 2003, 16, 175–182 10.1002/poc.591. [DOI] [Google Scholar]
Dahl B. J.; Branchaud B. P. Synthesis and Characterization of a Functionalized Chiral Biaryl Capable of Exhibiting Unidirectional Bond Rotation. Tetrahedron Lett. 2004, 45, 9599–9602 10.1016/j.tetlet.2004.10.147. [DOI] [Google Scholar]
Lin Y.; Dahl B. J.; Branchaud B. P. Net Directed 180° Aryl–aryl Bond Rotation in a Prototypical Achiral Biaryl Lactone Synthetic Molecular Motor. Tetrahedron Lett. 2005, 46, 8359–8362 10.1016/j.tetlet.2005.09.151. [DOI] [Google Scholar]
Fletcher S. P.; Dumur F.; Pollard M. M.; Feringa B. L. A Reversible, Unidirectional Molecular Rotary Motor Driven by Chemical Energy. Science 2005, 310, 80–82 10.1126/science.1117090. [DOI] [PubMed] [Google Scholar]
Siegel J. Chemistry. Inventing the Nanomolecular Wheel. Science 2005, 310, 63–64 10.1126/science.1118765. [DOI] [PubMed] [Google Scholar]
Tashiro K.; Konishi K.; Aida T. Enantiomeric Resolution of Chiral Metallobis(porphyrin)s: Studies on Rotatbility of Electronically Coupled Porphyrin Ligands. Angew. Chem., Int. Ed. Engl. 1997, 36, 856–858 10.1002/anie.199708561. [DOI] [Google Scholar]
Tashiro K.; Fujiwara T.; Konishi K.; Aida T. Chem. Commun. 1998, 1121–1122 10.1039/a801350k. [DOI] [Google Scholar]
Ikeda M.; Takeuchi M.; Shinkai S.; Tani F.; Naruta Y. Synthesis of New Diaryl-Substituted Triple-Decker and Tetraaryl-substituted Double-Decker Lanthanum(III) Porphyrins and Their Porphyrin Ring Rotational Speed as Compared with that of Double-Decker Cerium(IV) Porphyrins. Bull. Chem. Soc. Jpn. 2001, 74, 739–746 10.1246/bcsj.74.739. [DOI] [Google Scholar]
Tashiro K.; Konishi K.; Aida T. Metal Bisporphyrin Double-decker Complexes as Redox-Responsive Rotating Modules. Studies on Ligand Rotation Activities of the Reduced and Oxidized Forms Using Chirality as a Probe. J. Am. Chem. Soc. 2000, 122, 7921–7926 10.1021/ja000356a. [DOI] [Google Scholar]
Buchler J. W.; Decian A.; Fischer J.; Hammerschmitt P.; Loffler J.; Scharbert B.; Weiss R. Metal-Complexes with Tetrapyrrole Ligands 0.54. Synthesis, Spectra, Structure, and Redox Properties of Cerium(Iv) Bisporphyrinates with Identical and Different Porphyrin Rings in the Sandwich System. Chem. Ber. 1989, 122, 2219–2228 10.1002/cber.19891221203. [DOI] [Google Scholar]
Takeuchi M.; Imada I.; Shinkai S. A Strong Positive Allosteric Effect in the Molecular Recognition of Dicarboxylic Acids by a Cerium(IV)Bis[tetrakis(4-pyridyl)-porphyrinte] Double Decker. Angew. Chem., Int. Ed. 1998, 37, 2096–2099. [DOI] [PubMed] [Google Scholar]
Sugasaki A.; Ikeda M.; Takeuchi M.; Robertson A.; Shinkai S. Efficient Chirality Transcription Utilizing a Cerium(IV) Double Decker Porphyrin: A Prototype for Development of a Molecular Memory Systems. J. Chem. Soc., Perkin Trans. 1 1999, 3259–3264 10.1039/a904890a. [DOI] [Google Scholar]
Yamamoto M.; Sugasaki A.; Ikeda M.; Takeuchi M.; Frimat K.; James T. D.; Shinkai S. Efficient Anion Binding to Cerium(IV)Bis(porphyrinate) Double Decker Utilizing Positive Homotropic Allosterim. Chem. Lett. 2001, 520–521 10.1246/cl.2001.520. [DOI] [Google Scholar]
Robertson A.; Ikeda M.; Takeuchi M.; Shinkai S. Allosteric Binding of K⁺ to Crown Ether Macrocycles Appended to a Lanthanum Double Decker System. Bull. Chem. Soc. Jpn. 2001, 74, 883–888 10.1246/bcsj.74.883. [DOI] [Google Scholar]
Sugasaki A.; Ikeda M.; Takeuchi M.; Shinkai S. Novel Oligosaccharide Binding to the Cerium(IV) Bis(porphyrinoate) Double Decker: Effective Amplification of a Binding Signal through Positive Homotropic Allosterism. Angew. Chem., Int. Ed. 2000, 39, 3839–3842. [DOI] [PubMed] [Google Scholar]
Ikeda M.; Shinkai S.; Osuka A. Meso–meso-linked Porphyrin Dimer as a Novel Scaffold for the Selective Binding of Oligosaccharides. Chem. Commun. 2000, 1047–1048 10.1039/b003365k. [DOI] [Google Scholar]
Sugasaki A.; Ikeda M.; Takeuchi M.; Koumoto K.; Shinkai S. The First Example of Positive Allosterism in an Aqueous Saccharide-Binding System Designed on a Ce(IV) Bis(porphyrinate) Double Decker Scaffold. Tetrahedron 2000, 56, 4717–4723 10.1016/S0040-4020(00)00395-1. [DOI] [Google Scholar]
Ikeda M.; Tanida T.; Takeuchi M.; Shinkai S. Allosteric Silver (I) Ion Binding with Peripheral π Clefts of a Ce (IV) Double Decker Porphyrin. Org. Lett. 2000, 2, 1803–1805 10.1021/ol005807a. [DOI] [PubMed] [Google Scholar]
Ikeda M.; Takeuchi M.; Shinkai S.; Tani F.; Naruta Y.; Sakamoto S.; Yamaguchi K. Allosteric Binding of a Ag⁺ Ion to Cerium (IV) Bis-porphyrinates Enhances the Rotational Activity of Porphyrin Ligands. Chem. - Eur. J. 2002, 8, 5541–5550. [DOI] [PubMed] [Google Scholar]
Kubo Y.; Ikeda M.; Sugasaki A.; Takeuchi M.; Shinkai S. A Porphyrin Tetramer for a Positive Homotropic Allosteric Recognition System: Efficient Binding Information Transduction Through Butadiynyl Axis Rotation. Tetrahedron Lett. 2001, 42, 7435–7438 10.1016/S0040-4039(01)01546-5. [DOI] [Google Scholar]
Shinkai S.; Ikeda M.; Sugasaki A.; Takeuchi M. Positive Allosteric Systems Designed on Dynamic Supramolecular Scaffolds: Toward Switching and Amplification of Guest Affinity and Selectivity. Acc. Chem. Res. 2001, 34, 494–503 10.1021/ar000177y. [DOI] [PubMed] [Google Scholar]
Takeuchi M.; Ikeda M.; Sugasaki A.; Shinkai S. Molecular Design of Artificial Molecular and Ion Recognition Systems with Allosteric Guest Responses. Acc. Chem. Res. 2001, 34, 865–873 10.1021/ar0000410. [DOI] [PubMed] [Google Scholar]
Ayabe M.; Ikeda A.; Kubo Y.; Takeuchi M.; Shinkai S. A Dendritic Porphyrin Receptor for C₆₀ Which Features a Profound Positive Allosteric Effect. Angew. Chem., Int. Ed. 2002, 41, 2790–2792. [DOI] [PubMed] [Google Scholar]
Kubo Y.; Sugasaki A.; Ikeda M.; Sugiyasu K.; Sonoda K.; Ikeda A.; Takeuchi M.; Shinkai S. Cooperative C-60 Binding to a Porphyrin Tetramer Arranged Around a p-Terphenyl Axis in 1:2 Host-guest Stoichiometry. Org. Lett. 2002, 4, 925–928 10.1021/ol017299q. [DOI] [PubMed] [Google Scholar]
Ercolani G. The Origin of Cooperativity in Double-Wheel Receptors. Freezing of Internal Rotation or Ligand-Induced Torsional Strain?. Org. Lett. 2005, 7, 803–805 10.1021/ol047620f. [DOI] [PubMed] [Google Scholar]
Shinkai S.; Takeuchi M. Molecular Design of Synthetic Receptors with Dynamic, Imprinting, and Allosteric Functions. Bull. Chem. Soc. Jpn. 2005, 78, 40–51 10.1246/bcsj.78.40. [DOI] [PubMed] [Google Scholar]
Ikeda T.; Tsukahara T.; Iino R.; Takeuchi M.; Noji H. Motion Capture and Manipulation of a Single Synthetic Molecular Rotor by Optical Microscopy. Angew. Chem., Int. Ed. 2014, 53, 10082–10085 10.1002/anie.201403091. [DOI] [PubMed] [Google Scholar]
Tanaka H.; Ikeda T.; Takeuchi M.; Sada K.; Shinkai S.; Kawai T. Molecular Rotation in Self-Assembled Multidecker Porphyrin Complexes. ACS Nano 2011, 5, 9575–9582 10.1021/nn203773p. [DOI] [PubMed] [Google Scholar]
Ogi S.; Ikeda T.; Wakabayashi R.; Shinkai S.; Takeuchi M. A Bevel-gear-shaped Rotor Bearing a Double-decker Porphyrin Complex. Chem. - Eur. J. 2010, 16, 8285–8290 10.1002/chem.201000276. [DOI] [PubMed] [Google Scholar]
Ogi S.; Ikeda T.; Wakabayashi R.; Shinkai S.; Takeuchi M. Mechanically Interlocked Porphyrin Gears Propagating Two Different Rotational Frequencies. Eur. J. Org. Chem. 2011, 2011, 1831–1836 10.1002/ejoc.201001656. [DOI] [Google Scholar]
Ogi S.; Ikeda T.; Takeuchi M. Synthetic Molecular Gear Based on Double-Decker Porphyrin Complexes. J. Inorg. Organomet. Polym. Mater. 2013, 23, 193–199 10.1007/s10904-012-9749-x. [DOI] [Google Scholar]
Shibata M.; Tanaka S.; Ikeda T.; Shinkai S.; Kaneko K.; Ogi S.; Takeuchi M. Stimuli-Responsive Folding and Unfolding of a Polymer Bearing Multiple Cerium(IV) Bis(porphyrinate) Joints: Mechano-imitation of the Action of a Folding Ruler. Angew. Chem., Int. Ed. 2013, 52, 397–400 10.1002/anie.201205584. [DOI] [PubMed] [Google Scholar]
Hiraoka S.; Hisanaga Y.; Shiro M.; Shionoya M. A Molecular Double Ball Bearing: An Ag^I–Pt^II Dodecanuclear Quadruple-Decker Complex with Three Rotors. Angew. Chem., Int. Ed. 2010, 49, 1669–1673 10.1002/anie.200905947. [DOI] [PubMed] [Google Scholar]
Bohn R. K.; Haaland A. On the Molecular Structure of Ferrocene, Fe(C₅H₅)₂. J. Organomet. Chem. 1966, 5, 470–476 10.1016/S0022-328X(00)82382-7. [DOI] [Google Scholar]
Wang X. B.; Dai B.; Woo H. K.; Wang L. S. Intramolecular Rotation Through Proton Transfer: [Fe(η⁵-C₅H₄CO₂-)₂] versus [(η⁵-C₅H₄CO₂-)Fe(η⁵-C₅H₄CO₂H)]. Angew. Chem., Int. Ed. 2005, 44, 6022–6024 10.1002/anie.200501564. [DOI] [PubMed] [Google Scholar]
Crowley J. D.; Steele I. M.; Bosnich B. Protonmotive Force: Development of Electrostatic Drivers for Synthetic Molecular Motors. Chem. - Eur. J. 2006, 12, 8935–8951 10.1002/chem.200500519. [DOI] [PubMed] [Google Scholar]
Iordache A.; Oltean M.; Milet A.; Thomas F.; Baptiste B.; Saint-Aman E.; Bucher C. Redox Control of Rotary Motions in Ferrocene-based Elemental Ball Bearings. J. Am. Chem. Soc. 2012, 134, 2653–2671 10.1021/ja209766e. [DOI] [PubMed] [Google Scholar]
Fukino T.; Joo H.; Hisada Y.; Obana M.; Yamagishi H.; Hikima T.; Takata M.; Fujita N.; Aida T. Manipulation of Discrete Nanostructures by Selective Modulation of Noncovalent Forces. Science 2014, 344, 499–504 10.1126/science.1252120. [DOI] [PubMed] [Google Scholar]
Warren L. F. Jr.; Hawthorne M. F. The Chemistry of the Bis[π-(3)-1,2-dicarbollyl] Metalates of Nickel and Palladium. J. Am. Chem. Soc. 1970, 92, 1157–1173 10.1021/ja00708a009. [DOI] [Google Scholar]
St. Clair D.; Zalkin A.; Templeton D. H. The Crystal Structure of 3,3′-commo-Bis[undecahydro-1,2-dicarba-3-nickela-closo-dodecaborane], a Nickel(IV) Complex of the Dicarbollide Ion. J. Am. Chem. Soc. 1970, 92, 1173–1179 10.1021/ja00708a010. [DOI] [Google Scholar]
Gold K.; Churchill M. R. The Crystal Structure and Molecular Configuration of an Asymmetric 1,2-Dimethyl-1,2-dicarbollide Complex of Nickel, Racemic (3,4′)-[(CH₈)₂B₉C₂H₉]₂Ni. J. Am. Chem. Soc. 1970, 92, 1180–1187 10.1021/ja00708a011. [DOI] [Google Scholar]
Hawthorne M. F.; Dunks G. B. Metallocarboranes That Exhibit Novel Chemical Features: A Virtually Unlimited Variety of Structural and Dynamic Features are Observed in Metallocarborane Chemistry. Science 1972, 178, 462–471 10.1126/science.178.4060.462. [DOI] [PubMed] [Google Scholar]
Hawthorne M. F.; Zink J. I.; Skelton J. M.; Bayer M. J.; Liu C.; Livshits E.; Baer R.; Neuhauser D. Electrical or Photocontrol of the Rotary Motion of a Metallacarborane. Science 2004, 303, 1849–1851 10.1126/science.1093846. [DOI] [PubMed] [Google Scholar]
Rebek J. Binding Forces, Equilibria and Rates: New Models for Enzymic Catalysis. Acc. Chem. Res. 1984, 17, 258–264 10.1021/ar00103a006. [DOI] [Google Scholar]
Rebek J.; Trend J. E.; Wattley R. V.; Chakravorti S. Allosteric Effects in Organic Chemistry. Site-specific Binding. J. Am. Chem. Soc. 1979, 101, 4333–4337 10.1021/ja00509a047. [DOI] [Google Scholar]
Rebek J.; Wattley R. V. Allosteric Effects. Remote Control of Ion Transport Selectivity. J. Am. Chem. Soc. 1980, 102, 4853–4854 10.1021/ja00534a058. [DOI] [Google Scholar]
Rebek J.; Costello T.; Marshall L.; Wattley R.; Gadwood R. C.; Onan K. Allosteric Effects in Organic Chemistry: Binding Cooperativity in a Model for Subunit Interactions. J. Am. Chem. Soc. 1985, 107, 7481–7487 10.1021/ja00311a043. [DOI] [Google Scholar]
van Veggel F. C. J. M.; Verboom W.; Reinhoudt D. N. Metallomacrocycles: Supramolecular Chemistry with Hard and Soft Metal Cations in Action. Chem. Rev. 1994, 94, 279–299 10.1021/cr00026a001. [DOI] [Google Scholar]
Linton B.; Hamilton A. D. Formation of Artificial Receptors by Metal-Templated Self-Assembly. Chem. Rev. 1997, 97, 1669–1680 10.1021/cr960375w. [DOI] [PubMed] [Google Scholar]
Robertson A.; Shinkai S. Cooperative Binding in Selective Sensors, Catalysts and Actuators. Coord. Chem. Rev. 2000, 205, 157–199 10.1016/S0010-8545(00)00243-5. [DOI] [Google Scholar]
Shinkai S.; Ikeda M.; Sugasaki A.; Takeuchi M. Positive Allosteric Systems Designed on Dynamic Supramolecular Scaffolds: Toward Switching and Amplification of Guest Affinity and Selectivity. Acc. Chem. Res. 2001, 34, 494–503 10.1021/ar000177y. [DOI] [PubMed] [Google Scholar]
Kovbasyuk L.; Krämer R. Allosteric Supramolecular Receptors and Catalysts. Chem. Rev. 2004, 104, 3161–3188 10.1021/cr030673a. [DOI] [PubMed] [Google Scholar]
Chong Y. S.; Smith M. D.; Shimizu K. D. A Conformationally Programmable Ligand. J. Am. Chem. Soc. 2001, 123, 7463–7464 10.1021/ja0158713. [DOI] [PubMed] [Google Scholar]
Degenhardt C. F.; Lavin J. M.; Smith M. D.; Shimizu K. D. Conformationally Imprinted Receptors: Atropisomers with “Write”, “Save”, and “Erase” Recognition Properties. Org. Lett. 2005, 7, 4079–4081 10.1021/ol051325t. [DOI] [PubMed] [Google Scholar]
Leighton P.; Sanders J. K. M. A Molecular Switch for Control of Conformation: Strained Intramolecular Co-ordination in 4,4′-Bipyridyl-capped Zinc Porphyrins. J. Chem. Soc., Chem. Commun. 1984, 854–856 10.1039/c39840000854. [DOI] [Google Scholar]
Abraham R. J.; Leighton P.; Sanders J. K. M. = Coordination Chemistry and Geometries of Some 4,4′-Bipyridyl-capped Porphyrins. Proton- and Ligand-induced Switching of Conformations. J. Am. Chem. Soc. 1985, 107, 3472–3478 10.1021/ja00298a012. [DOI] [Google Scholar]
Mendez-Arroyo J.; Barroso-Flores J.; Lifschitz A. M.; Sarjeant A. A.; Stern C. L.; Mirkin C. A. A Multi-state, Allosterically-regulated Molecular Receptor with Switchable Selectivity. J. Am. Chem. Soc. 2014, 136, 10340–10348 10.1021/ja503506a. [DOI] [PubMed] [Google Scholar]
Kennedy R. D.; Machan C. W.; McGuirk C. M.; Rosen M. S.; Stern C. L.; Sarjeant A. A.; Mirkin C. A. General Strategy for the Synthesis of Rigid Weak-link Approach Platinum(II) Complexes: Tweezers, Triple-layer Complexes, and Macrocycles. Inorg. Chem. 2013, 52, 5876–5888 10.1021/ic302855f. [DOI] [PubMed] [Google Scholar]
Kuwabara J.; Yoon H. J.; Mirkin C. A.; DiPasquale A. G.; Rheingold A. L. Pseudo-allosteric Regulation of the Anion Binding Affinity of a Macrocyclic Coordination Complex. Chem. Commun. 2009, 4557–4559 10.1039/b905150c. [DOI] [PubMed] [Google Scholar]
Shinkai S.; Nakaji T.; Ogawa T.; Shigematsu K.; Manabe O. Photoresponsive Crown Ethers. 2. Photocontrol of Ion Extraction and Ion Transport by a Bis(crown ether) with a Butterfly-like Motion. J. Am. Chem. Soc. 1981, 103, 111–115 10.1021/ja00391a021. [DOI] [Google Scholar]
Hunter C. A.; Anderson H. L. What is Cooperativity?. Angew. Chem., Int. Ed. 2009, 48, 7488–7499 10.1002/anie.200902490. [DOI] [PubMed] [Google Scholar]
Klarner F. G.; Kahlert B. Molecular Tweezers and Clips as Synthetic Receptors. Molecular Recognition and Dynamics in Receptor-substrate Complexes. Acc. Chem. Res. 2003, 36, 919–932 10.1021/ar0200448. [DOI] [PubMed] [Google Scholar]
Harmata M. Chiral Molecular Tweezers. Acc. Chem. Res. 2004, 37, 862–873 10.1021/ar030164v. [DOI] [PubMed] [Google Scholar]
Poulsen T.; Nielsen K. A.; Bond A. D.; Jeppesen J. O. Bis(tetrathiafulvalene)-Calix[2]pyrrole[2]- thiophene and Its Complexation with TCNQ. Org. Lett. 2007, 9, 5485–5488 10.1021/ol7024235. [DOI] [PubMed] [Google Scholar]
Sijbesma R. P.; Wijmenga S. S.; Nolte R. J. M. A Molecular Clip That Binds Aromatic Guests by an Induced-fit Mechanism. J. Am. Chem. Soc. 1992, 114, 9807–9813 10.1021/ja00051a013. [DOI] [Google Scholar]
Rowan A. E.; Elemans J. A. A. W.; Nolte R. J. M. Molecular and Supramolecular Objects from Glycoluril. Acc. Chem. Res. 1999, 32, 995–1006 10.1021/ar9702684. [DOI] [Google Scholar]
Reek J. N. H.; Engelkamp H.; Rowan A. E.; Elemans J. A. A. W.; Nolte R. J. M. Conformational Behavior and Binding Properties of Naphthalene-Walled Clips. Chem. - Eur. J. 1998, 4, 716–722. [DOI] [Google Scholar]
Sijbesma R. P.; Nolte R. J. M. A Molecular Clip with Allosteric Binding Properties. J. Am. Chem. Soc. 1991, 113, 6695–6696 10.1021/ja00017a063. [DOI] [Google Scholar]
Klarner F. G.; Benkhoff J.; Boese R.; Burkert U.; Kamieth M.; Naatz U. Molecular Tweezers as Synthetic Receptors in Host-guest Chemistry: Inclusion of Cyclohexane and Self-assembly of Aliphatic Side Chains. Angew. Chem., Int. Ed. Engl. 1996, 35, 1130–1133 10.1002/anie.199611301. [DOI] [Google Scholar]
Petitjean A.; Khoury R. G.; Kyritsakas N.; Lehn J.-M. Dynamic Devices. Shape Switching and Substrate Binding in Ion-Controlled Nanomechanical Molecular Tweezers. J. Am. Chem. Soc. 2004, 126, 6637–6647 10.1021/ja031915r. [DOI] [PubMed] [Google Scholar]
Hoffmann R. W. Flexible Molecules with Defined Shape—Conformational Design. Angew. Chem., Int. Ed. Engl. 1992, 31, 1124–1134 10.1002/anie.199211241. [DOI] [Google Scholar]
Yuasa H.; Hashimoto H. Bending Trisaccharides by a Chelation-Induced Ring Flip of a Hinge-Like Monosaccharide Unit. J. Am. Chem. Soc. 1999, 121, 5089–5090 10.1021/ja984062p. [DOI] [Google Scholar]
Izumi T.; Hashimoto H.; Yuasa H. Switching Extended 1,3-Diequatorial and Bent 1,3-Diaxial States of a Disubstituted Hinge Sugar by Ligand Exchange Reactions on Pt(II). Chem. Commun. 2004, 94–95 10.1039/b311811h. [DOI] [PubMed] [Google Scholar]
Menger F. M.; Chicklo P. A.; Sherrod M. J. Ion-induced Conformational Changes in Kemp’s Triacid. Tetrahedron Lett. 1989, 30, 6943–6946 10.1016/S0040-4039(01)93393-3. [DOI] [Google Scholar]
Shirodkar S. M.; Weisman G. R. Cyclohexane-based 1,3-Dipodands: Complexation and Conformational Biasing. J. Chem. Soc., Chem. Commun. 1989, 236–238 10.1039/c39890000236. [DOI] [Google Scholar]
Raban M.; Burch D. L.; Hortelano E. R.; Durocher D.; Kost D. Complete Conformational Switching in a Calcium Ionophore. J. Org. Chem. 1994, 59, 1283–1287 10.1021/jo00085a014. [DOI] [Google Scholar]
Kemp D. S.; Petrakis K. S. Synthesis and Conformational Analysis of cis,cis-1,3,5-Trimethylcyclohexane-1,3,5-tricarboxylic acid. J. Org. Chem. 1981, 46, 5140–5143 10.1021/jo00338a014. [DOI] [Google Scholar]
Samoshin V. V.; Chertkov V. A.; Vatlina L. P.; Dobretsova E. K.; Simonov N. A.; Kastorsky L. P.; Gremyachinsky D. E.; Schneider H.-J. trans-1,2-Cyclohexanedicarboxylic Acid Derivatives as pH-Trigger for Conformationally Controlled Crowns. Tetrahedron Lett. 1996, 37, 3981–3984 10.1016/0040-4039(96)00761-7. [DOI] [Google Scholar]
Gil de Oliveira Santos A.; Klute W.; Torode J.; P. W. Bohm V.; Cabrita E.; Runsink J.; W. Hoffmann R. Flexible Molecules with Defined Shape. X. Synthesis and Conformational Study of 1,5-Diaza-cis-decalin. New J. Chem. 1998, 22, 993–997 10.1039/a801160e. [DOI] [Google Scholar]
Collin J.-P.; Durola F.; Heitz V.; Reviriego F.; Sauvage J.-P.; Trolez Y. A Cyclic [4]rotaxane that Behaves as a Switchable Molecular Receptor: Formation of a Rigid Scaffold from a Collapsed Structure by Complexation with Copper(I) Ions. Angew. Chem., Int. Ed. 2010, 49, 10172–10175 10.1002/anie.201004008. [DOI] [PubMed] [Google Scholar]
Haberhauer G. Control of Planar Chirality: The Construction of a Copper-Ion-Controlled Chiral Molecular Hinge. Angew. Chem., Int. Ed. 2008, 47, 3635–3638 10.1002/anie.200800062. [DOI] [PubMed] [Google Scholar]
Haberhauer G. A Metal-Ion-Driven Supramolecular Chirality Pendulum. Angew. Chem., Int. Ed. 2010, 49, 9286–9289 10.1002/anie.201004460. [DOI] [PubMed] [Google Scholar]
Haberhauer G.; Kallweit C. A Bridged Azobenzene Derivative as a Reversible, Light-Induced Chirality Switch. Angew. Chem., Int. Ed. 2010, 49, 2418–2421 10.1002/anie.200906731. [DOI] [PubMed] [Google Scholar]
Timmerman P.; Verboom W.; Reinhoudt D. N. Resorcinarenes. Tetrahedron 1996, 52, 2663–2704 10.1016/0040-4020(95)00984-1. [DOI] [Google Scholar]
Moran J. R.; Ericson J. L.; Dalcanale E.; Bryant J. A.; Knobler C. B.; Cram D. J. Vases and Kites as Cavitands. J. Am. Chem. Soc. 1991, 113, 5707–5714 10.1021/ja00015a026. [DOI] [Google Scholar]
Moran J. R.; Karbach S.; Cram D. J. Cavitands: Synthetic Molecular Vessels. J. Am. Chem. Soc. 1982, 104, 5826–5828 10.1021/ja00385a064. [DOI] [Google Scholar]
Skinner P. J.; Cheetham A. G.; Beeby A.; Gramlich V.; Diederich F. Conformational Switching of Resorcin[4]arene Cavitands by Protonation, Preliminary Communication. Helv. Chim. Acta 2001, 84, 2146–2153. [DOI] [Google Scholar]
Azov V. A.; Diederich F.; Lill Y.; Hecht B. Synthesis and Conformational Switching of Partially and Differentially Bridged Resorcin[4]arenes Bearing Fluorescent Dye Labels. Preliminary Communication. Helv. Chim. Acta 2003, 86, 2149–2155 10.1002/hlca.200390172. [DOI] [Google Scholar]
Azov V. A.; Jaun B.; Diederich F. NMR Investigations into the Vase-Kite Conformational Switching of Resorcin[4]arene Cavitands. Helv. Chim. Acta 2004, 87, 449–462 10.1002/hlca.200490043. [DOI] [Google Scholar]
Frei M.; Marotti F.; Diederich F. Zn^II-induced Conformational Control of Amphiphilic Cavitands in Langmuir Monolayers. Chem. Commun. 2004, 1362–1363 10.1039/b405331a. [DOI] [PubMed] [Google Scholar]
Pochorovski I.; Ebert M.-O.; Gisselbrecht J.-P.; Boudon C.; Schweizer W. B.; Diederich F. Redox-Switchable Resorcin[4]arene Cavitands: Molecular Grippers. J. Am. Chem. Soc. 2012, 134, 14702–14705 10.1021/ja306473x. [DOI] [PubMed] [Google Scholar]
Pochorovski I.; Milić J.; Kolarski D.; Gropp C.; Schweizer W. B.; Diederich F. Evaluation of Hydrogen-Bond Acceptors for Redox-Switchable Resorcin[4]arene Cavitands. J. Am. Chem. Soc. 2014, 136, 3852–3858 10.1021/ja411429b. [DOI] [PubMed] [Google Scholar]
Rudkevich D. M.; Hilmersson G.; Rebek J. Intramolecular Hydrogen Bonding Controls the Exchange Rates of Guests in a Cavitand. J. Am. Chem. Soc. 1997, 119, 9911–9912 10.1021/ja971592x. [DOI] [Google Scholar]
Rudkevich D. M.; Hilmersson G.; Rebek J. Self-Folding Cavitands. J. Am. Chem. Soc. 1998, 120, 12216–12225 10.1021/ja982970g. [DOI] [Google Scholar]
Ma S.; Rudkevich D. M.; Rebek J. J. Supramolecular Isomerism in Caviplexes. Angew. Chem., Int. Ed. 1999, 38, 2600–2602. [DOI] [PubMed] [Google Scholar]
Tucci F. C.; Rudkevich D. M.; Rebek J. J. Velcrands with Snaps and Their Conformational Control. Chem. - Eur. J. 2000, 6, 1007–1016. [DOI] [PubMed] [Google Scholar]
Haino T.; Rudkevich D. M.; Shivanyuk A.; Rissanen K.; Rebek J. J. Induced-Fit Molecular Recognition with Water-Soluble Cavitands. Chem. - Eur. J. 2000, 6, 3797–3805. [DOI] [PubMed] [Google Scholar]
Far A. R.; Shivanyuk A.; Rebek J. Water-Stabilized Cavitands. J. Am. Chem. Soc. 2002, 124, 2854–2855 10.1021/ja012453p. [DOI] [PubMed] [Google Scholar]
Amrhein P.; Wash P. L.; Shivanyuk A.; Rebek J. Metal Ligation Regulates Conformational Equilibria and Binding Properties of Cavitands. Org. Lett. 2002, 4, 319–321 10.1021/ol0167661. [DOI] [PubMed] [Google Scholar]
Tucker J. A.; Knobler C. B.; Trueblood K. N.; Cram D. J. Host-guest Complexation. 49. Cavitands Containing Two Binding Cavities. J. Am. Chem. Soc. 1989, 111, 3688–3699 10.1021/ja00192a028. [DOI] [Google Scholar]
Amrhein P.; Shivanyuk A.; Johnson D. W.; Rebek J. Metal-Switching and Self-Inclusion of Functional Cavitands. J. Am. Chem. Soc. 2002, 124, 10349–10358 10.1021/ja0204269. [DOI] [PubMed] [Google Scholar]
Ikeda A.; Shinkai S. Novel Cavity Design Using Calix[n]arene Skeletons: Toward Molecular Recognition and Metal Binding. Chem. Rev. 1997, 97, 1713–1734 10.1021/cr960385x. [DOI] [PubMed] [Google Scholar]
Ashton P. R.; Ballardini R.; Balzani V.; Boyd S. E.; Credi A.; Gandolfi M. T.; Gómez-López M.; Iqbal S.; Philp D.; Preece J. A. Simple Mechanical Molecular and Supramolecular Machines: Photochemical and Electrochemical Control of Switching Processes. Chem. - Eur. J. 1997, 3, 152–170 10.1002/chem.19970030123. [DOI] [Google Scholar]
Ashton P. R.; Gómez-López M.; Iqbal S.; Preece J. A.; Stoddart J. F. A Self-Complexing Macrocycle Acting as a Chromophoric Receptor. Tetrahedron Lett. 1997, 38, 3635–3638 10.1016/S0040-4039(97)00688-6. [DOI] [Google Scholar]
Brondsted Nielsen M.; Becher J. ’Self-complexing’ Tetrathiafulvalene Macrocycles; A Tetrathiafulvalene Switch. Chem. Commun. 1998, 475–476 10.1039/a707026h. [DOI] [Google Scholar]
Brøndsted Nielsen M.; Hansen J. G.; Becher J. Self-Complexing Tetrathiafulvalene-Based Donor–Acceptor Macrocycles. Eur. J. Org. Chem. 1999, 1999, 2807–2815. [DOI] [Google Scholar]
Balzani V.; Ceroni P.; Credi A.; Gomez-Lopez M.; Hamers C.; Stoddart J. F.; Wolf R. Controlled Dethreading/rethreading of a Scorpion-like Pseudorotaxane and a Related Macrobicyclic Self-complexing System. New J. Chem. 2001, 25, 25–31 10.1039/b004934o. [DOI] [Google Scholar]
Liu Y.; Flood A. H.; Stoddart J. F. Thermally and Electrochemically Controllable Self-Complexing Molecular Switches. J. Am. Chem. Soc. 2004, 126, 9150–9151 10.1021/ja048164t. [DOI] [PubMed] [Google Scholar]
Qu D.-H.; Feringa B. L. Controlling Molecular Rotary Motion with a Self-Complexing Lock. Angew. Chem., Int. Ed. 2010, 49, 1107–1110 10.1002/anie.200906064. [DOI] [PubMed] [Google Scholar]
Jones I. M.; Lingard H.; Hamilton A. D. pH-Dependent Conformational Switching in 2,6-Benzamidodiphenylacetylenes. Angew. Chem., Int. Ed. 2011, 50, 12569–12571 10.1002/anie.201106241. [DOI] [PubMed] [Google Scholar]
Pramanik S.; De S.; Schmittel M. Bidirectional Chemical Communication between Nanomechanical Switches. Angew. Chem., Int. Ed. 2014, 53, 4709–4713 10.1002/anie.201400804. [DOI] [PubMed] [Google Scholar]
Dolain C.; Maurizot V.; Huc I. Protonation-Induced Transition between Two Distinct Helical Conformations of a Synthetic Oligomer via a Linear Intermediate. Angew. Chem., Int. Ed. 2003, 42, 2738–2740 10.1002/anie.200351080. [DOI] [PubMed] [Google Scholar]
Piguet C.; Bernardinelli G.; Hopfgartner G. Helicates as Versatile Supramolecular Complexes. Chem. Rev. 1997, 97, 2005–2062 10.1021/cr960053s. [DOI] [PubMed] [Google Scholar]
Hill D. J.; Mio M. J.; Prince R. B.; Hughes T. S.; Moore J. S. A Field Guide to Foldamers. Chem. Rev. 2001, 101, 3893–4012 10.1021/cr990120t. [DOI] [PubMed] [Google Scholar]
Cheng R. P.; Gellman S. H.; DeGrado W. F. β-Peptides: From Structure to Function. Chem. Rev. 2001, 101, 3219–3232 10.1021/cr000045i. [DOI] [PubMed] [Google Scholar]
Albrecht M. Let’s Twist Again”Double-Stranded, Triple-Stranded, and Circular Helicates. Chem. Rev. 2001, 101, 3457–3498 10.1021/cr0103672. [DOI] [PubMed] [Google Scholar]
Williams A. Helical Complexes and Beyond. Chem. - Eur. J. 1997, 3, 15–19 10.1002/chem.19970030104. [DOI] [Google Scholar]
Gellman S. H. Foldamers: A Manifesto. Acc. Chem. Res. 1998, 31, 173–180 10.1021/ar960298r. [DOI] [Google Scholar]
Rowan A. E.; Nolte R. J. M. Helical Molecular Programming. Angew. Chem., Int. Ed. 1998, 37, 63–68. [DOI] [Google Scholar]
Cubberley M. S.; Iverson B. L. Models of Higher-order Structure: Foldamers and Beyond. Curr. Opin. Chem. Biol. 2001, 5, 650–653 10.1016/S1367-5931(01)00261-7. [DOI] [PubMed] [Google Scholar]
Schmuck C. Molecules with Helical Structure: How To Build a Molecular Spiral Staircase. Angew. Chem., Int. Ed. 2003, 42, 2448–2452 10.1002/anie.200201625. [DOI] [PubMed] [Google Scholar]
Albrecht M. Artificial Molecular Double-Stranded Helices. Angew. Chem., Int. Ed. 2005, 44, 6448–6451 10.1002/anie.200501472. [DOI] [PubMed] [Google Scholar]
Gong B. Crescent Oligoamides: From Acyclic “Macrocycles” to Folding Nanotubes. Chem. - Eur. J. 2001, 7, 4336–4342. [DOI] [PubMed] [Google Scholar]
Sanford A. R.; Yamato K.; Yang X.; Yuan L.; Han Y.; Gong B. Well-defined Secondary Structures. Eur. J. Biochem. 2004, 271, 1416–1425 10.1111/j.1432-1033.2004.04062.x. [DOI] [PubMed] [Google Scholar]
Huc I. Aromatic Oligoamide Foldamers. Eur. J. Org. Chem. 2004, 2004, 17–29 10.1002/ejoc.200300495. [DOI] [Google Scholar]
Constable E. C. Oligopyridines as Helicating Ligands. Tetrahedron 1992, 48, 10013–10059 10.1016/S0040-4020(01)89035-9. [DOI] [Google Scholar]
Seebach D.; Matthews J. β-Peptides: A Surprise at Every Turn. Chem. Commun. 1997, 2015–2022 10.1039/a704933a. [DOI] [Google Scholar]
Nielsen P. E.; Haaima G. Peptide Nucleic Acid (PNA). A DNA Mimic with a Pseudopeptide Backbone. Chem. Soc. Rev. 1997, 26, 73–78 10.1039/cs9972600073. [DOI] [Google Scholar]
Nowick J. S. Chemical Models of Protein β-Sheets. Acc. Chem. Res. 1999, 32, 287–296 10.1021/ar970204t. [DOI] [Google Scholar]
Stigers K. D.; Soth M. J.; Nowick J. S. Designed Molecules that Fold to Mimic Protein Secondary Structures. Curr. Opin. Chem. Biol. 1999, 3, 714–723 10.1016/S1367-5931(99)00030-7. [DOI] [PubMed] [Google Scholar]
Nielsen P. E. Peptide Nucleic Acid. A Molecule with Two Identities. Acc. Chem. Res. 1999, 32, 624–630 10.1021/ar980010t. [DOI] [Google Scholar]
Kirshenbaum K.; Zuckermann R. N.; Dill K. A. Designing Polymers That Mimic Biomolecules. Curr. Opin. Struct. Biol. 1999, 9, 530–535 10.1016/S0959-440X(99)80075-X. [DOI] [PubMed] [Google Scholar]
Herdewijn P. Conformationally Restricted Carbohydrate-modified Nucleic Acids and Antisense Technology. Biochim. Biophys. Acta, Gene Struct. Expression 1999, 1489, 167–179 10.1016/S0167-4781(99)00152-9. [DOI] [PubMed] [Google Scholar]
Patch J. A.; Barron A. E. Mimicry of Bioactive Peptides via Non-natural, Sequence-specific Peptidomimetic Oligomers. Curr. Opin. Chem. Biol. 2002, 6, 872–877 10.1016/S1367-5931(02)00385-X. [DOI] [PubMed] [Google Scholar]
Martinek T. A.; Fülöp F. Side-chain Control of β-Peptide Secondary Structures. Eur. J. Biochem. 2003, 270, 3657–3666 10.1046/j.1432-1033.2003.03756.x. [DOI] [PubMed] [Google Scholar]
Cheng R. P. Beyond de novo Protein Design — de novo Design of Non-natural Folded Oligomers. Curr. Opin. Struct. Biol. 2004, 14, 512–520 10.1016/j.sbi.2004.07.001. [DOI] [PubMed] [Google Scholar]
Licini G.; Prins L. J.; Scrimin P. Oligopeptide Foldamers: From Structure to Function. Eur. J. Org. Chem. 2005, 2005, 969–977 10.1002/ejoc.200400521. [DOI] [Google Scholar]
Nelson J. C.; Saven J. G.; Moore J. S.; Wolynes P. G. Solvophobically Driven Folding of Nonbiological Oligomers. Science 1997, 277, 1793–1796 10.1126/science.277.5333.1793. [DOI] [PubMed] [Google Scholar]
Prince R. B.; Saven J. G.; Wolynes P. G.; Moore J. S. Cooperative Conformational Transitions in Phenylene Ethynylene Oligomers: Chain-Length Dependence. J. Am. Chem. Soc. 1999, 121, 3114–3121 10.1021/ja983995i. [DOI] [Google Scholar]
Lahiri S.; Thompson J. L.; Moore J. S. Solvophobically Driven π-Stacking of Phenylene Ethynylene Macrocycles and Oligomers. J. Am. Chem. Soc. 2000, 122, 11315–11319 10.1021/ja002129e. [DOI] [Google Scholar]
Hill D. J.; Moore J. S. Helicogenicity of Solvents in the Conformational Equilibrium of Oligo(m-phenylene ethynylene)s: Implications for Foldamer Research. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 5053–5057 10.1073/pnas.072642799. [DOI] [PMC free article] [PubMed] [Google Scholar]
Hofacker A. L.; Parquette J. R. Dendrimer Folding in Aqueous Media: An Example of Solvent-Mediated Chirality Switching. Angew. Chem., Int. Ed. 2005, 44, 1053–1057 10.1002/anie.200460943. [DOI] [PubMed] [Google Scholar]
Berl V.; Huc I.; Khoury R. G.; Krische M. J.; Lehn J.-M. Interconversion of Single and Double Helices Formed from Synthetic Molecular Strands. Nature 2000, 407, 720–723 10.1038/35037545. [DOI] [PubMed] [Google Scholar]
Berl V.; Huc I.; Khoury R. G.; Lehn J.-M. Helical Molecular Programming: Folding of Oligopyridine-dicarboxamides into Molecular Single Helices. Chem. - Eur. J. 2001, 7, 2798–2809. [DOI] [PubMed] [Google Scholar]
Berl V.; Huc I.; Khoury R. G.; Lehn J.-M. Helical Molecular Programming: Supramolecular Double Helices by Dimerization of Helical Oligopyridine-dicarboxamide Strands. Chem. - Eur. J. 2001, 7, 2810–2820. [DOI] [PubMed] [Google Scholar]
Hanan G. S.; Lehn J.-M.; Kyritsakas N.; Fischer J. Molecular Helicity: A General Approach for Helicity Induction in a Polyheterocyclic Molecular Strand. J. Chem. Soc., Chem. Commun. 1995, 765–766 10.1039/c39950000765. [DOI] [Google Scholar]
Bassani D. M.; Lehn J.-M.; Baum G.; Fenske D. Designed Self-Generation of an Extended Helical Structure From an Achiral Polyheterocylic Strand. Angew. Chem., Int. Ed. Engl. 1997, 36, 1845–1847 10.1002/anie.199718451. [DOI] [Google Scholar]
Ohkita M.; Lehn J.-M.; Baum G.; Fenske D. Helicity Coding: Programmed Molecular Self-Organization of Achiral Nonbiological Strands into Multiturn Helical Superstructures: Synthesis and Characterization of Alternating Pyridine–Pyrimidine Oligomers. Chem. - Eur. J. 1999, 5, 3471–3481. [DOI] [Google Scholar]
Stadler A.-M.; Kyritsakas N.; Lehn J.-M. Reversible Folding/unfolding of Linear Molecular Strands into Helical Channel-like Complexes upon Proton-modulated Binding and Release of Metal Ions. Chem. Commun. 2004, 2024–2025 10.1039/b407168a. [DOI] [PubMed] [Google Scholar]
Kolomiets E.; Berl V.; Odriozola I.; Stadler A.-M.; Kyritsakas N.; Lehn J.-M. Contraction/extension Molecular Motion by Protonation/deprotonation Induced Structural Switching of Pyridine Derived Oligoamides. Chem. Commun. 2003, 2868–2869 10.1039/b311578j. [DOI] [PubMed] [Google Scholar]
Barboiu M.; Lehn J.-M. Dynamic Chemical Devices: Modulation of Contraction/extension Molecular Motion by Coupled-ion Binding/pH Change-induced Structural Switching. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 5201–5206 10.1073/pnas.082099199. [DOI] [PMC free article] [PubMed] [Google Scholar]
Barboiu M.; Vaughan G.; Kyritsakas N.; Lehn J.-M. Dynamic Chemical Devices: Generation of Reversible Extension/Contraction Molecular Motion by Ion-Triggered Single/Double Helix Interconversion. Chem. - Eur. J. 2003, 9, 763–769 10.1002/chem.200390085. [DOI] [PubMed] [Google Scholar]
Stadler A.-M.; Lehn J.-M. P. Coupled Nanomechanical Motions: Metal-Ion-Effected, pH-Modulated, Simultaneous Extension/Contraction Motions of Double-Domain Helical/Linear Molecular Strands. J. Am. Chem. Soc. 2014, 136, 3400–3409 10.1021/ja408752m. [DOI] [PubMed] [Google Scholar]
Dugave C.; Demange L. cis-trans Isomerization of Organic Molecules and Biomolecules: Implications and Applications. Chem. Rev. 2003, 103, 2475–2532 10.1021/cr0104375. [DOI] [PubMed] [Google Scholar]
Waldeck D. H. Photoisomerization Dynamics of Stilbenes. Chem. Rev. 1991, 91, 415–436 10.1021/cr00003a007. [DOI] [Google Scholar]
Bandara H. M.; Burdette S. C. Photoisomerization in Different Classes of Azobenzene. Chem. Soc. Rev. 2012, 41, 1809–1825 10.1039/C1CS15179G. [DOI] [PubMed] [Google Scholar]
Cheetham A. G.; Hutchings M. G.; Claridge T. D. W.; Anderson H. L. Enzymatic Synthesis and Photoswitchable Enzymatic Cleavage of a Peptide-linked Rotaxane. Angew. Chem., Int. Ed. 2006, 45, 1596–1599 10.1002/anie.200504064. [DOI] [PubMed] [Google Scholar]
Haberhauer G.; Kallweit C.; Wölper C.; Bläser D. An Azobenzene Unit Embedded in a Cyclopeptide as a Type-Specific and Spatially Directed Switch. Angew. Chem., Int. Ed. 2013, 52, 7879–7882 10.1002/anie.201301516. [DOI] [PubMed] [Google Scholar]
Clever G. H.; Tashiro S.; Shionoya M. Light-Triggered Crystallization of a Molecular Host-Guest Complex. J. Am. Chem. Soc. 2010, 132, 9973–9975 10.1021/ja103620z. [DOI] [PubMed] [Google Scholar]
Irie M. Diarylethenes for Memories and Switches. Chem. Rev. 2000, 100, 1685–1716 10.1021/cr980069d. [DOI] [PubMed] [Google Scholar]
Irie M. Photochromism: Memories and Switches - Introduction. Chem. Rev. 2000, 100, 1683–1683 10.1021/cr980068l. [DOI] [PubMed] [Google Scholar]
van Herpt J. T.; Areephong J.; Stuart M. C.; Browne W. R.; Feringa B. L. Light-controlled Formation of Vesicles and Supramolecular Organogels by a Cholesterol-bearing Amphiphilic Molecular Switch. Chem. - Eur. J. 2014, 20, 1737–1742 10.1002/chem.201302902. [DOI] [PubMed] [Google Scholar]
Hou L.; Zhang X.; Pijper T. C.; Browne W. R.; Feringa B. L. Reversible Photochemical Control of Singlet Oxygen Generation Using Diarylethene Photochromic Switches. J. Am. Chem. Soc. 2014, 136, 910–913 10.1021/ja4122473. [DOI] [PubMed] [Google Scholar]
Kudernac T.; Kobayashi T.; Uyama A.; Uchida K.; Nakamura S.; Feringa B. L. Tuning the Temperature Dependence for Switching in Dithienylethene Photochromic Switches. J. Phys. Chem. A 2013, 117, 8222–8229 10.1021/jp404924q. [DOI] [PubMed] [Google Scholar]
Yokoyama Y. Fulgides for Memories and Switches. Chem. Rev. 2000, 100, 1717–1739 10.1021/cr980070c. [DOI] [PubMed] [Google Scholar]
Santiago A.; Becker R. S. Photochromic Fulgides - Spectroscopy and Mechanism of Photoreactions. J. Am. Chem. Soc. 1968, 90, 3654–3658 10.1021/ja01016a009. [DOI] [Google Scholar]
Berkovic G.; Weiss V. Spiropyrans and Spirooxazines for Memories and Switches. Chem. Rev. 2000, 100, 1741–1753 10.1021/cr9800715. [DOI] [PubMed] [Google Scholar]
Feringa B. L.; Huck N. P. M.; Schoevaars A. M. Chiroptical Molecular Switches. Adv. Mater. 1996, 8, 681–684 10.1002/adma.19960080819. [DOI] [Google Scholar]
Feringa B. L.; van Delden R. A.; Koumura N.; Geertsema E. M. Chiroptical Molecular Switches. Chem. Rev. 2000, 100, 1789–1816 10.1021/cr9900228. [DOI] [PubMed] [Google Scholar]
Browne B. L. F. a. W.Molecular Switches, 2nd ed.; Wiley-VCH: Weinheim, 2011. [Google Scholar]
Shinkai S.; Honda Y.; Kusano Y.; Manabe O. A Photoresponsive Cylindrical Ionophore. J. Chem. Soc., Chem. Commun. 1982, 848–850 10.1039/c39820000848. [DOI] [Google Scholar]
Feringa B. L.; Jager W. F.; de Lange B. Organic Materials for Reversible Optical Data Storage. Tetrahedron 1993, 49, 8267–8310 10.1016/S0040-4020(01)81913-X. [DOI] [Google Scholar]
Momotake A.; Arai T. Synthesis, Excited State Properties, and Dynamic Structural Change of Photoresponsive Dendrimers. Polymer 2004, 45, 5369–5390 10.1016/j.polymer.2004.05.075. [DOI] [Google Scholar]
Momotake A.; Arai T. Photochemistry and Photophysics of Stilbene Dendrimers and Related Compounds. J. Photochem. Photobiol., C 2004, 5, 1–25 10.1016/j.jphotochemrev.2004.01.001. [DOI] [Google Scholar]
Tie C.; Gallucci J. C.; Parquette J. R. Helical Conformational Dynamics and Photoisomerism of Alternating Pyridinedicarboxamide/m-(Phenylazo)azobenzene Oligomers. J. Am. Chem. Soc. 2006, 128, 1162–1171 10.1021/ja0547228. [DOI] [PubMed] [Google Scholar]
Yager K. G.; Barrett C. J. Novel Photo-switching Using Azobenzene Functional Materials. J. Photochem. Photobiol., A 2006, 182, 250–261 10.1016/j.jphotochem.2006.04.021. [DOI] [Google Scholar]
Russew M. M.; Hecht S. Photoswitches: From Molecules to Materials. Adv. Mater. 2010, 22, 3348–3360 10.1002/adma.200904102. [DOI] [PubMed] [Google Scholar]
Fischer G. Peptidyl-Prolyl cis/trans Isomerases and Their Effectors. Angew. Chem., Int. Ed. Engl. 1994, 33, 1415–1436 10.1002/anie.199414151. [DOI] [Google Scholar]
Fischer G. Chemical Aspects of Peptide Bond Isomerization. Chem. Soc. Rev. 2000, 29, 119–127 10.1039/a803742f. [DOI] [Google Scholar]
Beharry A. A.; Woolley G. A. Azobenzene Photoswitches for Biomolecules. Chem. Soc. Rev. 2011, 40, 4422–4437 10.1039/c1cs15023e. [DOI] [PubMed] [Google Scholar]
Beharry A. A.; Wong L.; Tropepe V.; Woolley G. A. Fluorescence Imaging of Azobenzene Photoswitching In Vivo. Angew. Chem., Int. Ed. 2011, 50, 1325–1327 10.1002/anie.201006506. [DOI] [PubMed] [Google Scholar]
Szymanski W.; Beierle J. M.; Kistemaker H. A.; Velema W. A.; Feringa B. L. Reversible Photocontrol of Biological Systems by the Incorporation of Molecular Photoswitches. Chem. Rev. 2013, 113, 6114–6178 10.1021/cr300179f. [DOI] [PubMed] [Google Scholar]
Kienzler M. A.; Reiner A.; Trautman E.; Yoo S.; Trauner D.; Isacoff E. Y. A Red-Shifted, Fast-Relaxing Azobenzene Photoswitch for Visible Light Control of an Ionotropic Glutamate Receptor. J. Am. Chem. Soc. 2013, 135, 17683–17686 10.1021/ja408104w. [DOI] [PMC free article] [PubMed] [Google Scholar]
Kamiya Y.; Asanuma H. Light-Driven DNA Nanomachine with a Photoresponsive Molecular Engine. Acc. Chem. Res. 2014, 47, 1663–1672 10.1021/ar400308f. [DOI] [PubMed] [Google Scholar]
Velema W. A.; Szymanski W.; Feringa B. L. Photopharmacology: Beyond Proof of Principle. J. Am. Chem. Soc. 2014, 136, 2178–2191 10.1021/ja413063e. [DOI] [PubMed] [Google Scholar]
Velema W. A.; van der Berg J. P.; Hansen M. J.; Szymanski W.; Driessen A. J.; Feringa B. L. Optical Control of Antibacterial Activity. Nat. Chem. 2013, 5, 924–928 10.1038/nchem.1750. [DOI] [PubMed] [Google Scholar]
Szymanski W.; Yilmaz D.; Kocer A.; Feringa B. L. Bright Ion Channels and Lipid Bilayers. Acc. Chem. Res. 2013, 46, 2910–2923 10.1021/ar4000357. [DOI] [PubMed] [Google Scholar]
Kocer A.; Walko M.; Meijberg W.; Feringa B. L. A Light-actuated Nanovalve Derived from a Channel Protein. Science 2005, 309, 755–758 10.1126/science.1114760. [DOI] [PubMed] [Google Scholar]
Muraoka T.; Kinbara K.; Aida T. Mechanical Twisting of a Guest by a Photoresponsive Host. Nature 2006, 440, 512–515 10.1038/nature04635. [DOI] [PubMed] [Google Scholar]
Muraoka T.; Kinbara K.; Aida T. Reversible Operation of Chiral Molecular Scissors by Redox and UV Light. Chem. Commun. 2007, 1441–1443 10.1039/b618248h. [DOI] [PubMed] [Google Scholar]
Merino E.; Ribagorda M. Control Over Molecular Motion Using the cis-trans Photoisomerization of the Azo Group. Beilstein J. Org. Chem. 2012, 8, 1071–1090 10.3762/bjoc.8.119. [DOI] [PMC free article] [PubMed] [Google Scholar]
Marchi E.; Baroncini M.; Bergamini G.; Van Heyst J.; Vogtle F.; Ceroni P. Photoswitchable Metal Coordinating Tweezers Operated by Light-harvesting Dendrimers. J. Am. Chem. Soc. 2012, 134, 15277–15280 10.1021/ja307522f. [DOI] [PubMed] [Google Scholar]
Raymo F. M. Intermolecular Coupling of Motion Under Photochemical Control. Angew. Chem., Int. Ed. 2006, 45, 5249–5251 10.1002/anie.200602516. [DOI] [PubMed] [Google Scholar]
Kai H.; Nara S.; Kinbara K.; Aida T. Toward Long-distance Mechanical Communication: Studies on a Ternary Complex Interconnected by a Bridging Rotary Module. J. Am. Chem. Soc. 2008, 130, 6725–6727 10.1021/ja801646b. [DOI] [PubMed] [Google Scholar]
Muraoka T.; Kinbara K.; Kobayashi Y.; Aida T. Light-Driven Open-Close Motion of Chiral Molecular Scissors. J. Am. Chem. Soc. 2003, 125, 5612–5613 10.1021/ja034994f. [DOI] [PubMed] [Google Scholar]
Norikane Y.; Tamaoki N. Light-Driven Molecular Hinge: A New Molecular Machine Showing a Light-Intensity-Dependent Photoresponse that Utilizes the Trans-Cis Isomerization of Azobenzene. Org. Lett. 2004, 6, 2595–2598 10.1021/ol049082c. [DOI] [PubMed] [Google Scholar]
Muraoka T.; Kinbara K. Development of Photoresponsive Supramolecular Machines Inspired by Biological Molecular Systems. J. Photochem. Photobiol., C 2012, 13, 136–147 10.1016/j.jphotochemrev.2012.04.001. [DOI] [Google Scholar]
Li Z.; Liang J.; Xue W.; Liu G.; Liu S. H.; Yin J. Switchable Azo-macrocycles: From Molecules to Functionalisation. Supramol. Chem. 2014, 26, 54–65 10.1080/10610278.2013.822970. [DOI] [Google Scholar]
Basheer M. C.; Oka Y.; Mathews M.; Tamaoki N. A Light-controlled Molecular Brake with Complete ON-OFF Rotation. Chem. - Eur. J. 2010, 16, 3489–3496 10.1002/chem.200902123. [DOI] [PubMed] [Google Scholar]
Hashim P. K.; Thomas R.; Tamaoki N. Induction of Molecular Chirality by Circularly Polarized Light in Cyclic Azobenzene with a Photoswitchable Benzene Rotor. Chem. - Eur. J. 2011, 17, 7304–7312 10.1002/chem.201003526. [DOI] [PubMed] [Google Scholar]
Baroncini M.; Silvi S.; Venturi M.; Credi A. Reversible Photoswitching of Rotaxane Character and Interplay of Thermodynamic Stability and Kinetic Lability in a Self-assembling Ring-axle Molecular System. Chem. - Eur. J. 2010, 16, 11580–11587 10.1002/chem.201001409. [DOI] [PubMed] [Google Scholar]
Liu F.; Morokuma K. Computational Study on the Working Mechanism of a Stilbene Light-Driven Molecular Rotary Motor: Sloped Minimal Energy Path and Unidirectional Nonadiabatic Photoisomerization. J. Am. Chem. Soc. 2012, 134, 4864–4876 10.1021/ja211441n. [DOI] [PubMed] [Google Scholar]
Pospíšil L.; Bednárová L.; Štěpánek P.; Slavíček P.; Vávra J.; Hromadová M.; Dlouhá H.; Tarábek J.; Teplý F. Intense Chiroptical Switching in a Dicationic Helicene-Like Derivative: Exploration of a Viologen-Type Redox Manifold of a Non-Racemic Helquat. J. Am. Chem. Soc. 2014, 136, 10826–10829 10.1021/ja500220j. [DOI] [PubMed] [Google Scholar]
Ruangsupapichat N.; Pollard M. M.; Harutyunyan S. R.; Feringa B. L. Reversing the Direction in a Light-driven Rotary Molecular Motor. Nat. Chem. 2011, 3, 53–60 10.1038/nchem.872. [DOI] [PubMed] [Google Scholar]
Feringa B. L. In Control of Motion: From Molecular Switches to Molecular Motors. Acc. Chem. Res. 2001, 34, 504–513 10.1021/ar0001721. [DOI] [PubMed] [Google Scholar]
Feringa B. L.; van Delden R. A.; ter Wiel M. K. J. In Control of Switching, Motion, and Organization. Pure Appl. Chem. 2003, 75, 563–575 10.1351/pac200375050563. [DOI] [Google Scholar]
Feringa B. L. The Art of Building Small: From Molecular Switches to Molecular Motors. J. Org. Chem. 2007, 72, 6635–6652 10.1021/jo070394d. [DOI] [PubMed] [Google Scholar]
Feringa B. L.; Koumura N.; van Delden R. A.; ter Wiel M. K. J. Light-driven Molecular Switches and Motors. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 301–308 10.1007/s003390201338. [DOI] [Google Scholar]
Feringa B. L. Molecular Switches and Motors. AIP Conf. Proc. 2013, 1519, 73–75 10.1063/1.4794713. [DOI] [Google Scholar]
Cnossen A.; Browne W. R.; Feringa B. L. Unidirectional Light-Driven Molecular Motors Based on Overcrowded Alkenes. Top. Curr. Chem. 2014, 354, 139–162 10.1007/128_2013_512. [DOI] [PubMed] [Google Scholar]
Koumura N.; Zijlstra R. W. J.; van Delden R. A.; Harada N.; Feringa B. L. Light-driven Monodirectional Molecualr Rotor. Nature 1999, 401, 152–155 10.1038/43646. [DOI] [PubMed] [Google Scholar]
Harada N.; Koumura N.; Feringa B. L. Chemistry of Unique Chiral Olefins. 3. synthesis and Absolute Stereochemistry of trans-and cis-1,1′,2,2′3,3′,4,4′-Octahydro-3,3′-dimethyl-4,4′-biphenanthrylidenes. J. Am. Chem. Soc. 1997, 119, 7256–7264 10.1021/ja970669e. [DOI] [Google Scholar]
Harada N.; Saito A.; Koumura N.; Uda H.; deLange B.; Jager W. F.; Wynberg H.; Feringa B. L. Chemistry of Unique Chiral Olefins 0.1. Synthesis, Enantioresolution, Circular Dichroism, and Theoretical Determination of the Absolute Stereochemistry of trans- and cis-1,1′,2,2′,3,3′,4,4′-octahydro-4,4′-biphenanthrylidenes. J. Am. Chem. Soc. 1997, 119, 7241–7248 10.1021/ja970667u. [DOI] [Google Scholar]
Harada N.; Saito A.; Koumura N.; Roe D. C.; Jager W. F.; Zijlstra R. W. J.; deLange B.; Feringa B. L. Chemistry of Unique Chiral Olefins 0.2. Unexpected Thermal Racemization of cis-1,1′,2,2′,3,3′,4,4′-octahydro-4,4′-biphenanthrylidene. J. Am. Chem. Soc. 1997, 119, 7249–7255 10.1021/ja970668m. [DOI] [Google Scholar]
Zijlstra R. W. J.; van Duijnen P. T.; Feringa B. L.; Steffen T.; Duppen K.; Wiersma D. A. Excited-State Dynamics of Tetraphenylethylene: Ultrafast Stokes Shift, Isomerization, and Charge Separation. J. Phys. Chem. A 1997, 101, 9828–9836 10.1021/jp971763k. [DOI] [Google Scholar]
Koumura N.; Harada N. Photochemistry and Absolute Stereochemistry of Unique Chiral Olefins, trans- and cis-1,1′,2,2′,3,3′,4,4′-Octahydro-3,3′-dimethyl-4,4′-biphenanthrylidenes. Chem. Lett. 1998, 1151–1152 10.1246/cl.1998.1151. [DOI] [Google Scholar]
Zijlstra R. W. J.; Jager W. F.; de Lange B.; van Duijnen P. Th.; Feringa B. L.; Goto H.; Saito A.; Koumura N.; Harada N. Chemistry of Unique Chiral Olefins. 4. Theoretical Studies of the Racemization Mechanism of trans- and cis-1,1′,2,2′,3,3′,4,4′-Octahydro-4,4′-biphenanthrylidenes. J. Org. Chem. 1999, 64, 1667–1674 10.1021/jo982381t. [DOI] [PubMed] [Google Scholar]
Zijlstra R. W. J.; Jager W. F.; de Lange B.; van Duijnen P. T.; Feringa B. L.; Goto H.; Saito A.; Koumura N.; Harada N. Chemistry of Unique Chiral Olefins. 4. Theoretical Studies of the Racemization Mechanism of trans- and cis-1,1 ′,2,2 ′,3,3 ′,4,4 ′-octahydro-4,4 ′-biphenanthrylidenes. J. Org. Chem. 1999, 64, 1667–1674 10.1021/jo982381t. [DOI] [PubMed] [Google Scholar]
ter Wiel M. K. J.; Koumura N.; Van Delden R. A.; Meetsma A.; Harada N.; Feringa B. L. Chiral Overcrowded Alkenes; Asymmetric Synthesis of (3S,3′S)-(M,M)-(E)-(+)-1,1′,2,2′,3,3′,4,4′-octahydro-3,3′,7,7′-Tetramethyl-4,4′-biphenanthrylidenes. Chirality 2000, 12, 734–741. [DOI] [PubMed] [Google Scholar]
ter Wiel M. K. J.; van Delden R. A.; Meetsma A.; Feringa B. L. Increased Speed of Rotation for The Smallest Light-Driven Molecular Motor. J. Am. Chem. Soc. 2003, 125, 15076–15086 10.1021/ja036782o. [DOI] [PubMed] [Google Scholar]
ter Wiel M. K. J.; van Delden R. A.; Meetsma A.; Feringa B. L. Light-Driven Molecular Motors: Stepwise Thermal Helix Inversion during Unidirectional Rotation of sterically Overcrowded Biphenanthrylidenes. J. Am. Chem. Soc. 2005, 127, 14208–14222 10.1021/ja052201e. [DOI] [PubMed] [Google Scholar]
Kuwahara S.; Fujita T.; Harada N. A New Model of Light-Powered Chiral Molecular Motor with Higher Speed of Rotation, Part 2 - Dynamics of Motor Rotation. Eur. J. Org. Chem. 2005, 2005, 4544–4556 10.1002/ejoc.200500323. [DOI] [Google Scholar]
Klok M.; Walko M.; Geertsema E. M.; Ruangsupapichat N.; Kistemaker J. C. M.; Meetsma A.; Feringa B. L. New Mechanistic Insight in the Thermal Helix Inversion of Second - Second Generation Moelcular Motors. Chem. - Eur. J. 2008, 14, 11183–11193 10.1002/chem.200800969. [DOI] [PubMed] [Google Scholar]
ter Wiel M. K.; Kwit M. G.; Meetsma A.; Feringa B. L. Synthesis, Stereochemistry, and Photochemical and Thermal Behavior of Bis-tert-butyl Substituted Overcrowded Alkenes. Org. Biomol. Chem. 2007, 5, 87–96 10.1039/B611070C. [DOI] [PubMed] [Google Scholar]
Pollard M. M.; Meetsma A.; Feringa B. L. A Redesign of Light-driven Rotary Molecular Motors. Org. Biomol. Chem. 2008, 6, 507–512 10.1039/B715652A. [DOI] [PubMed] [Google Scholar]
Caroli G.; Kwit M. G.; Feringa B. L. Photochemical and Thermal Behavior of Light-driven Unidirectional Molecular Motor with Long Alkyl Chains. Tetrahedron 2008, 64, 5956–5962 10.1016/j.tet.2008.03.098. [DOI] [Google Scholar]
Koumura N.; Geertsma E. M.; Meetsma A.; Feringa B. L. Light-Driven Molecular Rotor: Unidirectional Rotation Controlled by a Single Stereogenic Center. J. Am. Chem. Soc. 2000, 122, 12005–12006 10.1021/ja002755b. [DOI] [PubMed] [Google Scholar]
Pollard M. M.; ter Wiel M. K. J.; van Delden R. A.; Vicario J.; Koumura N.; van den Brom J. R.; Meetsma A.; Feringa B. L. Light-Driven Rotary Molecular Motors on Gold Nanoparticles. Chem. - Eur. J. 2008, 14, 11610–11622 10.1002/chem.200800814. [DOI] [PubMed] [Google Scholar]
van Delden R. A.; Koumura N.; Schoevaars A.; Meetsma A.; Feringa B. L. A Donor–acceptor Substituted Molecular Motor: Unidirectional Rotation Driven by Visible Light. Org. Biomol. Chem. 2003, 1, 33–35 10.1039/b209378b. [DOI] [PubMed] [Google Scholar]
Geertsema E. M.; Koumura N.; ter Wiel M. K. J.; Meetsma A.; Feringa B. L. In Control of the Speed of Rotation in Molecular Motors. Unexpected Retardation of Rotary Motion. Chem. Commun. 2002, 2962–2963 10.1039/b208323j. [DOI] [PubMed] [Google Scholar]
Koumura N.; Geertsema E. M.; van Gelder M. B.; Meetsma A.; Feringa B. L. Second Generation Light-Driven Molecular Motors. Unidirectional Rotation Controlled by a Single Stereogenic Center with Near-Perfect Photoequilibria and Acceleration of the Speed of Rotation by Structural Modification. J. Am. Chem. Soc. 2002, 124, 5037–5051 10.1021/ja012499i. [DOI] [PubMed] [Google Scholar]
ter Wiel M. K.; van Delden R. A.; Meetsma A.; Feringa B. L. Increased Speed of Rotation for the Smallest Light-Driven Molecular Motor. J. Am. Chem. Soc. 2003, 125, 15076–15086 10.1021/ja036782o. [DOI] [PubMed] [Google Scholar]
Pijper D.; van Delden R. A.; Meetsma A.; Feringa B. L. Acceleration of a Nanomotor: Electronic Control of the Rotary Speed of a Light-Driven Molecular Rotor. J. Am. Chem. Soc. 2005, 127, 17612–17613 10.1021/ja054499e. [DOI] [PubMed] [Google Scholar]
Vicario J.; Walko M.; Meetsma A.; Feringa B. L. Fine Tuning of the Rotary Motion by Structural Modification in Light-driven Unidirectional Molecular Motors. J. Am. Chem. Soc. 2006, 128, 5127–5135 10.1021/ja058303m. [DOI] [PubMed] [Google Scholar]
Conyard J.; Addison K.; Heisler I. A.; Cnossen A.; Browne W. R.; Feringa B. L.; Meech S. R. Ultrafast Dynamics in the Power Stroke of a Molecular Rotary Motor. Nat. Chem. 2012, 4, 547–551 10.1038/nchem.1343. [DOI] [PubMed] [Google Scholar]
Schoevaars A. M.; Kruizinga W.; Zijlstra R. W. J.; Veldman N.; Spek A. L.; Feringa B. L. Toward a Switchable Molecular Rotor. Unexpected Dynamic Behavior of Functionalized Overcrowded Alkenes. J. Org. Chem. 1997, 62, 4943–4948 10.1021/jo962210t. [DOI] [Google Scholar]
ter Wiel M. K.; van Delden R. A.; Meetsma A.; Feringa B. L. Control of Rotor Motion in a Light-driven Molecular Motor: Towards a Molecular Gearbox. Org. Biomol. Chem. 2005, 3, 4071–4076 10.1039/b510641a. [DOI] [PubMed] [Google Scholar]
Greb L.; Lehn J.-M. Light-Driven Molecular Motors: Imines as Four-Step or Two-Step Unidirectional Rotors. J. Am. Chem. Soc. 2014, 136, 13114–13117 10.1021/ja506034n. [DOI] [PubMed] [Google Scholar]
Padwa A. Photochemistry of the Crbon-Nitrogen Double Bond. Chem. Rev. 1977, 77, 37–68 10.1021/cr60305a004. [DOI] [Google Scholar]
Pratt A. C. The Photochemistry of Imines. Chem. Soc. Rev. 1977, 6, 63–81 10.1039/cs9770600063. [DOI] [Google Scholar]
Pierre Courot R. P.; le Saint Jaques Photochromisme par Isomerization Syn-anti de Phenylhydrazones-2 de Tricetones-1,2,3 et de Dicetones-1,2 Substituees. Tetrahedron Lett. 1976, 17, 1181–1184 10.1016/S0040-4039(00)78012-9. [DOI] [Google Scholar]
Pichon R.; le Saint J.; Courtot P. Photoisomerization d’Arylhydrazones-2 de Dicetones-1,2 Substituees en 2 Mecanisme d’Isomerization Thermique de la Double Liaison C=N. Tetrahedron 1981, 37, 1517–1524 10.1016/S0040-4020(01)92091-5. [DOI] [Google Scholar]
Chaur M. N.; Collado D.; Lehn J.-M. Configurational and Constitutional Information Storage: Multiple Dynamics in Systems Based on Pyridyl and Acyl Hydrazones. Chem. - Eur. J. 2011, 17, 248–258 10.1002/chem.201002308. [DOI] [PubMed] [Google Scholar]
Burdette S. C. Molecular Switches: Hydrazones Double Down on Zinc. Nat. Chem. 2012, 4, 695–696 10.1038/nchem.1438. [DOI] [PubMed] [Google Scholar]
Tatum L. A.; Su X.; Aprahamian I. Simple Hydrazone Building Blocks for Complicated Functional Materials. Acc. Chem. Res. 2014, 47, 2141–2149 10.1021/ar500111f. [DOI] [PubMed] [Google Scholar]
Su X.; Aprahamian I. Hydrazone-based Switches, Metallo-assemblies and Sensors. Chem. Soc. Rev. 2014, 43, 1963–1981 10.1039/c3cs60385g. [DOI] [PubMed] [Google Scholar]
Su X.; Aprahamian I. Zinc(II)-Regulation of Hydrazone Switch Isomerization Kinetics. Org. Lett. 2013, 15, 5952–5955 10.1021/ol402789y. [DOI] [PubMed] [Google Scholar]
Croteau M. L.; Su X.; Wilcox D. E.; Aprahamian I. Metal Coordination and Isomerization of a Hydrazone Switch. ChemPlusChem 2014, 79, 1214–1224 10.1002/cplu.201402134. [DOI] [Google Scholar]
Foy J. T.; Ray D.; Aprahamian I. Regulating Signal Enhancement with Coordination-coupled Deprotonation of a Hydrazone Switch. Chem. Sci. 2015, 6, 209–213 10.1039/C4SC02882A. [DOI] [PMC free article] [PubMed] [Google Scholar]
Langde S. M.; Aprahamian I. A ph Activated Configurational Rotary Switch: Controlling the E/Z Isomerization in Hydrazones. J. Am. Chem. Soc. 2009, 131, 18269–18271 10.1021/ja909149z. [DOI] [PubMed] [Google Scholar]
Su X.; Robbins T. F.; Aprahamian I. Switching Through Coordination-coupled Proton Transfer. Angew. Chem., Int. Ed. 2011, 50, 1841–1844 10.1002/anie.201006982. [DOI] [PubMed] [Google Scholar]
Landge S. M.; Tkatchouk E.; Benitez D.; Lanfranchi D. A.; Elhabiri M.; Goddard W. A. III; Aprahamian I. Isomerization Mechanism in Hydrazone-based Rotary Switches: Lateral Shift, Rotation, or Tautomerization?. J. Am. Chem. Soc. 2011, 133, 9812–9823 10.1021/ja200699v. [DOI] [PubMed] [Google Scholar]
Ray D.; Foy J. T.; Hughes R. P.; Aprahamian I. A Switching Cascade of Hydrazone-based Rotary Switches Through Coordination-coupled Proton Relays. Nat. Chem. 2012, 4, 757–762 10.1038/nchem.1408. [DOI] [PubMed] [Google Scholar]
Su X.; Voskian S.; Hughes R. P.; Aprahamian I. Manipulating Liquid-Crystal Properties Using a pH Activated Hydrazone Switch. Angew. Chem., Int. Ed. 2013, 52, 10734–10739 10.1002/anie.201305514. [DOI] [PubMed] [Google Scholar]
Siegel J. S. Supramolecular Chemistry. Concepts and Perspectives - Lehn, J. -M. Science 1996, 271, 949–949 10.1126/science.271.5251.949. [DOI] [Google Scholar]
Amendola V.; Fabbrizzi L.; Mangano C.; Pallavicini P. Molecular Movements and Translocations Controlled by Transition Metals and Signaled by Light Emission. Struct. Bonding (Berlin) 2001, 99, 79–115. [Google Scholar]
Miyazawa A.; Fujiyoshi Y.; Unwin N. Structure and Gating Mechanism of the Acetylcholine Receptor Pore. Nature 2003, 423, 949–955 10.1038/nature01748. [DOI] [PubMed] [Google Scholar]
Kaempfer R. Ribosomal Subunit Exchange during Protein Synthesis. Proc. Natl. Acad. Sci. U. S. A. 1968, 61, 106–113 10.1073/pnas.61.1.106. [DOI] [PMC free article] [PubMed] [Google Scholar]
Nakahata M.; Takashima Y.; Hashidzume A.; Harada A. Redox-Generated Mechanical Motion of a Supramolecular Polymeric Actuator Based on Host-Guest Interactions. Angew. Chem., Int. Ed. 2013, 52, 5731–5735 10.1002/anie.201300862. [DOI] [PubMed] [Google Scholar]
De Santis G.; Fabbrizzi L.; Iacopino D.; Pallavicini P.; Perotti A.; Poggi A. Electrochemically Switched Anion Translocation in a Multicomponent Coordination Compound. Inorg. Chem. 1997, 36, 827–832 10.1021/ic960892x. [DOI] [Google Scholar]
Akutagawa T.; Koshinaka H.; Sato D.; Takeda S.; Noro S. I.; Takahashi H.; Kumai R.; Tokura Y.; Nakamura T. Ferroelectricity and Polarity Control in Solid-state Flip-flop Supramolecular Rotators. Nat. Mater. 2009, 8, 342–347 10.1038/nmat2377. [DOI] [PubMed] [Google Scholar]
Ikeda A.; Tsudera T.; Shinkai S. Molecular Design of a ’’Molecular Syringe’’ Mimic for Metal Cations Using a 1,3-Alternate Calix[4]arene Cavity. J. Org. Chem. 1997, 62, 3568–3574 10.1021/jo962040k. [DOI] [PubMed] [Google Scholar]
Knipe P. C.; Thompson S.; Hamilton A. D. Ion-mediated Conformational Switches. Chem. Sci. 2015, 6, 1630–1639 10.1039/C4SC03525A. [DOI] [PMC free article] [PubMed] [Google Scholar]
Su X.; Robbins T. F.; Aprahamian I. Switching Through Coordination-Coupled Proton Transfer. Angew. Chem., Int. Ed. 2011, 50, 1841–1844 10.1002/anie.201006982. [DOI] [PubMed] [Google Scholar]
Su X.; Voskian S.; Hughes R. P.; Aprahamian I. Manipulating Liquid-Crystal Properties Using a pH Activated Hydrazone Switch. Angew. Chem., Int. Ed. 2013, 52, 10734–10739 10.1002/anie.201305514. [DOI] [PubMed] [Google Scholar]
Su X.; Lessing T.; Aprahamian I. The Importance of the Rotor in Hydrazone-based Molecular Switches. Beilstein J. Org. Chem. 2012, 8, 872–876 10.3762/bjoc.8.98. [DOI] [PMC free article] [PubMed] [Google Scholar]
Su X.; Aprahamian I. Switching Around Two Axles: Controlling the Configuration and Conformation of a Hydrazone-Based Switch. Org. Lett. 2011, 13, 30–33 10.1021/ol102422h. [DOI] [PubMed] [Google Scholar]
del Barrio J.; Horton P. N.; Lairez D.; Lloyd G. O.; Toprakcioglu C.; Scherman O. A. Photocontrol over Cucurbit[8]uril Complexes: Stoichiometry and Supramolecular Polymers. J. Am. Chem. Soc. 2013, 135, 11760–11763 10.1021/ja406556h. [DOI] [PubMed] [Google Scholar]
Lan Y.; Wu Y. C.; Karas A.; Scherman O. A. Photoresponsive Hybrid Raspberry-Like Colloids Based on Cucurbit[8]uril Host-Guest Interactions. Angew. Chem., Int. Ed. 2014, 53, 2166–2169 10.1002/anie.201309204. [DOI] [PubMed] [Google Scholar]
Ashton P. R.; Campbell P. J.; Chrystal E. J. T.; Glink P. T.; Menzer S.; Philp D.; Spencer N.; Stoddart J. F.; Tasker P. A.; Williams D. J. Dialkylammonium Ion Crown-Ether Complexes - the Forerunners of a New Family of Interlocked Molecules. Angew. Chem., Int. Ed. Engl. 1995, 34, 1865–1869 10.1002/anie.199518651. [DOI] [Google Scholar]
Ashton P. R.; Chrystal E. J. T.; Glink P. T.; Menzer S.; Schiavo C.; Stoddart J. F.; Tasker P. A.; Williams D. J. Doubly Encircled and Double-Stranded Pseudorotaxanes. Angew. Chem., Int. Ed. Engl. 1995, 34, 1869–1871 10.1002/anie.199518691. [DOI] [Google Scholar]
Ashton P. R.; Chrystal E. J. T.; Glink P. T.; Menzer S.; Schiavo C.; Spencer N.; Stoddart J. F.; Tasker P. A.; White A. J. P.; Williams D. J. Pseudorotaxanes Formed Between Secondary Dialkylammonium Salts and Crown Ethers. Chem. - Eur. J. 1996, 2, 709–728 10.1002/chem.19960020616. [DOI] [Google Scholar]
Ashton P. R.; Fyfe M. C. T.; Glink P. T.; Menzer S.; Stoddart J. F.; White A. J. P.; Williams D. J. Molecular Meccano, Part 24. Multiply Stranded and Multiply Encircled Pseudorotaxanes. J. Am. Chem. Soc. 1997, 119, 12514–12524 10.1021/ja9714806. [DOI] [Google Scholar]
Ashton P. R.; Fyfe M. C. T.; Martinez-Diaz M. V.; Menzer S.; Schiavo C.; Stoddart J. F.; White A. J. P.; Williams D. J. Molecular Meccano. Part 39 - Doubly Docked Pseudorotaxanes. Chem. - Eur. J. 1998, 4, 1523–1534. [DOI] [Google Scholar]
Loeb S. J.; Tiburcio J.; Vella S. J. [2]Pseudorotaxane Formation with N-benzylanilinium Axles and 24-Crown-8 Ether Wheels. Org. Lett. 2005, 7, 4923–4926 10.1021/ol051786e. [DOI] [PubMed] [Google Scholar]
Baroncini M.; Gao C.; Carboni V.; Credi A.; Previtera E.; Semeraro M.; Venturi M.; Silvi S. Light Control of Stoichiometry and Motion in Pseudorotaxanes Comprising a Cucurbit[7]uril Wheel and an Azobenzene-Bipyridinium Axle. Chem. - Eur. J. 2014, 20, 10737–10744 10.1002/chem.201402821. [DOI] [PubMed] [Google Scholar]
Credi A.; Dumas S.; Silvi S.; Venturi M.; Arduini A.; Pochini A.; Secchi A. Viologen-calix[6]arene Pseudorotaxanes. Ion-pair Recognition and Threading/dethreading Molecular Motions. J. Org. Chem. 2004, 69, 5881–5887 10.1021/jo0494127. [DOI] [PubMed] [Google Scholar]
Balzani V.; Credi A.; Marchioni F.; Stoddart J. F. Artificial Molecular-level Machines. Dethreading-rethreading of a Pseudorotaxane Powered Exclusively by Light Energy. Chem. Commun. 2001, 1860–1861 10.1039/b105160c. [DOI] [PubMed] [Google Scholar]
Baroncini M.A Simple Molecular Machine Operated by Photoinduced Proton Transfer. Springer Theses; Springer: New York, 2011; Chapter 7, pp 71–76; 10.1007/978-3-642-19285-2_7. [DOI] [PubMed] [Google Scholar]
Jeppesen J. O.; Becher J.; Stoddart J. F. Poised on the Brink Between a Bistable Complex and a Compound. Org. Lett. 2002, 4, 557–560 10.1021/ol0171362. [DOI] [PubMed] [Google Scholar]
Rekharsky M. V.; Yamamura H.; Kawai M.; Osaka I.; Arakawa R.; Sato A.; Ko Y. H.; Selvapalam N.; Kim K.; Inoue Y. Sequential Formation of a Ternary Complex Among Dihexylammonium, Cucurbit[6]uril, and Cyclodextrin with Positive Cooperativity. Org. Lett. 2006, 8, 815–818 10.1021/ol0528742. [DOI] [PubMed] [Google Scholar]
Balzani V.; Credi A.; Venturi M. Controlled Disassembling of Self-assembling Systems: Toward Artificial Molecular-level Devices and Machines. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4814–4817 10.1073/pnas.022631599. [DOI] [PMC free article] [PubMed] [Google Scholar]
Huang F.; Fronczek F. R.; Gibson H. W. A Cryptand/bisparaquat [3]Pseudorotaxane by Cooperative Complexation. J. Am. Chem. Soc. 2003, 125, 9272–9273 10.1021/ja0355877. [DOI] [PubMed] [Google Scholar]
Huang F.; Gibson H. W.; Bryant W. S.; Nagvekar D. S.; Fronczek F. R. First Pseudorotaxane-like [3]Complexes based on Cryptands and Paraquat: Self-assembly and Crystal Structures. J. Am. Chem. Soc. 2003, 125, 9367–9371 10.1021/ja034968h. [DOI] [PubMed] [Google Scholar]
Inoue Y.; Kanbara T.; Yamamoto T. Construction of New [2]Pseudorotaxanes by Hydrogen Bonding Assembly of Macrocyclic Tetrathiolactam with Amides and an Ester. Tetrahedron Lett. 2004, 45, 4603–4606 10.1016/j.tetlet.2004.04.114. [DOI] [Google Scholar]
Sambrook M. R.; Beer P. D.; Wisner J. A.; Paul R. L.; Cowley A. R.; Szemes F.; Drew M. G. Anion-templated Assembly of Pseudorotaxanes: Importance of Anion Template, Strength of Ion-pair Thread Association, and Macrocycle Ring Size. J. Am. Chem. Soc. 2005, 127, 2292–2302 10.1021/ja046278z. [DOI] [PubMed] [Google Scholar]
Yonemura H.; Kusano S.; Matsuo T.; Yamada S. Effect of pi-System on Long-range Photoinduced Electron Transfer in Through-ring alpha-Cyclodextrin Complexes of Carbazole-viologen Linked Compounds. Tetrahedron Lett. 1998, 39, 6915–6918 10.1016/S0040-4039(98)01451-8. [DOI] [Google Scholar]
Montalti M.; Ballardini R.; Prodi L.; Balzani V. Electronic Energy Transfer in Adducts of Aromatic Crown Ethers with Protonated 9-Methylaminomethylanthracene. Chem. Commun. 1996, 2011–2012 10.1039/cc9960002011. [DOI] [Google Scholar]
Asakawa M.; Ashton P. R.; Balzani V.; Credi A.; Mattersteig G.; Matthews O. A.; Montalti M.; Spencer N.; Stoddart J. F.; Venturi M. Electrochemically Induced Molecular Motions in Pseudorotaxanes: A Case of Dual-mode (Oxidative and Reductive) Dethreading. Chem. - Eur. J. 1997, 3, 1992–1996 10.1002/chem.19970031214. [DOI] [Google Scholar]
Credi A.; Balzani V.; Langford S. J.; Stoddart J. F. Logic Operations at the Molecular Level. An XOR Gate Based on a Molecular Machine. J. Am. Chem. Soc. 1997, 119, 2679–2681 10.1021/ja963572l. [DOI] [Google Scholar]
Ashton P. R.; Ballardini R.; Balzani V.; GomezLopez M.; Lawrence S. E.; MartinezDiaz M. V.; Montalti M.; Piersanti A.; Prodi L.; Stoddart J. F.; et al. Molecular Meccano. 26. Hydrogen-bonded Complexes of Aromatic Crown Ethers with (9-Anthracenyl)methylammonium Derivatives. Supramolecular Photochemistry and Photophysics. pH-Controllable Supramolecular Switching. J. Am. Chem. Soc. 1997, 119, 10641–10651 10.1021/ja9715760. [DOI] [Google Scholar]
Devonport W.; Blower M. A.; Bryce M. R.; Goldenberg L. M. A Redox-active Tetrathiafulvalene [2]Pseudorotaxane: Spectroelectrochemical and Cyclic Voltammetric Studies of the Highly-reversible Complexation/decomplexation Process. J. Org. Chem. 1997, 62, 885–887 10.1021/jo960951o. [DOI] [Google Scholar]
Montalti M.; Prodi L. A Supramolecular Assembly Controlled by Anions: Threading and Unthreading of a Pseudorotaxane. Chem. Commun. 1998, 1461–1462 10.1039/a802157k. [DOI] [Google Scholar]
Matthews O. A.; Raymo F. M.; Stoddart J. F.; White A. J. P.; Williams D. J. Acid/Base-controlled Supramolecular Switch. New J. Chem. 1998, 22, 1131–1134 10.1039/a804742a. [DOI] [Google Scholar]
Asakawa M.; Ashton P. R.; Balzani V.; Boyd S. E.; Credi A.; Mattersteig G.; Menzer S.; Montalti M.; Raymo F. M.; Ruffilli C.; et al. Molecular Meccano, 49 - Pseudorotaxanes and Catenanes Containing a Redox-active Unit Derived from Tetrathiafulvalene. Eur. J. Org. Chem. 1999, 1999, 985–994. [DOI] [Google Scholar]
Balzani V. V.; Credi A.; Mattersteig G.; Matthews O. A.; Raymo F. M.; Stoddart J. F.; Venturi M.; White A. J.; Williams D. J. Switching of Pseudorotaxanes and Catenanes Incorporating a Tetrathiafulvalene Unit by Redox and Chemical Inputs. J. Org. Chem. 2000, 65, 1924–1936 10.1021/jo991781t. [DOI] [PubMed] [Google Scholar]
Balzani V. V.; Becher J.; Credi A.; Nielsen M. B.; Raymo F. M.; Stoddart J. F.; Talarico A. M.; Venturi M. The Electrochemically-driven Decomplexation/recomplexation of Inclusion Adducts of Ferrocene Derivatives with an Electron-accepting Receptor. J. Org. Chem. 2000, 65, 1947–1956 10.1021/jo991467z. [DOI] [PubMed] [Google Scholar]
Fujimoto T.; Nakamura A.; Inoue Y.; Sakata Y.; Kaneda T. Photoswitching of the Association of a Permethylated alpha-Cyclodextrin-azobenzene Dyad Forming a Janus [2]Pseudorotaxane. Tetrahedron Lett. 2001, 42, 7987–7989 10.1016/S0040-4039(01)01563-5. [DOI] [Google Scholar]
Kuwabara J.; Stern C. L.; Mirkin C. A. A Coordination Chemistry Approach to a Multieffector Enzyme Mimic. J. Am. Chem. Soc. 2007, 129, 10074–10075 10.1021/ja073447h. [DOI] [PubMed] [Google Scholar]
Zheng Y.; Yu Z. Y.; Parker R. M.; Wu Y. C.; Abell C.; Scherman O. A. Interfacial Assembly of Dendritic Microcapsules with Host-guest Chemistry. Nat. Commun. 2014, 5, 5772. 10.1038/ncomms6772. [DOI] [PubMed] [Google Scholar]
Horie M.; Suzaki Y.; Osakada K. Formation of Pseudorotaxane Induced by Electrochemical Oxidation of Ferrocene-containing Axis Molecule in the Presence of Crown Ether. J. Am. Chem. Soc. 2004, 126, 3684–3685 10.1021/ja039899l. [DOI] [PubMed] [Google Scholar]
Ballardini R.; Balzani V.; Credi A.; Gandolfi M. T.; Langford S. J.; Menzer S.; Prodi L.; Stoddart J. F.; Venturi M.; Williams D. J. Simple Molecular Machines: Chemically Driven Unthreading and Rethreading of a [2]Pseudorotaxane. Angew. Chem., Int. Ed. Engl. 1996, 35, 978–981 10.1002/anie.199609781. [DOI] [Google Scholar]
Ballardini R.; Balzani V.; Gandolfi M. T.; Prodi L.; Venturi M.; Philp D.; Ricketts H. G.; Stoddart J. F. A Photochemically Driven Molecular Machine. Angew. Chem., Int. Ed. Engl. 1993, 32, 1301–1303 10.1002/anie.199313011. [DOI] [Google Scholar]
Mock W. L.; Pierpont J. A Cucurbituril-Based Molecular Switch. J. Chem. Soc., Chem. Commun. 1990, 1509–1511 10.1039/c39900001509. [DOI] [Google Scholar]
Asakawa M.; Ashton P. R.; Balzani V.; Brown C. L.; Credi A.; Matthews O. A.; Newton S. P.; Raymo F. M.; Shipway A. N.; Spencer N.; et al. Photoactive Azobenzene-containing Supramolecular Complexes and Related Interlocked Molecular Compounds. Chem. - Eur. J. 1999, 5, 860–875. [DOI] [Google Scholar]
Jeppesen J. O.; Vignon S. A.; Stoddart J. F. In the Twilight Zone Between [2]Pseudorotaxanes and [2]Rotaxanes. Chem. - Eur. J. 2003, 9, 4611–4625 10.1002/chem.200304798. [DOI] [PubMed] [Google Scholar]
Jun S. I.; Lee J. W.; Sakamoto S.; Yamaguchi K.; Kim K. Rotaxane-based Molecular Switch with Fluorescence Signaling. Tetrahedron Lett. 2000, 41, 471–475 10.1016/S0040-4039(99)02094-8. [DOI] [Google Scholar]
Asakawa M.; Iqbal S.; Stoddart J. F.; Tinker N. D. Prototype of an Optically Responsive Molecular Switch Based on Pseudorotaxane. Angew. Chem., Int. Ed. Engl. 1996, 35, 976–978 10.1002/anie.199609761. [DOI] [Google Scholar]
Ashton P. R.; Balzani V.; Kocian O.; Prodi L.; Spencer N.; Stoddart J. F. A Light-fueled ″Piston Cylinder″ Molecular-level Machine. J. Am. Chem. Soc. 1998, 120, 11190–11191 10.1021/ja981889a. [DOI] [Google Scholar]
Ishow E.; Credi A.; Balzani V.; Spadola F.; Mandolini L. A Molecular-level Plug/socket System: Electronic Energy Transfer From a Binaphthyl Unit Incorporated into a Crown Ether to an Anthracenyl Unit Linked to an Ammonium Ion. Chem. - Eur. J. 1999, 5, 984–989. [DOI] [Google Scholar]
Ballardini R.; Balzani V.; Clemente-Leon M.; Credi A.; Gandolfi M. T.; Ishow E.; Perkins J.; Stoddart J. F.; Tseng H. R.; Wenger S. Photoinduced Electron Transfer in a Triad That can be Assembled/disassembled by Two Different External Inputs. Toward Molecular-level Electrical Extension Cables. J. Am. Chem. Soc. 2002, 124, 12786–12795 10.1021/ja025813x. [DOI] [PubMed] [Google Scholar]
Jeon W. S.; Ziganshina A. Y.; Lee J. W.; Ko Y. H.; Kang J. K.; Lee C.; Kim K. A [2]Pseudorotaxane-based Molecular Machine: Reversible Formation of a Molecular Loop Driven by Electrochemical and Photochemical Stimuli. Angew. Chem., Int. Ed. 2003, 42, 4097–4100 10.1002/anie.200351925. [DOI] [PubMed] [Google Scholar]
Jeon W. S.; Kim E.; Ko Y. H.; Hwang I.; Lee J. W.; Kim S. Y.; Kim H. J.; Kim K. Molecular Loop Lock: A Redox-driven Molecular Machine Based on a Host-stabilized Charge-transfer Complex. Angew. Chem., Int. Ed. 2005, 44, 87–91 10.1002/anie.200461806. [DOI] [PubMed] [Google Scholar]
Credi A.; Montalti M.; Balzani V.; Langford S. J.; Raymo F. M.; Stoddart J. F. Simple Molecular-level Machines. Interchange Between Different Threads in Pseudorotaxanes. New J. Chem. 1998, 22, 1061–1065 10.1039/a804787a. [DOI] [Google Scholar]
Ashton P. R.; Balzani V.; Becher J.; Credi A.; Fyfe M. C. T.; Mattersteig G.; Menzer S.; Nielsen M. B.; Raymo F. M.; Stoddart J. F.; et al. A Three-pole Supramolecular Switch. J. Am. Chem. Soc. 1999, 121, 3951–3957 10.1021/ja984341c. [DOI] [Google Scholar]
Chang K. J.; An Y. J.; Uh H.; Jeong K. S. Reversible Control of Assembly and Disassembly of Interlocked Supermolecules. J. Org. Chem. 2004, 69, 6556–6563 10.1021/jo0490548. [DOI] [PubMed] [Google Scholar]
Kaiser G.; Jarrosson T.; Otto S.; Ng Y. F.; Bond A. D.; Sanders J. K. M. Lithium-templated Synthesis of a Donor-acceptor Pseudorotaxane and Catenane. Angew. Chem., Int. Ed. 2004, 43, 1959–1962 10.1002/anie.200353075. [DOI] [PubMed] [Google Scholar]
Venturi M.; Dumas S.; Balzani V.; Cao J. G.; Stoddart J. F. Threading/dethreading Processes in Pseudorotaxanes. A Thermodynamic and Kinetic Study. New J. Chem. 2004, 28, 1032–1037 10.1039/b315933g. [DOI] [Google Scholar]
Nygaard S.; Laursen B. W.; Flood A. H.; Hansen C. N.; Jeppesen J. O.; Stoddart J. F. Quantifying the Working Stroke of Tetrathiafulvalene-based Electrochemically-driven Linear Motor-molecules. Chem. Commun. 2006, 144–146 10.1039/B511575B. [DOI] [PubMed] [Google Scholar]
Mirzoian A.; Kaifer A. E. Reactive Pseudorotaxanes: Inclusion Complexation of Reduced Viologens by the Hosts beta-Cyclodextrin and Heptakis(2,6-di-O-methyl)-beta-cyclodextrin. Chem. - Eur. J. 1997, 3, 1052–1058 10.1002/chem.19970030711. [DOI] [Google Scholar]
Eliadou K.; Yannakopoulou K.; Rontoyianni A.; Mavridis I. M. NMR Detection of Simultaneous Formation of [2]- and [3]Pseudorotaxanes in Aqueous Solution Between alpha-Cyclodextrin and Linear Aliphatic alpha,omega-Amino Acids, an alpha,omega-Diamine and an alpha,omega-Diacid of Similar Length, and Comparison with the Solid-state Structures. J. Org. Chem. 1999, 64, 6217–6226 10.1021/jo990021f. [DOI] [Google Scholar]
Huh K. M.; Ooya T.; Sasaki S.; Yui N. Polymer Inclusion Complex Consisting of Poly(epsilon-lysine) and alpha-Cyclodextrin. Macromolecules 2001, 34, 2402–2404 10.1021/ma0018648. [DOI] [Google Scholar]
Wisner J. A.; Beer P. D.; Drew M. G. B. A Demonstration of Anion Templation and Selectivity in Pseudorotaxane Formation. Angew. Chem., Int. Ed. 2001, 40, 3606–3609. [DOI] [PubMed] [Google Scholar]
Wisner J. A.; Beer P. D.; Berry N. G.; Tomapatanaget B. Anion Recognition as a Method for Templating Pseudorotaxane Formation. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4983–4986 10.1073/pnas.062637999. [DOI] [PMC free article] [PubMed] [Google Scholar]
Anelli P. L.; Ashton P. R.; Spencer N.; Slawin A. M. Z.; Stoddart J. F.; Williams D. J. Self-Assembling [2]Pseudorotaxanes. Angew. Chem., Int. Ed. Engl. 1991, 30, 1036–1039 10.1002/anie.199110361. [DOI] [Google Scholar]
Kraus T.; Budesinsky M.; Cvacka J. C.; Sauvage J.-P. Copper(I)-directed Formation of a Cyclic Pseudorotaxane Tetramer and its Trimeric Homologue. Angew. Chem., Int. Ed. 2006, 45, 258–261 10.1002/anie.200503163. [DOI] [PubMed] [Google Scholar]
Ashton P. R.; Baxter I.; Fyfe M. C. T.; Raymo F. M.; Spencer N.; Stoddart J. F.; White A. J. P.; Williams D. J. Rotaxane or Pseudorotaxane? That is the Question!. J. Am. Chem. Soc. 1998, 120, 2297–2307 10.1021/ja9731276. [DOI] [Google Scholar]
Collin J.-P.; Gavina P.; Sauvage J.-P. Electrochemically Induced Molecular Motions in a Copper(I) Complex Pseudorotaxane. Chem. Commun. 1996, 2005–2006 10.1039/cc9960002005. [DOI] [Google Scholar]
Wezenberg S. J.; Vlatkovic M.; Kistemaker J. C.; Feringa B. L. Multi-state Regulation of the Dihydrogen Phosphate Binding Affinity to a Light- and Heat-responsive Bis-urea Receptor. J. Am. Chem. Soc. 2014, 136, 16784–16787 10.1021/ja510700j. [DOI] [PubMed] [Google Scholar]
Terashima T.; Mes T.; De Greef T. F.; Gillissen M. A.; Besenius P.; Palmans A. R.; Meijer E. W. Single-chain Folding of Polymers for Catalytic Systems in Water. J. Am. Chem. Soc. 2011, 133, 4742–4745 10.1021/ja2004494. [DOI] [PubMed] [Google Scholar]
Giuseppone N.; Lutz J. F. Materials Chemistry: Catalytic Accordions. Nature 2011, 473, 40–41 10.1038/473040a. [DOI] [PubMed] [Google Scholar]
Zayed J. M.; Nouvel N.; Rauwald U.; Scherman O. A. Chemical Complexity--supramolecular Self-assembly of Synthetic and Biological Building Blocks in Water. Chem. Soc. Rev. 2010, 39, 2806–2816 10.1039/b922348g. [DOI] [PubMed] [Google Scholar]
Lee T. C.; Kalenius E.; Lazar A. I.; Assaf K. I.; Kuhnert N.; Grun C. H.; Janis J.; Scherman O. A.; Nau W. M. Chemistry Inside Molecular Containers in the Gas Phase. Nat. Chem. 2013, 5, 376–382 10.1038/nchem.1618. [DOI] [PubMed] [Google Scholar]
Zhang J.; Coulston R. J.; Jones S. T.; Geng J.; Scherman O. A.; Abell C. One-step Fabrication of Supramolecular Microcapsules from Microfluidic Droplets. Science 2012, 335, 690–694 10.1126/science.1215416. [DOI] [PubMed] [Google Scholar]
Goldup S. Artificial Molecular Machines: Two Steps Uphill. Nat. Nanotechnol. 2015, 10, 488–489 10.1038/nnano.2015.116. [DOI] [PubMed] [Google Scholar]
Nakamura T.; Takashima Y.; Hashidzume A.; Yamaguchi H.; Harada A. A Metal-ion-responsive Adhesive Material via Switching of Molecular Recognition Properties. Nat. Commun. 2014, 5, 4622. 10.1038/ncomms5622. [DOI] [PMC free article] [PubMed] [Google Scholar]
Adams H.; Chekmeneva E.; Hunter C. A.; Misuraca M. C.; Navarro C.; Turega S. M. Quantification of the Effect of Conformational Restriction on Supramolecular Effective Molarities. J. Am. Chem. Soc. 2013, 135, 1853–1863 10.1021/ja310221t. [DOI] [PubMed] [Google Scholar]
Ariga K.; Ito H.; Hill J. P.; Tsukube H. Molecular Recognition: From Solution Science to Nano/materials Technology. Chem. Soc. Rev. 2012, 41, 5800–5835 10.1039/c2cs35162e. [DOI] [PubMed] [Google Scholar]
Rieth S.; Hermann K.; Wang B. Y.; Badjic J. D. Controlling the Dynamics of Molecular Encapsulation and Gating. Chem. Soc. Rev. 2011, 40, 1609–1622 10.1039/C005254J. [DOI] [PubMed] [Google Scholar]
Witlicki E. H.; Johnsen C.; Hansen S. W.; Silverstein D. W.; Bottomley V. J.; Jeppesen J. O.; Wong E. W.; Jensen L.; Flood A. H. Molecular Logic Gates Using Surface-Enhanced Raman-Scattered Light. J. Am. Chem. Soc. 2011, 133, 7288–7291 10.1021/ja200992x. [DOI] [PubMed] [Google Scholar]
Berryman O. B.; Sather A. C.; Rebek J. A Light Controlled Cavitand Wall Regulates Guest Binding. Chem. Commun. 2011, 47, 656–658 10.1039/C0CC03865B. [DOI] [PMC free article] [PubMed] [Google Scholar]
Dube H.; Ajami D.; Rebek J. Photochemical Control of Reversible Encapsulation. Angew. Chem., Int. Ed. 2010, 49, 3192–3195 10.1002/anie.201000876. [DOI] [PubMed] [Google Scholar]
Rogez G.; Ribera B. F.; Credi A.; Ballardini R.; Gandolfi M. T.; Balzani V.; Liu Y.; Northrop B. H.; Stoddart J. F. A Molecular Plug-socket Connector. J. Am. Chem. Soc. 2007, 129, 4633–4642 10.1021/ja067739e. [DOI] [PubMed] [Google Scholar]
Arduini A.; Bussolati R.; Credi A.; Secchi A.; Silvi S.; Semeraro M.; Venturi M. Toward Directionally Controlled Molecular Motions and Kinetic Intra- and Intermolecular Self-Sorting: Threading Processes of Nonsymmetric Wheel and Axle Components. J. Am. Chem. Soc. 2013, 135, 9924–9930 10.1021/ja404270c. [DOI] [PubMed] [Google Scholar]
Baroncini M.; Silvi S.; Venturi M.; Credi A. Photoactivated Directionally Controlled Transit of a Non-Symmetric Molecular Axle Through a Macrocycle. Angew. Chem., Int. Ed. 2012, 51, 4223–4226 10.1002/anie.201200555. [DOI] [PubMed] [Google Scholar]
Cao D.; Amelia M.; Klivansky L. M.; Koshkakaryan G.; Khan S. I.; Semeraro M.; Silvi S.; Venturi M.; Credi A.; Liu Y. Probing Donor-Acceptor Interactions and Co-Conformational Changes in Redox Active Desymmetrized [2]Catenanes. J. Am. Chem. Soc. 2010, 132, 1110–1122 10.1021/ja909041g. [DOI] [PubMed] [Google Scholar]
Leblond J.; Petitjean A. Molecular Tweezers: Concepts and Applications. ChemPhysChem 2011, 12, 1043–1051 10.1002/cphc.201001050. [DOI] [PubMed] [Google Scholar]
Legouin B.; Gayral M.; Uriac P.; Cupif J. F.; Levoin N.; Toupet L.; van de Weghe P. Molecular Tweezers: Synthesis and Formation of Host-Guest Complexes. Eur. J. Org. Chem. 2010, 2010, 5503–5508 10.1002/ejoc.201000729. [DOI] [Google Scholar]
Bier D.; Rose R.; Bravo-Rodriguez K.; Bartel M.; Ramirez-Anguita J. M.; Dutt S.; Wilch C.; Klarner F. G.; Sanchez-Garcia E.; Schrader T.; Ottmann C. Molecular Tweezers Modulate 14–3-3 Protein-protein Interactions. Nat. Chem. 2013, 5, 234–239 10.1038/nchem.1570. [DOI] [PubMed] [Google Scholar]
Colquhoun H. M.; Zhu Z. X. Recognition of Polyimide Sequence Information by a Molecular Tweezer. Angew. Chem., Int. Ed. 2004, 43, 5040–5045 10.1002/anie.200460382. [DOI] [PubMed] [Google Scholar]
Gianneschi N. C.; Cho S. H.; Nguyen S. T.; Mirkin C. A. Reversibly Addressing an Allosteric Catalyst in situ: Catalytic Molecular Tweezers. Angew. Chem., Int. Ed. 2004, 43, 5503–5507 10.1002/anie.200460932. [DOI] [PubMed] [Google Scholar]
Guther R.; Nieger M.; Vogtle F. Molecular Tweezers with a Hydrocarbon Skeleton and Convergent Carboxyl Groups. Angew. Chem., Int. Ed. Engl. 1993, 32, 601–603 10.1002/anie.199306011. [DOI] [Google Scholar]
Hardouin-Lerouge M.; Hudhomme P.; Salle M. Molecular Clips and Tweezers Hosting Neutral Guests. Chem. Soc. Rev. 2011, 40, 30–43 10.1039/B915145C. [DOI] [PubMed] [Google Scholar]
Klarner F. G.; Schrader T. Aromatic Interactions by Molecular Tweezers and Clips in Chemical and Biological Systems. Acc. Chem. Res. 2013, 46, 967–978 10.1021/ar300061c. [DOI] [PubMed] [Google Scholar]
Leblond J.; Gao H.; Petitjean A.; Leroux J. C. pH-Responsive Molecular Tweezers. J. Am. Chem. Soc. 2010, 132, 8544–8545 10.1021/ja103153t. [DOI] [PubMed] [Google Scholar]
Zimmerman S. C. Rigid Molecular Tweezers as Hosts for the Complexation of Neutral Guests. Top. Curr. Chem. 1993, 165, 71–102. [Google Scholar]
Shinkai S.; Nakaji T.; Ogawa T.; Shigematsu K.; Manabe O. Photoresponsive Crown Ethers 0.2. Photocontrol of Ion Extraction and Ion-Transport by a Bis(Crown Ether) with a Butterfly-Like Motion. J. Am. Chem. Soc. 1981, 103, 111–115 10.1021/ja00391a021. [DOI] [Google Scholar]
Shinkai S.; Ishihara M.; Ueda K.; Manabe O. Photoresponsive Crown Ethers 0.14. Photoregulated Crown Metal Complexation by Competitive Intramolecular Tail(Ammonium)-Biting. J. Chem. Soc., Perkin Trans. 2 1985, 511–518 10.1039/p29850000511. [DOI] [Google Scholar]
Perez E. M.; Sanchez L.; Fernandez G.; Martin N. exTTF as a Building Block for Fullerene Receptors. Unexpected Solvent-dependent Positive Homotropic Cooperativity. J. Am. Chem. Soc. 2006, 128, 7172–7173 10.1021/ja0621389. [DOI] [PubMed] [Google Scholar]
Zimmerman S. C.; Vanzyl C. M.; Hamilton G. S. Rigid Molecular Tweezers - Preorganized Hosts for Electron-Donor Acceptor Complexation in Organic-Solvents. J. Am. Chem. Soc. 1989, 111, 1373–1381 10.1021/ja00186a035. [DOI] [Google Scholar]
Molt O.; Rubeling D.; Schrader T. A Selective Biomimetic Tweezer for Noradrenaline. J. Am. Chem. Soc. 2003, 125, 12086–12087 10.1021/ja035212l. [DOI] [PubMed] [Google Scholar]
Etxebarria J.; Vidal-Ferran A.; Ballester P. The Effect of Complex Stoichiometry in Supramolecular Chirality Transfer to Zinc Bisporphyrin Systems. Chem. Commun. 2008, 5939–5941 10.1039/b812819g. [DOI] [PubMed] [Google Scholar]
Ulrich S.; Petitjean A.; Lehn J.-M. Metallo-Controlled Dynamic Molecular Tweezers: Design, Synthesis, and Self-Assembly by Metal-Ion Coordination. Eur. J. Inorg. Chem. 2010, 2010, 1913–1928 10.1002/ejic.200901262. [DOI] [Google Scholar]
Petitjean A.; Khoury R. G.; Kyritsakas N.; Lehn J.-M. Dynamic Devices. Shape Switching and Substrate Binding in Ion-controlled Nanomechanical Molecular Tweezers. J. Am. Chem. Soc. 2004, 126, 6637–6647 10.1021/ja031915r. [DOI] [PubMed] [Google Scholar]
Petitjean A.; Kyritsakas N.; Lehn J.-M. Ion-triggered Multistate Molecular Switching Device Based on Regioselective Coordination-controlled Ion Binding. Chem. - Eur. J. 2005, 11, 6818–6828 10.1002/chem.200500625. [DOI] [PubMed] [Google Scholar]
Linke-Schaetzel M.; Anson C. E.; Powell A. K.; Buth G.; Palomares E.; Durrant J. D.; Balaban T. S.; Lehn J.-M. Dynamic Chemical Devices: Photoinduced Electron Transfer and its Ion-triggered Switching in Nanomechanical Butterfly-type Bis(porphyrin)terpyridines. Chem. - Eur. J. 2006, 12, 1931–1940 10.1002/chem.200500602. [DOI] [PubMed] [Google Scholar]
Oliveri C. G.; Ulmann P. A.; Wiester M. J.; Mirkin C. A. Heteroligated Supramolecular Coordination Complexes Formed via the Halide-Induced Ligand Rearrangement Reaction. Acc. Chem. Res. 2008, 41, 1618–1629 10.1021/ar800025w. [DOI] [PMC free article] [PubMed] [Google Scholar]
Oliveri C. G.; Nguyen S. T.; Mirkin C. A. A Highly Modular and Convergent Approach for the Synthesis of Stimulant-responsive Heteroligated Cofacial Porphyrin Tweezer Complexes. Inorg. Chem. 2008, 47, 2755–2763 10.1021/ic702150y. [DOI] [PubMed] [Google Scholar]
Skibinski M.; Gomez R.; Lork E.; Azov V. A. Redox Responsive Molecular Tweezers with Tetrathiafulvalene Units: Synthesis, Electrochemistry, and Binding Properties. Tetrahedron 2009, 65, 10348–10354 10.1016/j.tet.2009.10.052. [DOI] [Google Scholar]
Tian F.; Jiao D. Z.; Biedermann F.; Scherman O. A. Orthogonal Switching of a Single Supramolecular Complex. Nat. Commun. 2012, 3, 1207. 10.1038/ncomms2198. [DOI] [PubMed] [Google Scholar]
Miwa K.; Furusho Y.; Yashima E. Ion-triggered Spring-like Motion of a Double helicate Accompanied by Anisotropic Twisting. Nat. Chem. 2010, 2, 444–449 10.1038/nchem.649. [DOI] [PubMed] [Google Scholar]
Yamamoto S.; Iida H.; Yashima E. Guest-Induced Unidirectional Dual Rotary and Twisting Motions of a Spiroborate-Based Double-Stranded Helicate Containing a Bisporphyrin Unit. Angew. Chem., Int. Ed. 2013, 52, 6849–6853 10.1002/anie.201302560. [DOI] [PubMed] [Google Scholar]
Ferrand Y.; Gan Q.; Kauffmann B.; Jiang H.; Huc I. Template-Induced Screw Motions within an Aromatic Amide Foldamer Double Helix. Angew. Chem., Int. Ed. 2011, 50, 7572–7575 10.1002/anie.201101697. [DOI] [PubMed] [Google Scholar]
Hua Y.; Liu Y.; Chen C. H.; Flood A. H. Hydrophobic Collapse of Foldamer Capsules Drives Picomolar-level Chloride Binding in Aqueous Acetonitrile Solutions. J. Am. Chem. Soc. 2013, 135, 14401–14412 10.1021/ja4074744. [DOI] [PubMed] [Google Scholar]
Juwarker H.; Jeong K. S. Anion-controlled Foldamers. Chem. Soc. Rev. 2010, 39, 3664–3674 10.1039/b926162c. [DOI] [PubMed] [Google Scholar]
Gan Q.; Ronson T. K.; Vosburg D. A.; Thoburn J. D.; Nitschke J. R. Cooperative Loading and Release Behavior of a Metal-Organic Receptor. J. Am. Chem. Soc. 2015, 137, 1770–1773 10.1021/ja5120437. [DOI] [PubMed] [Google Scholar]
Hua Y. R.; Flood A. H. Flipping the Switch on Chloride Concentrations with a Light-Active Foldamer. J. Am. Chem. Soc. 2010, 132, 12838–12840 10.1021/ja105793c. [DOI] [PubMed] [Google Scholar]
Li Y.; Flood A. H.; Pure C.-H. Hydrogen Bonding to Chloride Ions: A Preorganized and Rigid Macrocyclic Receptor. Angew. Chem., Int. Ed. 2008, 47, 2649–2652 10.1002/anie.200704717. [DOI] [PubMed] [Google Scholar]
Li Y.; Flood A. H. Strong, Size-selective, and Electronically Tunable C-H···Halide Binding with Steric Control over Aggregation From Synthetically Modular, Shape-persistent [34]Triazolophanes. J. Am. Chem. Soc. 2008, 130, 12111–12122 10.1021/ja803341y. [DOI] [PubMed] [Google Scholar]
Hua Y.; Flood A. H. Click Chemistry Generates Privileged CH Hydrogen-bonding Triazoles: The Latest Addition to Anion Supramolecular Chemistry. Chem. Soc. Rev. 2010, 39, 1262–1271 10.1039/b818033b. [DOI] [PubMed] [Google Scholar]
Juwarker H.; Lenhardt J. M.; Pham D. M.; Craig S. L. 1,2,3-Triazole CH···Cl^– Contacts Guide Anion Binding and Concomitant Folding in 1,4-Diaryl Triazole Oligomers. Angew. Chem., Int. Ed. 2008, 47, 3740–3743 10.1002/anie.200800548. [DOI] [PubMed] [Google Scholar]
Meudtner R. M.; Hecht S. Helicity Inversion in Responsive Foldamers Induced by Achiral Halide Ion Guests. Angew. Chem., Int. Ed. 2008, 47, 4926–4930 10.1002/anie.200800796. [DOI] [PubMed] [Google Scholar]
Lee S.; Hua Y. R.; Flood A. H. beta-Sheet-like Hydrogen Bonds Interlock the Helical Turns of a Photoswitchable Foldamer To Enhance the Binding and Release of Chloride. J. Org. Chem. 2014, 79, 8383–8396 10.1021/jo501595k. [DOI] [PubMed] [Google Scholar]
Lee S.; Flood A. H. Photoresponsive Receptors for Binding and Releasing Anions. J. Phys. Org. Chem. 2013, 26, 79–86 10.1002/poc.2973. [DOI] [Google Scholar]
Suk J.-m.; Naidu V. R.; Liu X.; Lah M. S.; Jeong K.-S. A Foldamer-Based Chiroptical Molecular Switch That Displays Complete Inversion of the Helical Sense upon Anion Binding. J. Am. Chem. Soc. 2011, 133, 13938–13941 10.1021/ja206546b. [DOI] [PubMed] [Google Scholar]
Campbell V. E.; de Hatten X.; Delsuc N.; Kauffmann B.; Huc I.; Nitschke J. R. Cascading Transformations within a Dynamic Self-assembled System. Nat. Chem. 2010, 2, 684–687 10.1038/nchem.693. [DOI] [PubMed] [Google Scholar]
Lanyi J. K. Bacteriorhodopsin as a Model for Proton Pumps. Nature 1995, 375, 461–463 10.1038/375461a0. [DOI] [PubMed] [Google Scholar]
Amendola V.; Fabbrizzi L.; Mangano C.; Pallavicini P. Molecular Machines Based on Metal Ion Translocation. Acc. Chem. Res. 2001, 34, 488–493 10.1021/ar010011c. [DOI] [PubMed] [Google Scholar]
Zhao J. Z.; Ji S. M.; Chen Y. H.; Guo H. M.; Yang P. Excited State Intramolecular Proton Transfer (ESIPT): From Principal Photophysics to the Development of New Chromophores and Applications in Fluorescent Molecular Probes and Luminescent Materials. Phys. Chem. Chem. Phys. 2012, 14, 8803–8817 10.1039/C2CP23144A. [DOI] [PubMed] [Google Scholar]
Iijima T.; Momotake A.; Shinohara Y.; Sato T.; Nishimura Y.; Arai T. Excited-State Intramolecular Proton Transfer of Naphthalene-Fused 2-(2′-Hydroxyaryl)benzazole Family. J. Phys. Chem. A 2010, 114, 1603–1609 10.1021/jp904370t. [DOI] [PubMed] [Google Scholar]
Fabbrizzi L.; Gatti F.; Pallavicini P.; Zambarbieri E. Redox-driven Intramolecular Anion Translocation Between Transition Metal Centers. Chem. - Eur. J. 1999, 5, 682–690. [DOI] [Google Scholar]
Yoo H. J.; Mirkin C. A.; DiPasquale A. G.; Rheingold A. L.; Stern C. L. Reversible CO-Induced Chloride Shuttling in Rh-I Tweezer Complexes Containing Urea-Functionalized Hemilabile Ligands. Inorg. Chem. 2008, 47, 9727–9729 10.1021/ic8008909. [DOI] [PubMed] [Google Scholar]
Zelikovich L.; Libman J.; Shanzer A. Molecular Redox Switches Based on Chemical Triggering of Iron Translocation in Triple-Stranded Helical Complexes. Nature 1995, 374, 790–792 10.1038/374790a0. [DOI] [Google Scholar]
Amendola V.; Fabbrizzi L.; Mangano C.; Miller H.; Pallavicini P.; Perotti A.; Taglietti A. Signal Amplification by a Fluorescent Indicator of a pH-Driven Intramolecular Translocation of a Copper(II) Ion. Angew. Chem., Int. Ed. 2002, 41, 2553–2356. [DOI] [PubMed] [Google Scholar]
Amendola V.; Fabbrizzi L.; Mangano C.; Pallavicini P.; Perotti A.; Taglietti A. pH-Controlled Translocation of Ni^II Within a Ditopic Receptor Bearing an Appended Anthracene Fragment: A Mechanical Switch of Fluorescence. J. Chem. Soc. Dalton 2000, 185–189 10.1039/a907966a. [DOI] [Google Scholar]
Colasson B.; Le Poul N.; Le Mest Y.; Reinaud O. Electrochemically Triggered Double Translocation of Two Different Metal Ions with a Ditopic Calix[6]arene Ligand. J. Am. Chem. Soc. 2010, 132, 4393–4398 10.1021/ja910676z. [DOI] [PubMed] [Google Scholar]
Dotz K. H.; Jahr H. C. Tunable Haptotropic Metal Migration in Fused Arenes: Towards Organometallic Switches. Chem. Rec. 2004, 4, 61–71 10.1002/tcr.20007. [DOI] [PubMed] [Google Scholar]
Murahashi T.; Shirato K.; Fukushima A.; Takase K.; Suenobu T.; Fukuzumi S.; Ogoshi S.; Kurosawa H. Redox-induced Reversible Metal Assembly Through Translocation and Reversible Ligand Coupling in Tetranuclear Metal Sandwich Frameworks. Nat. Chem. 2012, 4, 52–58 10.1038/nchem.1202. [DOI] [PubMed] [Google Scholar]
Wozny M.; Pawlowska J.; Osior A.; Swider P.; Bilewicz R.; Korybut-Daszkiewicz B. An Electrochemically Switchable Foldamer - A Surprising Feature of a Rotaxane with Equivalent Stations. Chem. Sci. 2014, 5, 2836–2842 10.1039/c4sc00449c. [DOI] [Google Scholar]
Chao S.; Romuald C.; Fournel-Marotte K.; Clavel C.; Coutrot F. A Strategy Utilizing a Recyclable Macrocycle Transporter for the Efficient Synthesis of a Triazolium-Based [2]Rotaxane. Angew. Chem., Int. Ed. 2014, 53, 6914–6919 10.1002/anie.201403765. [DOI] [PubMed] [Google Scholar]
Langton M. J.; Blackburn O. A.; Lang T.; Faulkner S.; Beer P. D. Nitrite-Templated Synthesis of Lanthanide-Containing [2]Rotaxanes for Anion Sensing. Angew. Chem., Int. Ed. 2014, 53, 11463–11466 10.1002/anie.201405131. [DOI] [PMC free article] [PubMed] [Google Scholar]
Nygaard S.; Laursen B. W.; Hansen T. S.; Bond A. D.; Flood A. H.; Jeppesen J. O. Preparation of Cyclobis(paraquat-p-phenylene)-Based [2]Rotaxanes Without Flexible Glycol Chains. Angew. Chem., Int. Ed. 2007, 46, 6093–6097 10.1002/anie.200701722. [DOI] [PubMed] [Google Scholar]
Klivansky L. M.; Koshkakaryan G.; Cao D.; Liu Y. Linear π-Acceptor-Templated Dynamic Clipping to Macrobicycles and [2]Rotaxanes. Angew. Chem., Int. Ed. 2009, 48, 4185–4189 10.1002/anie.200900716. [DOI] [PubMed] [Google Scholar]
Prikhod'ko A. I.; Sauvage J.-P. Passing Two Strings through the Same Ring Using an Octahedral Metal Center as Template: A New Synthesis of [3]Rotaxanes. J. Am. Chem. Soc. 2009, 131, 6794–6807 10.1021/ja809267z. [DOI] [PubMed] [Google Scholar]
Goldup S. M.; Leigh D. A.; Lusby P. J.; McBurney R. T.; Slawin A. M. Z. Active Template Synthesis of Rotaxanes and Molecular Shuttles with Switchable Dynamics by Four-Component Pd^II-Promoted Michael Additions. Angew. Chem., Int. Ed. 2008, 47, 3381–3384 10.1002/anie.200705859. [DOI] [PubMed] [Google Scholar]
Ikeda T.; Higuchi M.; Kurth D. G. From Thiophene [2]Rotaxane to Polythiophene Polyrotaxane. J. Am. Chem. Soc. 2009, 131, 9158–9159 10.1021/ja902992c. [DOI] [PubMed] [Google Scholar]
Collin J.-P.; Durola F.; Frey J.; Heitz V.; Reviriego F.; Sauvage J.-P.; Trolez Y.; Rissanen K. Templated Synthesis of Cyclic [4]Rotaxanes Consisting of Two Stiff Rods Threaded through Two Bis-macrocycles with a Large and Rigid Central Plate as Spacer. J. Am. Chem. Soc. 2010, 132, 6840–6850 10.1021/ja101759w. [DOI] [PubMed] [Google Scholar]
Xue Z.; Mayer M. F. Actuator Prototype: Capture and Release of a Self-Entangled [1]Rotaxane. J. Am. Chem. Soc. 2010, 132, 3274–3276 10.1021/ja9077655. [DOI] [PubMed] [Google Scholar]
Altieri A.; Aucagne V.; Carrillo R.; Clarkson G. J.; D’Souza D. M.; Dunnett J. A.; Leigh D. A.; Mullen K. M. Sulfur-containing Amide-based [2]Rotaxanes and Molecular Shuttles. Chem. Sci. 2011, 2, 1922–1928 10.1039/c1sc00335f. [DOI] [Google Scholar]
De Bo G.; De Winter J.; Gerbaux P.; Fustin C.-A. Rotaxane-Based Mechanically Linked Block Copolymers. Angew. Chem., Int. Ed. 2011, 50, 9093–9096 10.1002/anie.201103716. [DOI] [PubMed] [Google Scholar]
Zhang Z.-J.; Zhang H.-Y.; Wang H.; Liu Y. A Twin-Axial Hetero[7]rotaxane. Angew. Chem., Int. Ed. 2011, 50, 10834–10838 10.1002/anie.201105375. [DOI] [PubMed] [Google Scholar]
Li H.; Fahrenbach A. C.; Coskun A.; Zhu Z.; Barin G.; Zhao Y.-L.; Botros Y. Y.; Sauvage J.-P.; Stoddart J. F. A Light-Stimulated Molecular Switch Driven by Radical–Radical Interactions in Water. Angew. Chem., Int. Ed. 2011, 50, 6782–6788 10.1002/anie.201102510. [DOI] [PubMed] [Google Scholar]
Nepogodiev S. A.; Stoddart J. F. Cyclodextrin-Based Catenanes and Rotaxanes. Chem. Rev. 1998, 98, 1959–1976 10.1021/cr970049w. [DOI] [PubMed] [Google Scholar]
Dietrich-Buchecker C. O.; Sauvage J.-P. Interlocking of Molecular Threads: from the Statistical Approach to the Templated Synthesis of Catenands. Chem. Rev. 1987, 87, 795–810 10.1021/cr00080a007. [DOI] [Google Scholar]
Anderson S.; Anderson H. L.; Sanders J. K. M. Expanding Roles for Templates in Synthesis. Acc. Chem. Res. 1993, 26, 469–475 10.1021/ar00033a003. [DOI] [Google Scholar]
Fuller A.-M.; Leigh D. A.; Lusby P. J.; Oswald I. D. H.; Parsons S.; Walker D. B. A 3D Interlocked Structure from a 2D Template: Structural Requirements for the Assembly of a Square-Planar Metal-Coordinated [2]Rotaxane. Angew. Chem., Int. Ed. 2004, 43, 3914–3918 10.1002/anie.200353622. [DOI] [PubMed] [Google Scholar]
Cantrill S. J.; Chichak K. S.; Peters A. J.; Stoddart J. F. Nanoscale Borromean Rings. Acc. Chem. Res. 2005, 38, 1–9 10.1021/ar040226x. [DOI] [PubMed] [Google Scholar]
Chambron J.-C.; Collin J.-P.; Heitz V.; Jouvenot D.; Kern J.-M.; Mobian P.; Pomeranc D.; Sauvage J.-P. Rotaxanes and Catenanes Built Around Octahedral Transition Metals. Eur. J. Org. Chem. 2004, 2004, 1627–1638 10.1002/ejoc.200300341. [DOI] [Google Scholar]
Dietrich-Buchecker C.; Rapenne G.; Sauvage J.-P. Synthesis of Catenanes and Molecular Knots by Copper(I)-directed Formation of the Precursors Followed by Ruthenium(II)-Catalysed Ring-closing Metathesis. Coord. Chem. Rev. 1999, 185–186, 167–176 10.1016/S0010-8545(98)00266-5. [DOI] [Google Scholar]
Fujita M. Self-Assembly of [2]Catenanes Containing Metals in Their Backbones. Acc. Chem. Res. 1999, 32, 53–61 10.1021/ar9701068. [DOI] [Google Scholar]
Fujita M.; Ogura K. Transition-metal-directed Assembly of Well-defined Organic Architectures Possessing Large Voids: From Macrocycles to [2] Catenanes. Coord. Chem. Rev. 1996, 148, 249–264 10.1016/0010-8545(95)01212-5. [DOI] [Google Scholar]
Busch D. H.; Stephenson N. A. Molecular Organization, Portal to Supramolecular Chemistry: Structural Analysis of the Factors Associated with Molecular Organization in Coordination and Inclusion Chemistry, Including the Coordination Template Effect. Coord. Chem. Rev. 1990, 100, 119–154 10.1016/0010-8545(90)85007-F. [DOI] [Google Scholar]
Sauvage J.-P. Interlacing Molecular Threads on Transition Metals: Catenands, Catenates, and Knots. Acc. Chem. Res. 1990, 23, 319–327 10.1021/ar00178a001. [DOI] [Google Scholar]
Hubin T. J.; Busch D. H. Template Routes to Interlocked Molecular Structures and Orderly Molecular Entanglements. Coord. Chem. Rev. 2000, 200–202, 5–52 10.1016/S0010-8545(99)00242-8. [DOI] [Google Scholar]
Hoss R.; Vögtle F. Template Syntheses. Angew. Chem., Int. Ed. Engl. 1994, 33, 375–384 10.1002/anie.199403751. [DOI] [Google Scholar]
Claessens C. G.; Stoddart J. F. π–π Interactions in Self-Assembly. J. Phys. Org. Chem. 1997, 10, 254–272. [DOI] [Google Scholar]
Gillard R. E.; Raymo F. M.; Stoddart J. F. Controlling Self-Assembly. Chem. - Eur. J. 1997, 3, 1933–1940 10.1002/chem.19970031208. [DOI] [Google Scholar]
Philp D.; Stoddart J. F. Self-Assembly in Organic Synthesis. Synlett 1991, 1991, 445–458 10.1055/s-1991-20759. [DOI] [Google Scholar]
Hogg L.; Leigh D. A.; Lusby P. J.; Morelli A.; Parsons S.; Wong J. K. Y. A Simple General Ligand System for Assembling Octahedral Metal–Rotaxane Complexes. Angew. Chem., Int. Ed. 2004, 43, 1218–1221 10.1002/anie.200353186. [DOI] [PubMed] [Google Scholar]
Hannam J. S.; Kidd T. J.; Leigh D. A.; Wilson A. J. Magic Rod” Rotaxanes: The Hydrogen Bond-Directed Synthesis of Molecular Shuttles under Thermodynamic Control. Org. Lett. 2003, 5, 1907–1910 10.1021/ol0344927. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Lusby P. J.; Teat S. J.; Wilson A. J.; Wong J. K. Y. Benzylic Imine Catenates: Readily Accessible Octahedral Analogues of the Sauvage Catenates. Angew. Chem., Int. Ed. 2001, 40, 1538–1543. [DOI] [PubMed] [Google Scholar]
Kidd T. J.; Leigh D. A.; Wilson A. J. Organic “Magic Rings”: The Hydrogen Bond-Directed Assembly of Catenanes under Thermodynamic Control. J. Am. Chem. Soc. 1999, 121, 1599–1600 10.1021/ja983106r. [DOI] [Google Scholar]
Seel C.; Vögtle F. Templates, “Wheeled Reagents”, and a New Route to Rotaxanes by Anion Complexation: The Trapping Method. Chem. - Eur. J. 2000, 6, 21–24. [DOI] [PubMed] [Google Scholar]
Aucagne V.; Leigh D. A.; Lock J. S.; Thomson A. R. Rotaxanes of Cyclic Peptides. J. Am. Chem. Soc. 2006, 128, 1784–1785 10.1021/ja057206q. [DOI] [PubMed] [Google Scholar]
Biscarini F.; Cavallini M.; Leigh D. A.; León S.; Teat S. J.; Wong J. K. Y.; Zerbetto F. The Effect of Mechanical Interlocking on Crystal Packing: Predictions and Testing. J. Am. Chem. Soc. 2002, 124, 225–233 10.1021/ja0159362. [DOI] [PubMed] [Google Scholar]
Johnston A. G.; Leigh D. A.; Nezhat L.; Smart J. P.; Deegan M. D. Structurally Diverse and Dynamically Versatile Benzylic Amide [2]Catenanes Assembled Directly from Commercially Available Precursors. Angew. Chem., Int. Ed. Engl. 1995, 34, 1212–1216 10.1002/anie.199512121. [DOI] [Google Scholar]
Johnston A. G.; Leigh D. A.; Pritchard R. J.; Deegan M. D. Facile Synthesis and Solid-State Structure of a Benzylic Amide [2]Catenane. Angew. Chem., Int. Ed. Engl. 1995, 34, 1209–1212 10.1002/anie.199512091. [DOI] [Google Scholar]
Jäger R.; Vögtle F. A New Synthetic Strategy towards Molecules with Mechanical Bonds: Nonionic Template Synthesis of Amide-Linked Catenanes and Rotaxanes. Angew. Chem., Int. Ed. Engl. 1997, 36, 930–944 10.1002/anie.199709301. [DOI] [Google Scholar]
Aucagne V.; Hänni K. D.; Leigh D. A.; Lusby P. J.; Walker D. B. Catalytic “Click” Rotaxanes: A Substoichiometric Metal-Template Pathway to Mechanically Interlocked Architectures. J. Am. Chem. Soc. 2006, 128, 2186–2187 10.1021/ja056903f. [DOI] [PubMed] [Google Scholar]
Crowley J. D.; Hänni K. D.; Lee A.-L.; Leigh D. A. [2]Rotaxanes through Palladium Active-Template Oxidative Heck Cross-Couplings. J. Am. Chem. Soc. 2007, 129, 12092–12093 10.1021/ja075219t. [DOI] [PubMed] [Google Scholar]
Crowley J. D.; Hänni K. D.; Leigh D. A.; Slawin A. M. Z. Diels–Alder Active-Template Synthesis of Rotaxanes and Metal-Ion-Switchable Molecular Shuttles. J. Am. Chem. Soc. 2010, 132, 5309–5314 10.1021/ja101029u. [DOI] [PubMed] [Google Scholar]
Crowley J. D.; Goldup S. M.; Gowans N. D.; Leigh D. A.; Ronaldson V. E.; Slawin A. M. Z. An Unusual Nickel–Copper-Mediated Alkyne Homocoupling Reaction for the Active-Template Synthesis of [2]Rotaxanes. J. Am. Chem. Soc. 2010, 132, 6243–6248 10.1021/ja101121j. [DOI] [PubMed] [Google Scholar]
De Bo G.; Kuschel S.; Leigh D. A.; Lewandowski B.; Papmeyer M.; Ward J. W. Efficient Assembly of Threaded Molecular Machines for Sequence-Specific Synthesis. J. Am. Chem. Soc. 2014, 136, 5811–5814 10.1021/ja5022415. [DOI] [PubMed] [Google Scholar]
Goldup S. M.; Leigh D. A.; Lusby P. J.; McBurney R. T.; Slawin A. M. Z. Gold(I)-Template Catenane and Rotaxane Synthesis. Angew. Chem., Int. Ed. 2008, 47, 6999–7003 10.1002/anie.200801904. [DOI] [PubMed] [Google Scholar]
Goldup S. M.; Leigh D. A.; McBurney R. T.; McGonigal P. R.; Plant A. Ligand-assisted Nickel-catalysed sp³-sp³ Homocoupling of Unactivated Alkyl Bromides and its Application to the Active Template Synthesis of Rotaxanes. Chem. Sci. 2010, 1, 383–386 10.1039/c0sc00279h. [DOI] [Google Scholar]
Ahmed R.; Altieri A.; D’Souza D. M.; Leigh D. A.; Mullen K. M.; Papmeyer M.; Slawin A. M. Z.; Wong J. K. Y.; Woollins J. D. Phosphorus-Based Functional Groups as Hydrogen Bonding Templates for Rotaxane Formation. J. Am. Chem. Soc. 2011, 133, 12304–12310 10.1021/ja2049786. [DOI] [PubMed] [Google Scholar]
Cheng H. M.; Leigh D. A.; Maffei F.; McGonigal P. R.; Slawin A. M. Z.; Wu J. En Route to a Molecular Sheaf: Active Metal Template Synthesis of a [3]Rotaxane with Two Axles Threaded through One Ring. J. Am. Chem. Soc. 2011, 133, 12298–12303 10.1021/ja205167e. [DOI] [PubMed] [Google Scholar]
Lewandowski B.; De Bo G.; Ward J. W.; Papmeyer M.; Kuschel S.; Aldegunde M. J.; Gramlich P. M. E.; Heckmann D.; Goldup S. M.; D’Souza D. M.; Fernandes A. E.; Leigh D. A. Sequence-Specific Peptide Synthesis by an Artificial Small-Molecule Machine. Science 2013, 339, 189–193 10.1126/science.1229753. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Lusby P. J.; McBurney R. T.; Morelli A.; Slawin A. M. Z.; Thomson A. R.; Walker D. B. Getting Harder: Cobalt(III)-Template Synthesis of Catenanes and Rotaxanes. J. Am. Chem. Soc. 2009, 131, 3762–3771 10.1021/ja809627j. [DOI] [PubMed] [Google Scholar]
Berná J.; Goldup S. M.; Lee A.-L.; Leigh D. A.; Symes M. D.; Teobaldi G.; Zerbetto F. Cadiot–Chodkiewicz Active Template Synthesis of Rotaxanes and Switchable Molecular Shuttles with Weak Intercomponent Interactions. Angew. Chem., Int. Ed. 2008, 47, 4392–4396 10.1002/anie.200800891. [DOI] [PubMed] [Google Scholar]
Liu L.; Liu Y.; Liu P.; Wu J.; Guan Y.; Hu X.; Lin C.; Yang Y.; Sun X.; Ma J.; Wang L. Phosphine Oxide Functional Group Based Three-station Molecular Shuttle. Chem. Sci. 2013, 4, 1701–1706 10.1039/c3sc22048f. [DOI] [Google Scholar]
Xue M.; Yang Y.; Chi X.; Yan X.; Huang F. Development of Pseudorotaxanes and Rotaxanes: From Synthesis to Stimuli-Responsive Motions to Applications. Chem. Rev. 2015, 115, 7398. 10.1021/cr5005869. [DOI] [PubMed] [Google Scholar]
Franz M.; Januszewski J. A.; Wendinger D.; Neiss C.; Movsisyan L. D.; Hampel F.; Anderson H. L.; Gorling A.; Tykwinski R. R. Cumulene Rotaxanes: Stabilization and Study of [9]Cumulenes. Angew. Chem., Int. Ed. 2015, 54, 6645–6649 10.1002/anie.201501810. [DOI] [PubMed] [Google Scholar]
Langton M. J.; Matichak J. D.; Thompson A. L.; Anderson H. L. Template-directed Synthesis of π-Conjugated Porphyrin [2]Rotaxanes and a [4]Catenane Based on a Six-porphyrin Nanoring. Chem. Sci. 2011, 2, 1897–1901 10.1039/c1sc00358e. [DOI] [Google Scholar]
Lee S.; Chen C. H.; Flood A. H. A Pentagonal Cyanostar Macrocycle with Cyanostilbene CH Donors Binds Anions and Forms Dialkylphosphate [3]Rotaxanes. Nat. Chem. 2013, 5, 704–710 10.1038/nchem.1668. [DOI] [PubMed] [Google Scholar]
Lahlali H.; Jobe K.; Watkinson M.; Goldup S. M. Macrocycle Size Matters: ″Small″ Functionalized Rotaxanes in Excellent Yield Using the CuAAC Active Template Approach. Angew. Chem., Int. Ed. 2011, 50, 4151–4155 10.1002/anie.201100415. [DOI] [PubMed] [Google Scholar]
Winn J.; Pinczewska A.; Goldup S. M. Synthesis of a Rotaxane Cu(I) Triazolide under Aqueous Conditions. J. Am. Chem. Soc. 2013, 135, 13318–13321 10.1021/ja407446c. [DOI] [PubMed] [Google Scholar]
Bordoli R. J.; Goldup S. M. An Efficient Approach to Mechanically Planar Chiral Rotaxanes. J. Am. Chem. Soc. 2014, 136, 4817–4820 10.1021/ja412715m. [DOI] [PMC free article] [PubMed] [Google Scholar]
Hübner G. M.; Gläser J.; Seel C.; Vögtle F. High-Yielding Rotaxane Synthesis with an Anion Template. Angew. Chem., Int. Ed. 1999, 38, 383–386. [DOI] [PubMed] [Google Scholar]
Hiratani K.; Suga J.-i.; Nagawa Y.; Houjou H.; Tokuhisa H.; Numata M.; Watanabe K. A new Synthetic Method for Rotaxanes via Tandem Claisen Rearrangement, Diesterification, and Aminolysis. Tetrahedron Lett. 2002, 43, 5747–5750 10.1016/S0040-4039(02)01201-7. [DOI] [Google Scholar]
Hannam J. S.; Lacy S. M.; Leigh D. A.; Saiz C. G.; Slawin A. M. Z.; Stitchell S. G. Controlled Submolecular Translational Motion in Synthesis: A Mechanically Interlocking Auxiliary. Angew. Chem., Int. Ed. 2004, 43, 3260–3264 10.1002/anie.200353606. [DOI] [PubMed] [Google Scholar]
Kameta N.; Hiratani K.; Nagawa Y. A Novel Synthesis of Chiral Rotaxanes via Covalent Bond Formation. Chem. Commun. 2004, 466–467 10.1039/b314744d. [DOI] [PubMed] [Google Scholar]
Reuter C.; Wienand W.; Hübner G. M.; Seel C.; Vögtle F. High-Yield Synthesis of Ester, Carbonate, and Acetal Rotaxanes by Anion Template Assistance and their Hydrolytic Dethreading. Chem. - Eur. J. 1999, 5, 2692–2697. [DOI] [Google Scholar]
Schalley C. A.; Silva G.; Nising C. F.; Linnartz P. Analysis and Improvement of an Anion-Templated Rotaxane Synthesis. Helv. Chim. Acta 2002, 85, 1578–1596. [DOI] [Google Scholar]
Mahoney J. M.; Shukla R.; Marshall R. A.; Beatty A. M.; Zajicek J.; Smith B. D. Templated Conversion of a Crown Ether-Containing Macrobicycle into [2]Rotaxanes. J. Org. Chem. 2002, 67, 1436–1440 10.1021/jo0162787. [DOI] [PubMed] [Google Scholar]
Li X.-Y.; Illigen J.; Nieger M.; Michel S.; Schalley C. A. Tetra- and Octalactam Macrocycles and Catenanes with Exocyclic Metal Coordination Sites: Versatile Building Blocks for Supramolecular Chemistry. Chem. - Eur. J. 2003, 9, 1332–1347 10.1002/chem.200390153. [DOI] [PubMed] [Google Scholar]
Nagawa Y.; Suga J.-i.; Hiratani K.; Koyama E.; Kanesato M. [3]Rotaxane Synthesized via Covalent Bond Formation Can Recognize Cations Forming a Sandwich Structure. Chem. Commun. 2005, 749–751 10.1039/b413715a. [DOI] [PubMed] [Google Scholar]
Schill G.; Zollenkopf H.; Rotaxan-Verbindungen I. Justus Liebigs Ann. Chem. 1969, 721, 53–74 10.1002/jlac.19697210109. [DOI] [Google Scholar]
Langton M. J.; Robinson S. W.; Marques I.; Felix V.; Beer P. D. Halogen Bonding in Water Results in Enhanced Anion Recognition in Acyclic and Rotaxane Hosts. Nat. Chem. 2014, 6, 1039–1043 10.1038/nchem.2111. [DOI] [PubMed] [Google Scholar]
Aucagne V.; Berna J.; Crowley J. D.; Goldup S. M.; Hanni K. D.; Leigh D. A.; Lusby P. J.; Ronaldson V. E.; Slawin A. M.; Viterisi A.; Walker D. B. Catalytic ″Active-metal″ Template Synthesis of [2]Rotaxanes, [3]Rotaxanes, and Molecular Shuttles, and Some Observations on the Mechanism of the Cu(I)-Catalyzed Azide-alkyne 1,3-Cycloaddition. J. Am. Chem. Soc. 2007, 129, 11950–11963 10.1021/ja073513f. [DOI] [PubMed] [Google Scholar]
Browne C.; Ronson T. K.; Nitschke J. R. Palladium-Templated Subcomponent Self-Assembly of Macrocycles, Catenanes, and Rotaxanes. Angew. Chem., Int. Ed. 2014, 53, 10701–10705 10.1002/anie.201406164. [DOI] [PubMed] [Google Scholar]
Anelli P. L.; Spencer N.; Stoddart J. F. A Molecular Shuttle. J. Am. Chem. Soc. 1991, 113, 5131–5133 10.1021/ja00013a096. [DOI] [PubMed] [Google Scholar]
Ashton P. R.; Johnston M. R.; Stoddart J. F.; Tolley M. S.; Wheeler J. W. The Template-directed Synthesis of Porphyrin-stoppered [2]Rotaxanes. J. Chem. Soc., Chem. Commun. 1992, 1128–1131 10.1039/c39920001128. [DOI] [Google Scholar]
Ashton P. R.; Philp D.; Spencer N.; Stoddart J. F. A New Design Strategy for the Self-assembly of Molecular Shuttles. J. Chem. Soc., Chem. Commun. 1992, 1124–1128 10.1039/c39920001124. [DOI] [Google Scholar]
Lane A. S.; Leigh D. A.; Murphy A. Peptide-Based Molecular Shuttles. J. Am. Chem. Soc. 1997, 119, 11092–11093 10.1021/ja971224t. [DOI] [Google Scholar]
Leigh D. A.; Murphy A.; Smart J. P.; Slawin A. M. Z. Glycylglycine Rotaxanes—The Hydrogen Bond Directed Assembly of Synthetic Peptide Rotaxanes. Angew. Chem., Int. Ed. Engl. 1997, 36, 728–732 10.1002/anie.199707281. [DOI] [Google Scholar]
Leigh D. A.; Murphy A.; Smart J. P.; Deleuze M. S.; Zerbetto F. Controlling the Frequency of Macrocyclic Ring Rotation in Benzylic Amide [2]Catenanes. J. Am. Chem. Soc. 1998, 120, 6458–6467 10.1021/ja974065m. [DOI] [Google Scholar]
Leigh D. A.; Troisi A.; Zerbetto F. A Quantum-Mechanical Description of Macrocyclic Ring Rotation in Benzylic Amide [2]Catenanes. Chem. - Eur. J. 2001, 7, 1450–1454. [DOI] [PubMed] [Google Scholar]
Deleuze M. S.; Leigh D. A.; Zerbetto F. How Do Benzylic Amide [2]Catenane Rings Rotate?. J. Am. Chem. Soc. 1999, 121, 2364–2379 10.1021/ja9815273. [DOI] [Google Scholar]
Panman M. R.; Bakker B. H.; den Uyl D.; Kay E. R.; Leigh D. A.; Buma W. J.; Brouwer A. M.; Geenevasen J. A. J.; Woutersen S. Water Lubricates Hydrogen-bonded Molecular Machines. Nat. Chem. 2013, 5, 929–934 10.1038/nchem.1744. [DOI] [PubMed] [Google Scholar]
Ghosh P.; Federwisch G.; Kogej M.; Schalley C. A.; Haase D.; Saak W.; Lutzen A.; Gschwind R. M. Controlling the Rate of Shuttling Motions in [2]Rotaxanes by Electrostatic Interactions: A Cation as Solvent-tunable Brake. Org. Biomol. Chem. 2005, 3, 2691–2700 10.1039/b506756a. [DOI] [PubMed] [Google Scholar]
Cao J.; Fyfe M. C. T.; Stoddart J. F.; Cousins G. R. L.; Glink P. T. Molecular Shuttles by the Protecting Group Approach†. J. Org. Chem. 2000, 65, 1937–1946 10.1021/jo991397w. [DOI] [PubMed] [Google Scholar]
Jiang L.; Okano J.; Orita A.; Otera J. Intermittent Molecular Shuttle as a Binary Switch. Angew. Chem., Int. Ed. 2004, 43, 2121–2124 10.1002/anie.200353534. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Lusby P. J.; Slawin A. M. Z.; Walker D. B. Rare and Diverse Binding Modes Introduced through Mechanical Bonding. Angew. Chem., Int. Ed. 2005, 44, 4557–4564 10.1002/anie.200500004. [DOI] [PubMed] [Google Scholar]
Martinez-Cuezva A.; Berna J.; Orenes R.-A.; Pastor A.; Alajarin M. Small-Molecule Recognition for Controlling Molecular Motion in Hydrogen-Bond-Assembled Rotaxanes. Angew. Chem., Int. Ed. 2014, 53, 6762–6767 10.1002/anie.201402962. [DOI] [PubMed] [Google Scholar]
Berna J.; Alajarin M.; Marin-Rodriguez C.; Franco-Pujante C. Redox Divergent Conversion of a [2]Rotaxane into Two Distinct Degenerate Partners with Different Shuttling Dynamics. Chem. Sci. 2012, 3, 2314–2320 10.1039/c2sc20488f. [DOI] [Google Scholar]
Hirose K.; Shiba Y.; Ishibashi K.; Doi Y.; Tobe Y. A Shuttling Molecular Machine with Reversible Brake Function. Chem. - Eur. J. 2008, 14, 3427–3433 10.1002/chem.200702001. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Troisi A.; Zerbetto F. Reducing Molecular Shuttling to a Single Dimension. Angew. Chem., Int. Ed. 2000, 39, 350–353. [DOI] [PubMed] [Google Scholar]
Günbaş D. D.; Brouwer A. M. Degenerate Molecular Shuttles with Flexible and Rigid Spacers. J. Org. Chem. 2012, 77, 5724–5735 10.1021/jo300907r. [DOI] [PubMed] [Google Scholar]
Andersen S. S.; Share A. I.; Poulsen B. L. C.; Kørner M.; Duedal T.; Benson C. R.; Hansen S. W.; Jeppesen J. O.; Flood A. H. Mechanistic Evaluation of Motion in Redox-Driven Rotaxanes Reveals Longer Linkers Hasten Forward Escapes and Hinder Backward Translations. J. Am. Chem. Soc. 2014, 136, 6373–6384 10.1021/ja5013596. [DOI] [PubMed] [Google Scholar]
Young P. G.; Hirose K.; Tobe Y. Axle Length Does Not Affect Switching Dynamics in Degenerate Molecular Shuttles with Rigid Spacers. J. Am. Chem. Soc. 2014, 136, 7899–7906 10.1021/ja412671k. [DOI] [PubMed] [Google Scholar]
Yoon I.; Benítez D.; Zhao Y.-L.; Miljanić O. Š.; Kim S.-Y.; Tkatchouk E.; Leung K. C. F.; Khan S. I.; Goddard W. A. III; Stoddart J. F. Functionally Rigid and Degenerate Molecular Shuttles. Chem. - Eur. J. 2009, 15, 1115–1122 10.1002/chem.200802096. [DOI] [PubMed] [Google Scholar]
Benniston A. C.; Harriman A. A Light-Induced Molecular Shuttle Based on a [2]Rotaxane-Derived Triad. Angew. Chem., Int. Ed. Engl. 1993, 32, 1459–1461 10.1002/anie.199314591. [DOI] [Google Scholar]
Murakami H.; Kawabuchi A.; Kotoo K.; Kunitake M.; Nakashima N. A Light-driven Molecular Shuttle Based on a Rotaxane. J. Am. Chem. Soc. 1997, 119, 7605–7606 10.1021/ja971438a. [DOI] [Google Scholar]
Murakami H.; Kawabuchi A.; Matsumoto R.; Ido T.; Nakashima N. A Multi-mode-driven Molecular Shuttle: Photochemically and Thermally Reactive Azobenzene Rotaxanes. J. Am. Chem. Soc. 2005, 127, 15891–15899 10.1021/ja053690l. [DOI] [PubMed] [Google Scholar]
Clegg W.; Gimenez-Saiz C.; Leigh D. A.; Murphy A.; Slawin A. M. Z.; Teat S. J. ″Smart″ Rotaxanes: Shape Memory and Control in Tertiary Amide Peptido[2]rotaxanes. J. Am. Chem. Soc. 1999, 121, 4124–4129 10.1021/ja9841310. [DOI] [Google Scholar]
Asakawa M.; Brancato G.; Fanti M.; Leigh D. A.; Shimizu T.; Slawin A. M. Z.; Wong J. K. Y.; Zerbetto F.; Zhang S. W. Switching ″On″ and ″Off″ the Expression of Chirality in Peptide Rotaxanes. J. Am. Chem. Soc. 2002, 124, 2939–2950 10.1021/ja015995f. [DOI] [PubMed] [Google Scholar]
Dong S.; Yuan J.; Huang F. A Pillar[5]arene/imidazolium [2]Rotaxane: Solvent- and Thermo-driven Molecular Motions and Supramolecular Gel Formation. Chem. Sci. 2014, 5, 247–252 10.1039/C3SC52481G. [DOI] [Google Scholar]
Zhang Z.; Han C.; Yu G.; Huang F. A Solvent-driven Molecular Spring. Chem. Sci. 2012, 3, 3026–3031 10.1039/c2sc20728a. [DOI] [Google Scholar]
Bissell R. A.; Cordova E.; Kaifer A. E.; Stoddart J. F. A Chemically and Electrochemically Switchable Molecular Shuttle. Nature 1994, 369, 133–137 10.1038/369133a0. [DOI] [Google Scholar]
Castro R.; Berardi M. J.; Cordova E.; de Olza M. O.; Kaifer A. E.; Evanseck J. D. Unexpected Roles of Guest Polarizability and Maximum Hardness, and of Host Solvation in Supramolecular Inclusion Complexes: A Dual Theoretical and Experimental Study. J. Am. Chem. Soc. 1996, 118, 10257–10268 10.1021/ja960700x. [DOI] [Google Scholar]
Castro R.; Nixon K. R.; Evanseck J. D.; Kaifer A. E. Effects of Side Arm Length and Structure of para-Substituted Phenyl Derivatives on Their Binding to the Host Cyclobis(paraquat-p-phenylene). J. Org. Chem. 1996, 61, 7298–7303 10.1021/jo9610321. [DOI] [PubMed] [Google Scholar]
Kaminski G. A.; Jorgensen W. L. Host-guest Chemistry of Rotaxanes and Catenanes: Application of a Polarizable All-atom Force Field to Cyclobis(paraquat-p-phenylene) Complexes with Disubstituted Benzenes and Biphenyls. J. Chem. Soc., Perkin Trans. 2 1999, 2365–2375 10.1039/a905160k. [DOI] [Google Scholar]
Macias A. T.; Kumar K. A.; Marchand A. P.; Evanseck J. D. Computational Studies of Inclusion Phenomena and Synthesis of a Novel and Selective Molecular Receptor for 1,4-Disubstituted Benzenes and 4,4′-Disubstituted Biphenyls. J. Org. Chem. 2000, 65, 2083–2089 10.1021/jo991669v. [DOI] [PubMed] [Google Scholar]
Zhang K. C.; Liu L.; Mu T. W.; Guo Q. X. Ab initio Calculations on the Inclusion Complexation of Cyclobis(paraquat-p-phenylene). Chem. Phys. Lett. 2001, 333, 195–198 10.1016/S0009-2614(00)01337-3. [DOI] [Google Scholar]
Grabuleda X.; Ivanov P.; Jaime C. Shuttling Process in [2]Rotaxanes. Modeling by Molecular Dynamics and Free Energy Perturbation Simulations. J. Phys. Chem. B 2003, 107, 7582–7588 10.1021/jp034658l. [DOI] [PubMed] [Google Scholar]
Grabuleda X.; Jaime C. Molecular Shuttles. A Computational Study (MM and MD) on the Translational Isomerism in Some [2]Rotaxanes. J. Org. Chem. 1998, 63, 9635–9643 10.1021/jo980400t. [DOI] [Google Scholar]
Ercolani G.; Mencarelli P. Role of Face-to-face and Edge-to-face Aromatic Interactions in the Inclusion Complexation of Cyclobis(paraquat-p-phenylene): A Theoretical Study. J. Org. Chem. 2003, 68, 6470–6473 10.1021/jo026887u. [DOI] [PubMed] [Google Scholar]
Castro R.; Davidov P. D.; Kumar K. A.; Marchand A. P.; Evanseck J. D.; Kaifer A. E. Inclusion Complexation of Cyclobis(paraquat-p-phenylene) and Related Cyclophane Derivatives with Substituted Aromatics: Cooperative Non-covalent Cavity and External Interactions. J. Phys. Org. Chem. 1997, 10, 369–382. [DOI] [Google Scholar]
Grabuleda X.; Ivanov P.; Jaime C. Computational Studies on Pseudorotaxanes by Molecular Dynamics and Free Energy Perturbation Simulations. J. Org. Chem. 2003, 68, 1539–1547 10.1021/jo0265636. [DOI] [PubMed] [Google Scholar]
Martinez-Diaz M. V.; Spencer N.; Stoddart J. F. The Self-assembly of a Switchable [2]Rotaxane. Angew. Chem., Int. Ed. Engl. 1997, 36, 1904–1907 10.1002/anie.199719041. [DOI] [Google Scholar]
Badjic J. D.; Balzani V.; Credi A.; Silvi S.; Stoddart J. F. A Molecular Elevator. Science 2004, 303, 1845–1849 10.1126/science.1094791. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Thomson A. R. Switchable Dual Binding Mode Molecular Shuttle. Org. Lett. 2006, 8, 5377–5379 10.1021/ol062284j. [DOI] [PubMed] [Google Scholar]
Vella S. J.; Tiburcio J.; Loeb S. J. Optically Sensed, Molecular Shuttles Driven by Acid-base Chemistry. Chem. Commun. 2007, 4752–4754 10.1039/b710708k. [DOI] [PubMed] [Google Scholar]
Zheng H. Y.; Zhou W. D.; Lv J.; Yin X. D.; Li Y. J.; Liu H. B.; Li Y. L. A Dual-Response [2]Rotaxane Based on a 1,2,3-Triazole Ring as a Novel Recognition Station. Chem. - Eur. J. 2009, 15, 13253–13262 10.1002/chem.200901841. [DOI] [PubMed] [Google Scholar]
Tuncel D.; Katterle M. pH-triggered Dethreading-rethreading and Switching of Cucurbit[6]uril on Bistable [3]Pseudorotaxanes and [3]Rotaxanes. Chem. - Eur. J. 2008, 14, 4110–4116 10.1002/chem.200702003. [DOI] [PubMed] [Google Scholar]
Kolchinski A. G.; Busch D. H.; Alcock N. W. Gaining Control over Molecular Threading - Benefits of 2nd Coordination Sites and Aqueous-Organic Interfaces in Rotaxane Synthesis. J. Chem. Soc., Chem. Commun. 1995, 1289–1291 10.1039/c39950001289. [DOI] [Google Scholar]
Glink P. T.; Schiavo C.; Stoddart J. F.; Williams D. J. The Genesis of a New Range of Interlocked Molecules. Chem. Commun. 1996, 1483–1490 10.1039/cc9960001483. [DOI] [Google Scholar]
Cantrill S. J.; Pease A. R.; Stoddart J. F. A Molecular Meccano Kit. J. Chem. Soc. Dalton 2000, 3715–3734 10.1039/b003769i. [DOI] [Google Scholar]
Ashton P. R.; Glink P. T.; Stoddart J. F.; Tasker P. A.; White A. J. P.; Williams D. J. Self-assembling [2]- and [3]Rotaxanes from Secondary Dialkylammonium Salts and Crown Ethers. Chem. - Eur. J. 1996, 2, 729–736 10.1002/chem.19960020617. [DOI] [Google Scholar]
Ashton P. R.; Ballardini R.; Balzani V.; Baxter I.; Credi A.; Fyfe M. C. T.; Gandolfi M. T.; Gomez-Lopez M.; Martinez-Diaz M. V.; Piersanti A.; et al. Acid-base Controllable Molecular Shuttles. J. Am. Chem. Soc. 1998, 120, 11932–11942 10.1021/ja982167m. [DOI] [Google Scholar]
Garaudee S.; Silvi S.; Venturi M.; Credi A.; Flood A. H.; Stoddart J. F. Shuttling Dynamics in an Acid-base-switchable [2]Rotaxane. ChemPhysChem 2005, 6, 2145–2152 10.1002/cphc.200500295. [DOI] [PubMed] [Google Scholar]
Frankfort L.; Sohlberg K. Semi-empirical Study of a pH-switchable [2] Rotaxane. J. Mol. Struct.: THEOCHEM 2003, 621, 253–260 10.1016/S0166-1280(02)00641-3. [DOI] [Google Scholar]
Elizarov A. M.; Chiu S. H.; Stoddart J. F. An Acid-base Switchable [2]Rotaxane. J. Org. Chem. 2002, 67, 9175–9181 10.1021/jo020373d. [DOI] [PubMed] [Google Scholar]
Badjic J. D.; Ronconi C. M.; Stoddart J. F.; Balzani V.; Silvi S.; Credi A. Operating Molecular Elevators. J. Am. Chem. Soc. 2006, 128, 1489–1499 10.1021/ja0543954. [DOI] [PubMed] [Google Scholar]
Bruns C. J.; Stoddart J. F. Molecular Machines Muscle Up. Nat. Nanotechnol. 2012, 8, 9–10 10.1038/nnano.2012.239. [DOI] [PubMed] [Google Scholar]
Clark P. G.; Day M. W.; Grubbs R. H. Switching and Extension of a [c2]Daisy-Chain Dimer Polymer. J. Am. Chem. Soc. 2009, 131, 13631–13633 10.1021/ja905924u. [DOI] [PubMed] [Google Scholar]
Du G. Y.; Moulin E.; Jouault N.; Buhler E.; Giuseppone N. Muscle-like Supramolecular Polymers: Integrated Motion from Thousands of Molecular Machines. Angew. Chem., Int. Ed. 2012, 51, 12504–12508 10.1002/anie.201206571. [DOI] [PubMed] [Google Scholar]
Keaveney C. M.; Leigh D. A. Shuttling Through Anion Recognition. Angew. Chem., Int. Ed. 2004, 43, 1222–1224 10.1002/anie.200353248. [DOI] [PubMed] [Google Scholar]
Hesseler B.; Zindler M.; Herges R.; Lüning U. A Shuttle for the Transport of Protons Based on a [2]Rotaxane. Eur. J. Org. Chem. 2014, 2014, 3885–3901 10.1002/ejoc.201402249. [DOI] [Google Scholar]
Hesseler B.; Zindler M.; Herges R.; Lüning U. A Shuttle for the Transport of Protons Based on a [2]Rotaxane. Eur. J. Org. Chem. 2014, 2014, 3885–3901 10.1002/ejoc.201402249. [DOI] [Google Scholar]
Crowley J. D.; Leigh D. A.; Lusby P. J.; McBurney R. T.; Perret-Aebi L. E.; Petzold C.; Slawin A. M. Z.; Symes M. D. A Switchable Palladium-complexed Molecular Shuttle and its Metastable Positional Isomers. J. Am. Chem. Soc. 2007, 129, 15085–15090 10.1021/ja076570h. [DOI] [PubMed] [Google Scholar]
Buyukcakir O.; Yasar F. T.; Bozdemir O. A.; Icli B.; Akkaya E. U. Autonomous Shuttling Driven by an Oscillating Reaction: Proof of Principle in a Cucurbit[7]uril-Bodipy Pseudorotaxane. Org. Lett. 2013, 15, 1012–1015 10.1021/ol303495n. [DOI] [PubMed] [Google Scholar]
Joosten A.; Trolez Y.; Collin J.-P.; Heitz V.; Sauvage J.-P. Copper(I)-Assembled [3]Rotaxane Whose Two Rings Act as Flapping Wings. J. Am. Chem. Soc. 2012, 134, 1802–1809 10.1021/ja210113y. [DOI] [PubMed] [Google Scholar]
Ashton P. R.; Bissell R. A.; Spencer N.; Stoddart J. F.; Tolley M. S. Towards Controllable Molecular Shuttles - 1. Synlett 1992, 1992, 914–918 10.1055/s-1992-21540. [DOI] [Google Scholar]
Ashton P. R.; Bissell R. A.; Gorski R.; Philp D.; Spencer N.; Stoddart J. F.; Tolley M. S. Towards Controllable Molecular Shuttles - 2. Synlett 1992, 1992, 919–922 10.1055/s-1992-21541. [DOI] [Google Scholar]
Ashton P. R.; Bissell R. A.; Spencer N.; Stoddart J. F.; Tolley M. S. Towards Controllable Molecular Shuttles - 3. Synlett 1992, 1992, 923–926 10.1055/s-1992-21542. [DOI] [Google Scholar]
Anelli P. L.; Asakawa M.; Ashton P. R.; Bissell R. A.; Clavier G.; Gorski R.; Kaifer A. E.; Langford S. J.; Mattersteig G.; Menzer S.; et al. Toward Controllable Molecular Shuttles. Chem. - Eur. J. 1997, 3, 1113–1135 10.1002/chem.19970030719. [DOI] [Google Scholar]
Brouwer A. M.; Frochot C.; Gatti F. G.; Leigh D. A.; Mottier L.; Paolucci F.; Roffia S.; Wurpel G. W. H. Photoinduction of Fast, Reversible Translational Motion in a Hydrogen-bonded Molecular Shuttle. Science 2001, 291, 2124–2128 10.1126/science.1057886. [DOI] [PubMed] [Google Scholar]
Altieri A.; Gatti F. G.; Kay E. R.; Leigh D. A.; Martel D.; Paolucci F.; Slawin A. M. Z.; Wong J. K. Y. Electrochemically Switchable Hydrogen-bonded Molecular Shuttles. J. Am. Chem. Soc. 2003, 125, 8644–8654 10.1021/ja0352552. [DOI] [PubMed] [Google Scholar]
Zheng X. G.; Sohlberg K. Modeling of a Rotaxane-based Molecular Device. J. Phys. Chem. A 2003, 107, 1207–1215 10.1021/jp0267611. [DOI] [Google Scholar]
Raiteri P.; Bussi G.; Cucinotta C. S.; Credi A.; Stoddart J. F.; Parrinello M. Unravelling the Shuttling Mechanism in a Photoswitchable Multicomponent Bistable Rotaxane. Angew. Chem., Int. Ed. 2008, 47, 3536–3539 10.1002/anie.200705207. [DOI] [PubMed] [Google Scholar]
Tseng H. R.; Vignon S. A.; Stoddart J. F. Toward Chemically Controlled Nanoscale Molecular Machinery. Angew. Chem., Int. Ed. 2003, 42, 1491–1495 10.1002/anie.200250453. [DOI] [PubMed] [Google Scholar]
Fioravanti G.; Haraszkiewicz N.; Kay E. R.; Mendoza S. M.; Bruno C.; Marcaccio M.; Wiering P. G.; Paolucci F.; Rudolf P.; Brouwer A. M.; et al. Three State Redox-active Molecular Shuttle That Switches in Solution and on a Surface. J. Am. Chem. Soc. 2008, 130, 2593–2601 10.1021/ja077223a. [DOI] [PubMed] [Google Scholar]
Zhao Y. L.; Dichtel W. R.; Trabolsi A.; Saha S.; Aprahamian I.; Stoddart J. F. A Redox-switchable alpha-Cyclodextrin-based [2]Rotaxane. J. Am. Chem. Soc. 2008, 130, 11294–11296 10.1021/ja8036146. [DOI] [PubMed] [Google Scholar]
Saha S.; Flood A. H.; Stoddart J. F.; Impellizzeri S.; Silvi S.; Venturi M.; Credi A. A Redox-driven Multicomponent Molecular Shuttle. J. Am. Chem. Soc. 2007, 129, 12159–12171 10.1021/ja0724590. [DOI] [PubMed] [Google Scholar]
Barnes J. C.; Fahrenbach A. C.; Dyar S. M.; Frasconi M.; Giesener M. A.; Zhu Z. X.; Liu Z. C.; Hartlieb K. J.; Carmieli R.; Wasielewski M. R.; et al. Mechanically Induced Intramolecular Electron Transfer in a Mixed-valence Molecular Shuttle. Proc. Natl. Acad. Sci. U. S. A. 2012, 109, 11546–11551 10.1073/pnas.1201561109. [DOI] [PMC free article] [PubMed] [Google Scholar]
Amabilino D. B.; Ashton P. R.; Boyd S. E.; GomezLopez M.; Hayes W.; Stoddart J. F. Translational Isomerism in Some Two- and Three-station [2]Rotaxanes. J. Org. Chem. 1997, 62, 3062–3075 10.1021/jo9612584. [DOI] [PubMed] [Google Scholar]
Asakawa M.; Ashton P. R.; Balzani V.; Credi A.; Hamers C.; Mattersteig G.; Montalti M.; Shipway A. N.; Spencer N.; Stoddart J. F.; et al. A Chemically and Electrochemically Switchable [2]Catenane Incorporating a Tetrathiafulvalene Unit. Angew. Chem., Int. Ed. 1998, 37, 333–337. [DOI] [PubMed] [Google Scholar]
Jeppesen J. O.; Perkins J.; Becher J.; Stoddart J. F. Slow Shuttling in an Amphiphilic Bistable [2]Rotaxane Incorporating a Tetrathiafulvalene Unit. Angew. Chem., Int. Ed. 2001, 40, 1216–1221. [DOI] [PubMed] [Google Scholar]
Tseng H. R.; Vignon S. A.; Celestre P. C.; Perkins J.; Jeppesen J. O.; Di Fabio A.; Ballardini R.; Gandolfi M. T.; Venturi M.; Balzani V.; et al. Redox-controllable Amphiphilic [2]Rotaxanes. Chem. - Eur. J. 2004, 10, 155–172 10.1002/chem.200305204. [DOI] [PubMed] [Google Scholar]
Flood A. H.; Peters A. J.; Vignon S. A.; Steuerman D. W.; Tseng H. R.; Kang S.; Heath J. R.; Stoddart J. F. The Role of Physical Environment on Molecular Electromechanical Switching. Chem. - Eur. J. 2004, 10, 6558–6564 10.1002/chem.200401052. [DOI] [PubMed] [Google Scholar]
Jeppesen J. O.; Nygaard S.; Vignon S. A.; Stoddart J. F. Honing up a Genre of Amphiphilic Bistable [2]rotaxanes for Device Settings. Eur. J. Org. Chem. 2005, 2005, 196–220 10.1002/ejoc.200400530. [DOI] [Google Scholar]
Choi J. W.; Flood A. H.; Steuerman D. W.; Nygaard S.; Braunschweig A. B.; Moonen N. N. P.; Laursen B. W.; Luo Y.; DeIonno E.; Peters A. J.; et al. Ground-state Equilibrium Thermodynamics and Switching Kinetics of Bistable [2]Rotaxanes Switched in Solution, Polymer Gels, and Molecular Electronic Devices. Chem. - Eur. J. 2006, 12, 261–279 10.1002/chem.200500934. [DOI] [PubMed] [Google Scholar]
Kang S. S.; Vignon S. A.; Tseng H. R.; Stoddart J. F. Molecular Shuttles Based on Tetrathiafulvalene Units and 1,5-Dioxynaphthalene Ring Systems. Chem. - Eur. J. 2004, 10, 2555–2564 10.1002/chem.200305725. [DOI] [PubMed] [Google Scholar]
Jeppesen J. O.; Nielsen K. A.; Perkins J.; Vignon S. A.; Di Fabio A.; Ballardini R.; Gandolfi M. T.; Venturi M.; Balzani V.; Becher J.; et al. Amphiphilic Bistable Rotaxanes. Chem. - Eur. J. 2003, 9, 2982–3007 10.1002/chem.200204589. [DOI] [Google Scholar]
Ashton P. R.; Ballardini R.; Balzani V.; Credi A.; Dress K. R.; Ishow E.; Kleverlaan C. J.; Kocian O.; Preece J. A.; Spencer N.; et al. A Photochemically Driven Molecular-level Abacus. Chem. - Eur. J. 2000, 6, 3558–3574. [DOI] [PubMed] [Google Scholar]
Ballardini R.; Balzani V.; Dehaen W.; Dell’Erba A. E.; Raymo F. M.; Stoddart J. F.; Venturi M. Molecular Meccano, 56 - Anthracene-containing [2]Rotaxanes: Synthesis, Spectroscopic, and Electrochemical Properties. Eur. J. Org. Chem. 2000, 2000, 591–602. [DOI] [Google Scholar]
Kihara N.; Hashimoto M.; Takata T. Redox Behavior of Ferrocene-containing Rotaxane: Transposition of the Rotaxane Wheel by Redox Reaction of a Ferrocene Moiety Tethered at the End of the Axle. Org. Lett. 2004, 6, 1693–1696 10.1021/ol049817d. [DOI] [PubMed] [Google Scholar]
Armaroli N.; Balzani V.; Collin J.-P.; Gavina P.; Sauvage J.-P.; Ventura B. Rotaxanes Incorporating Two Different Coordinating Units in Their Thread: Synthesis and Electrochemically and Photochemically Induced Molecular Motions. J. Am. Chem. Soc. 1999, 121, 4397–4408 10.1021/ja984051w. [DOI] [Google Scholar]
Trabolsi A.; Khashab N.; Fahrenbach A. C.; Friedman D. C.; Colvin M. T.; Cotí K. K.; Benítez D.; Tkatchouk E.; Olsen J.-C.; Belowich M. E.; et al. Radically Enhanced Molecular Recognition. Nat. Chem. 2010, 2, 42–49 10.1038/nchem.479. [DOI] [PubMed] [Google Scholar]
Vignon S. A.; Jarrosson T.; Iijima T.; Tseng H. R.; Sanders J. K. M.; Stoddart J. F. Switchable Neutral Bistable Rotaxanes. J. Am. Chem. Soc. 2004, 126, 9884–9885 10.1021/ja048080k. [DOI] [PubMed] [Google Scholar]
Marlin D. S.; Cabrera D. G.; Leigh D. A.; Slawin A. M. Z. Complexation-induced Translational Isomerism: Shuttling Through Stepwise Competitive Binding. Angew. Chem., Int. Ed. 2006, 45, 77–83 10.1002/anie.200501761. [DOI] [PubMed] [Google Scholar]
Marlin D. S.; Cabrera D. G.; Leigh D. A.; Slawin A. M. Z. An Allosterically Regulated Molecular Shuttle. Angew. Chem., Int. Ed. 2006, 45, 1385–1390 10.1002/anie.200502624. [DOI] [PubMed] [Google Scholar]
Barrell M. J.; Leigh D. A.; Lusby P. J.; Slawin A. M. Z. An Ion-Pair Template for Rotaxane Formation and its Exploitation in an Orthogonal Interaction Anion-Switchahle Molecular Shuttle. Angew. Chem., Int. Ed. 2008, 47, 8036–8039 10.1002/anie.200802745. [DOI] [PubMed] [Google Scholar]
Spence G. T.; Pitak M. B.; Beer P. D. Anion-Induced Shuttling of a Naphthalimide Triazolium Rotaxane. Chem. - Eur. J. 2012, 18, 7100–7108 10.1002/chem.201200317. [DOI] [PubMed] [Google Scholar]
Caballero A.; Swan L.; Zapata F.; Beer P. D. Iodide-Induced Shuttling of a Halogen- and Hydrogen-Bonding Two-Station Rotaxane. Angew. Chem., Int. Ed. 2014, 53, 11854–11858 10.1002/anie.201407580. [DOI] [PubMed] [Google Scholar]
Collins C. G.; Peck E. M.; Kramer P. J.; Smith B. D. Squaraine Rotaxane Shuttle as a Ratiometric Deep-red Optical Chloride Sensor. Chem. Sci. 2013, 4, 2557–2563 10.1039/c3sc50535a. [DOI] [Google Scholar]
You Y. C.; Tzeng M. C.; Lai C. C.; Chiu S. H. Using Oppositely Charged Ions To Operate a Three-Station [2]Rotaxane in Two Different Switching Modes. Org. Lett. 2012, 14, 1046–1049 10.1021/ol203401d. [DOI] [PubMed] [Google Scholar]
Collin J.-P.; Frey J.; Heitz V.; Sauvage J.-P.; Tock C.; Allouche L. Adjustable Receptor Based on a [3]Rotaxane Whose Two Threaded Rings Are Rigidly Attached to Two Porphyrinic Plates: Synthesis and Complexation Studies. J. Am. Chem. Soc. 2009, 131, 5609–5620 10.1021/ja900565p. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Perez E. M. Shuttling Through Reversible Covalent Chemistry. Chem. Commun. 2004, 2262–2263 10.1039/b412570c. [DOI] [PubMed] [Google Scholar]
Abraham W.; Grubert L.; Grummt U. W.; Buck K. A Photoswitchable Rotaxane with a Folded Molecular Thread. Chem. - Eur. J. 2004, 10, 3562–3568 10.1002/chem.200400243. [DOI] [PubMed] [Google Scholar]
Schmidt-Schaffer S.; Grubert L.; Grummt U. W.; Buck K.; Abraham W. A Photoswitchable Rotaxane with an Unfolded Molecular Thread. Eur. J. Org. Chem. 2006, 2006, 378–398 10.1002/ejoc.200500421. [DOI] [Google Scholar]
Umehara T.; Kawai H.; Fujiwara K.; Suzuki T. Entropy- and Hydrolytic-driven Positional Switching of Macrocycle Between Imine- and Hydrogen-bonding Stations in Rotaxane-based Molecular Shuttles. J. Am. Chem. Soc. 2008, 130, 13981–13988 10.1021/ja804888b. [DOI] [PubMed] [Google Scholar]
Berna J.; Alajarin M.; Orenes R. A. Azodicarboxamides as Template Binding Motifs for the Building of Hydrogen-Bonded Molecular Shuttles. J. Am. Chem. Soc. 2010, 132, 10741–10747 10.1021/ja101151t. [DOI] [PubMed] [Google Scholar]
Balzani V.; Clemente-Leon M.; Credi A.; Ferrer B.; Venturi M.; Flood A. H.; Stoddart J. F. Autonomous Artificial Nanomotor Powered by Sunlight. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 1178–1183 10.1073/pnas.0509011103. [DOI] [PMC free article] [PubMed] [Google Scholar]
Wurpel G. W. H.; Brouwer A. M.; van Stokkum I. H. M.; Farran A.; Leigh D. A. Enhanced Hydrogen Bonding Induced by Optical Excitation: Unexpected Subnanosecond Photoinduced Dynamics in a Peptide-based [2]Rotaxane. J. Am. Chem. Soc. 2001, 123, 11327–11328 10.1021/ja015919c. [DOI] [PubMed] [Google Scholar]
Wang Q. C.; Qu D. H.; Ren J.; Chen K. C.; Tian H. A Lockable Light-driven Molecular Shuttle with a Fluorescent Signal. Angew. Chem., Int. Ed. 2004, 43, 2661–2665 10.1002/anie.200453708. [DOI] [PubMed] [Google Scholar]
Bottari G.; Dehez F.; Leigh D. A.; Nash P. J.; Perez E. M.; Wong J. K. Y.; Zerbetto F. Entropy-driven Translational Isomerism: A Tristable Molecular Shuttle. Angew. Chem., Int. Ed. 2003, 42, 5886–5889 10.1002/anie.200352176. [DOI] [PubMed] [Google Scholar]
Altieri A.; Bottari G.; Dehez F.; Leigh D. A.; Wong J. K. Y.; Zerbetto F. Remarkable Positional Discrimination in Bistable Light- and Heat-switchable Hydrogen-bonded Molecular Shuttles. Angew. Chem., Int. Ed. 2003, 42, 2296–2300 10.1002/anie.200250745. [DOI] [PubMed] [Google Scholar]
Qu D. H.; Wang G. C.; Ren J.; Tian H. A Light-driven Rotaxane Molecular Shuttle with Dual Fluorescence Addresses. Org. Lett. 2004, 6, 2085–2088 10.1021/ol049605g. [DOI] [PubMed] [Google Scholar]
Zhou W. D.; Li J. B.; He X. R.; Li C. H.; Lv J.; Li Y. L.; Wang S.; Liu H. B.; Zhu D. B. A Molecular Shuttle for Driving a Multilevel Fluorescence Switch. Chem. - Eur. J. 2008, 14, 754–763 10.1002/chem.200701105. [DOI] [PubMed] [Google Scholar]
Qu D. H.; Ji F. Y.; Wang Q. C.; Tian H. A Double INHIBIT Logic Gate Employing Configuration and Fluorescence Changes. Adv. Mater. 2006, 18, 2035–2038 10.1002/adma.200600235. [DOI] [Google Scholar]
Zhou W. D.; Chen D. G.; Li J. B.; Xu J. L.; Lv J.; Liu H. B.; Li Y. L. Photoisomerization of Spiropyran for Driving a Molecular Shuttle. Org. Lett. 2007, 9, 3929–3932 10.1021/ol7015862. [DOI] [PubMed] [Google Scholar]
Gunbas D. D.; Zalewski L.; Brouwer A. M. Solvatochromic Rotaxane Molecular Shuttles. Chem. Commun. 2011, 47, 4977–4979 10.1039/c0cc05755j. [DOI] [PubMed] [Google Scholar]
Hanke A.; Metzler R. Towards the Molecular Workshop: Entropy-driven Designer Molecules, Entropy Activation, and Nanomechanical Devices. Chem. Phys. Lett. 2002, 359, 22–26 10.1016/S0009-2614(02)00675-9. [DOI] [Google Scholar]
Gong C. G.; Gibson H. W. Controlling Microstructure in Polymeric Molecular Shuttles: Solvent-induced Localization of Macrocycles in Poly(urethane/crown Ether) Rotaxanes. Angew. Chem., Int. Ed. Engl. 1997, 36, 2331–2333 10.1002/anie.199723311. [DOI] [Google Scholar]
Meng Z.; Xiang J. F.; Chen C. F. Tristable [n]Rotaxanes: From Molecular Shuttle to Molecular Cable Car. Chem. Sci. 2014, 5, 1520–1525 10.1039/c3sc53295j. [DOI] [Google Scholar]
Busseron E.; Coutrot F. N-benzyltriazolium as Both Molecular Station and Barrier in [2]Rotaxane Molecular Machines. J. Org. Chem. 2013, 78, 4099–106 10.1021/jo400414f. [DOI] [PubMed] [Google Scholar]
Serreli V.; Lee C. F.; Kay E. R.; Leigh D. A. A Molecular Information Ratchet. Nature 2007, 445, 523–527 10.1038/nature05452. [DOI] [PubMed] [Google Scholar]
Alvarez-Perez M.; Goldup S. M.; Leigh D. A.; Slawin A. M. Z. A Chemically-driven Molecular Information Ratchet. J. Am. Chem. Soc. 2008, 130, 1836–1838 10.1021/ja7102394. [DOI] [PubMed] [Google Scholar]
Carlone A.; Goldup S. M.; Lebrasseur N.; Leigh D. A.; Wilson A. A Three-compartment Chemically-driven Molecular Information Ratchet. J. Am. Chem. Soc. 2012, 134, 8321–8323 10.1021/ja302711z. [DOI] [PubMed] [Google Scholar]
Li H.; Cheng C. Y.; McGonigal P. R.; Fahrenbach A. C.; Frasconi M.; Liu W. G.; Zhu Z. X.; Zhao Y. L.; Ke C. F.; Lei J. Y.; et al. Relative Unidirectional Translation in an Artificial Molecular Assembly Fueled by Light. J. Am. Chem. Soc. 2013, 135, 18609–18620 10.1021/ja4094204. [DOI] [PubMed] [Google Scholar]
Cheng C.; McGonigal P. R.; Schneebeli S. T.; Li H.; Vermeulen N. A.; Ke C.; Stoddart J. F. An Artificial Molecular Pump. Nat. Nanotechnol. 2015, 10, 547–553 10.1038/nnano.2015.96. [DOI] [PubMed] [Google Scholar]
Cheng C.; McGonigal P. R.; Liu W.-G.; Li H.; Vermeulen N. A.; Ke C.; Frasconi M.; Stern C. L.; Goddard W. A. III; Stoddart J. F. Energetically Demanding Transport in a Supramolecular Assembly. J. Am. Chem. Soc. 2014, 136, 14702–14705 10.1021/ja508615f. [DOI] [PubMed] [Google Scholar]
Baroncini M.; Silvi S.; Venturi M.; Credi A. Photoactivated Directionally Controlled Transit of a Non-Symmetric Molecular Axle Through a Macrocycle. Angew. Chem., Int. Ed. 2012, 51, 4223–4226 10.1002/anie.201200555. [DOI] [PubMed] [Google Scholar]
Ragazzon G.; Baroncini M.; Silvi S.; Venturi M.; Credi A. Light-powered Autonomous and Directional Molecular Motion of a Dissipative Self-assembling System. Nat. Nanotechnol. 2014, 10, 70–75 10.1038/nnano.2014.260. [DOI] [PubMed] [Google Scholar]
Martinez-Cuezva A.; Pastor A.; Cioncoloni G.; Orenes R.-A.; Alajarin M.; Symes M. D.; Berna J. Versatile Control of the Submolecular Motion of Di(acylamino)pyridine-based [2]Rotaxanes. Chem. Sci. 2015, 6, 3087–3094 10.1039/C5SC00790A. [DOI] [PMC free article] [PubMed] [Google Scholar]
Leigh D. A.; Lusby P. J.; Slawin A. M. Z.; Walker D. B. Half-rotation in a Kinetically Locked [2] Catenane Induced by Transition Metal Ion Substitution. Chem. Commun. 2012, 48, 5826–5828 10.1039/c2cc32418k. [DOI] [PubMed] [Google Scholar]
Letinois-Halbes U.; Hanss D.; Beierle J. M.; Collin J.-P.; Sauvage J.-P. A Fast-moving [2]Rotaxane Whose Stoppers are Remote from the Copper Complex Core. Org. Lett. 2005, 7, 5753–5756 10.1021/ol052051c. [DOI] [PubMed] [Google Scholar]
Nakatani Y.; Furusho Y.; Yashima E. Amidinium Carboxylate Salt Bridges as a Recognition Motif for Mechanically Interlocked Molecules: Synthesis of an Optically Active [2]Catenane and Control of Its Structure. Angew. Chem., Int. Ed. 2010, 49, 5463–5467 10.1002/anie.201002382. [DOI] [PubMed] [Google Scholar]
Bermudez V.; Capron N.; Gase T.; Gatti F. G.; Kajzar F.; Leigh D. A.; Zerbetto F.; Zhang S. W. Influencing Intramolecular Motion with an Alternating Electric Field. Nature 2000, 406, 608–611 10.1038/35020531. [DOI] [PubMed] [Google Scholar]
Brancato G.; Coutrot F.; Leigh D. A.; Murphy A.; Wong J. K. Y.; Zerbetto F. From Reactants to Products via Simple Hydrogen-bonding Networks: Information Transmission in Chemical Reactions. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4967–4971 10.1073/pnas.072695799. [DOI] [PMC free article] [PubMed] [Google Scholar]
Lukin O.; Kubota T.; Okamoto Y.; Schelhase F.; Yoneva A.; Muller W. M.; Muller U.; Vogtle F. Knotaxanes - Rotaxanes with Knots as Stoppers. Angew. Chem., Int. Ed. 2003, 42, 4542–4545 10.1002/anie.200351981. [DOI] [PubMed] [Google Scholar]
Kapitulnik A.; Casalnuovo S.; Lim K. C.; Heeger A. J. Electric-Field Coupling to Slow Elastic Modes in Gels of Conjugated Polymers. Phys. Rev. Lett. 1984, 53, 469–472 10.1103/PhysRevLett.53.469. [DOI] [Google Scholar]
Lim K. C.; Kapitulnik A.; Zacher R.; Heeger A. J. Conformation of Polydiacetylene Macromolecules in Solution - Field-Induced Birefringence and Rotational Diffusion Constant. J. Chem. Phys. 1985, 82, 516–521 10.1063/1.448773. [DOI] [Google Scholar]
Gatti F. G.; Lent S.; Wong J. K. Y.; Bottari G.; Altieri A.; Morales M. A. F.; Teat S. J.; Frochot C.; Leigh D. A.; Brouwer A. M.; et al. Photoisomerization of a Rotaxane Hydrogen Bonding Template: Light-induced Acceleration of a Large Amplitude Rotational Motion. Proc. Natl. Acad. Sci. U. S. A. 2003, 100, 10–14 10.1073/pnas.0134757100. [DOI] [PMC free article] [PubMed] [Google Scholar]
Leigh D. A.; Moody K.; Smart J. P.; Watson K. J.; Slawin A. M. Z. Catenane Chameleons: Environment-sensitive Translational Isomerism in Amphiphilic Benzylic Amide [2]Catenanes. Angew. Chem., Int. Ed. Engl. 1996, 35, 306–310 10.1002/anie.199603061. [DOI] [Google Scholar]
Kemsley J. Water Lubricates Molecular Machines. Chem. Eng. News 2013, 91, 43–43. [Google Scholar]
Rijs A. M.; Compagnon I.; Oomens J.; Hannam J. S.; Leigh D. A.; Buma W. J. Stiff, and Sticky in the Right Places: Binding Interactions in Isolated Mechanically Interlocked Molecules Probed by Mid-Infrared Spectroscopy. J. Am. Chem. Soc. 2009, 131, 2428–2429 10.1021/ja808788c. [DOI] [PubMed] [Google Scholar]
Rijs A. M.; Sändig N.; Blom M. N.; Oomens J.; Hannam J. S.; Leigh D. A.; Zerbetto F.; Buma W. J. Controlled Hydrogen-Bond Breaking in a Rotaxane by Discrete Solvation. Angew. Chem., Int. Ed. 2010, 49, 3896–3900 10.1002/anie.201001231. [DOI] [PubMed] [Google Scholar]
Linke M.; Chambron J. C.; Heitz V.; Sauvage J.-P.; Semetey V. Complete Rearrangement of a Multi-porphyrinic Rotaxane by Metallation-demetallation of the Central Coordination Site. Chem. Commun. 1998, 2469–2470 10.1039/a805746j. [DOI] [Google Scholar]
Raehm L.; Kern J. M.; Sauvage J.-P. A Transition Metal Containing Rotaxane in Motion: Electrochemically Induced Pirouetting of the Ring on the Threaded Dumbbell. Chem. - Eur. J. 1999, 5, 3310–3317. [DOI] [Google Scholar]
Kern J. M.; Raehm L.; Sauvage J.-P.; Divisia-Blohorn B.; Vidal P. L. Controlled Molecular Motions in Copper-complexed Rotaxanes: An XAS Study. Inorg. Chem. 2000, 39, 1555–1560 10.1021/ic991163v. [DOI] [PubMed] [Google Scholar]
Weber N.; Hamann C.; Kern J. M.; Sauvage J.-P. Synthesis of a Copper [3]Rotaxane Able to Function as an Electrochemically Driven Oscillatory Machine in Solution, and to Form SAMs on a Metal Surface. Inorg. Chem. 2003, 42, 6780–6792 10.1021/ic0347034. [DOI] [PubMed] [Google Scholar]
Poleschak I.; Kern J. M.; Sauvage J.-P. A Copper-complexed Rotaxane in Motion: Pirouetting of the Ring on the Millisecond Timescale. Chem. Commun. 2004, 474–476 10.1039/b315080a. [DOI] [PubMed] [Google Scholar]
Ballesteros B.; Faust T. B.; Lee C. F.; Leigh D. A.; Muryn C. A.; Pritchard R. G.; Schultz D.; Teat S. J.; Timco G. A.; Winpenny R. E. P. Synthesis, Structure, and Dynamic Properties of Hybrid Organic-Inorganic Rotaxanes. J. Am. Chem. Soc. 2010, 132, 15435–15444 10.1021/ja1074773. [DOI] [PubMed] [Google Scholar]
Lee C. F.; Leigh D. A.; Pritchard R. G.; Schultz D.; Teat S. J.; Timco G. A.; Winpenny R. E. P. Hybrid Organic-inorganic Rotaxanes and Molecular Shuttles. Nature 2009, 458, 314–318 10.1038/nature07847. [DOI] [PubMed] [Google Scholar]
van Quaethem A.; Lussis P.; Leigh D. A.; Duwez A. S.; Fustin C. A. Probing the Mobility of Catenane Rings in Single Molecules. Chem. Sci. 2014, 5, 1449–1452 10.1039/c3sc53113a. [DOI] [Google Scholar]
Evans N. H.; Serpell C. J.; Beer P. D. A [2]Catenane Displaying Pirouetting Motion Triggered by Debenzylation and Locked by Chloride Anion Recognition. Chem. - Eur. J. 2011, 17, 7734–7738 10.1002/chem.201101033. [DOI] [PubMed] [Google Scholar]
Andrievsky A.; Ahuis F.; Sessler J. L.; Vogtle F.; Gudat D.; Moini M. Bipyrrole-based [2]Catenane: A New Type of Anion Receptor. J. Am. Chem. Soc. 1998, 120, 9712–9713 10.1021/ja980755u. [DOI] [Google Scholar]
Leontiev A. V.; Serpell C. J.; White N. G.; Beer P. D. Cation-induced Molecular Motion of Spring-like [2]Catenanes. Chem. Sci. 2011, 2, 922–927 10.1039/c1sc00034a. [DOI] [Google Scholar]
Fang L.; Wang C.; Fahrenbach A. C.; Trabolsi A.; Botros Y. Y.; Stoddart J. F. Dual Stimulus Switching of a [2]Catenane in Water. Angew. Chem., Int. Ed. 2011, 50, 1805–1809 10.1002/anie.201006362. [DOI] [PubMed] [Google Scholar]
Amabilino D. B.; Dietrich-Buchecker C. O.; Livoreil A.; PerezGarcia L.; Sauvage J.-P.; Stoddart J. F. A Switchable Hybrid [2]-Catenane Based on Transition Metal Complexation and pi-Electron Donor-acceptor Interactions. J. Am. Chem. Soc. 1996, 118, 3905–3913 10.1021/ja954329+. [DOI] [PubMed] [Google Scholar]
Balzani V.; Credi A.; Langford S. J.; Raymo F. M.; Stoddart J. F.; Venturi M. Constructing Molecular Machinery: A Chemically-switchable [2]Catenane. J. Am. Chem. Soc. 2000, 122, 3542–3543 10.1021/ja994454b. [DOI] [Google Scholar]
Grunder S.; McGrier P. L.; Whalley A. C.; Boyle M. M.; Stern C.; Stoddart J. F. A Water-Soluble pH-Triggered Molecular Switch. J. Am. Chem. Soc. 2013, 135, 17691–17694 10.1021/ja409006y. [DOI] [PubMed] [Google Scholar]
Korybut-Daszkiewicz B.; Wieckowska A.; Bilewicz R.; Domagala S.; Wozniak K. An Electrochemically Controlled Molecular Shuttle. Angew. Chem., Int. Ed. 2004, 43, 1668–1672 10.1002/anie.200352528. [DOI] [PubMed] [Google Scholar]
Flamigni L.; Talarico A. M.; Serroni S.; Puntoriero F.; Gunter M. J.; Johnston M. R.; Jeynes T. P. Photoinduced Electron Transfer Between the Interlocked Components of Porphyrin Catenanes: Effect of the Presence of Nonequivalent Reduction Sites on the Charge Recombination Rate. Chem. - Eur. J. 2003, 9, 2649–2659 10.1002/chem.200204502. [DOI] [PubMed] [Google Scholar]
Zheng X. G.; Sohlberg K. Modeling Bistability and Switching in a [2]Catenane. Phys. Chem. Chem. Phys. 2004, 6, 809–815 10.1039/b310816c. [DOI] [Google Scholar]
Ceccarelli M.; Mercuri F.; Passerone D.; Parrinello M. The Microscopic Switching Mechanism of a [2]Catenane. J. Phys. Chem. B 2005, 109, 17094–17099 10.1021/jp051609v. [DOI] [PubMed] [Google Scholar]
Ashton P. R.; Baldoni V.; Balzani V.; Credi A.; Hoffmann H. D. A.; Martinez-Diaz M. V.; Raymo F. M.; Stoddart J. F.; Venturi M. Dual-mode ″Co-conformational″ Switching in Catenanes Incorporating Bipyridinium and Dialkylammonium Recognition Sites. Chem. - Eur. J. 2001, 7, 3482–3493. [DOI] [PubMed] [Google Scholar]
Hamilton D. G.; Montalti M.; Prodi L.; Fontani M.; Zanello P.; Sanders J. K. M. Photophysical and Electrochemical Characterization of the Interactions Between Components in Neutral pi-Associated [2]Catenanes. Chem. - Eur. J. 2000, 6, 608–617. [DOI] [PubMed] [Google Scholar]
Ashton P. R.; Ballardini R.; Balzani V.; Credi A.; Gandolfi M. T.; Menzer S.; Perezgarcia L.; Prodi L.; Stoddart J. F.; Venturi M. Molecular Meccano 0.4. The Self-Assembly of [2]Catenanes Incorporating Photoactive and Electroactive Pi-Extended Systems. J. Am. Chem. Soc. 1995, 117, 11171–11197 10.1021/ja00150a015. [DOI] [Google Scholar]
Ashton P. R.; Ballardini R.; Balzani V.; Gandolfi M. T.; Marquis D. J. F.; Perezgarcia L.; Prodi L.; Stoddart J. F.; Venturi M. The Self-Assembly of Controllable [2]Catenanes. J. Chem. Soc., Chem. Commun. 1994, 177–180 10.1039/c39940000177. [DOI] [Google Scholar]
Livoreil A.; Dietrich-Buchecker C. O.; Sauvage J.-P. Electrochemically Triggered Swinging of a [2]-Catenate. J. Am. Chem. Soc. 1994, 116, 9399–9400 10.1021/ja00099a095. [DOI] [PubMed] [Google Scholar]
Baumann F.; Livoreil A.; Kaim W.; Sauvage J.-P. Changeover in a Multimodal Copper(II) Catenate as Monitored by EPR Spectroscopy. Chem. Commun. 1997, 35–36 10.1039/a606282b. [DOI] [Google Scholar]
Livoreil A.; Sauvage J.-P.; Armaroli N.; Balzani V.; Flamigni L.; Ventura B. Electrochemically and Photochemically Driven Ring Motions in a Disymmetrical Copper [2]-Catenate. J. Am. Chem. Soc. 1997, 119, 12114–12124 10.1021/ja9720826. [DOI] [PubMed] [Google Scholar]
Cardenas D. J.; Livoreil A.; Sauvage J.-P. Redox Control of the Ring-gliding Motion in a Cu-complexed Catenane: A Process Involving Three Distinct Geometries. J. Am. Chem. Soc. 1996, 118, 11980–11981 10.1021/ja962774e. [DOI] [Google Scholar]
Dietrich-Buchecker C.; Sauvage J.-P. Templated Synthesis of Interlocked Macrocyclic Ligands, the Catenands - Preparation and Characterization of the Prototypical Bis-30 Membered Ring-System. Tetrahedron 1990, 46, 503–512 10.1016/S0040-4020(01)85433-8. [DOI] [Google Scholar]
Cesario M.; Dietrich-Buchecker C. O.; Guilhem J.; Pascard C.; Sauvage J.-P. Molecular-Structure of a Catenand and Its Copper(I) Catenate - Complete Rearrangement of the Interlocked Macrocyclic Ligands by Complexation. J. Chem. Soc., Chem. Commun. 1985, 244–247 10.1039/c39850000244. [DOI] [Google Scholar]
Cesario M.; Dietrich C. O.; Edel A.; Guilhem J.; Kintzinger J. P.; Pascard C.; Sauvage J.-P. Topological Enhancement of Basicity - Molecular-Structure and Solution Study of a Monoprotonated Catenand. J. Am. Chem. Soc. 1986, 108, 6250–6254 10.1021/ja00280a023. [DOI] [Google Scholar]
Albrechtgary A. M.; Dietrich-Buchecker C.; Saad Z.; Sauvage J.-P. Topological Kinetic Effects - Complexation of Interlocked Macrocyclic Ligands by Cationic Species. J. Am. Chem. Soc. 1988, 110, 1467–1472 10.1021/ja00213a018. [DOI] [Google Scholar]
Dietrich-Buchecker C.; Sauvage J.-P.; Kern J. M. Synthesis and Electrochemical Studies of Catenates - Stabilization of Low Oxidation-States by Interlocked Macrocyclic Ligands. J. Am. Chem. Soc. 1989, 111, 7791–7800 10.1021/ja00202a020. [DOI] [Google Scholar]
Albrechtgary A. M.; Dietrich-Buchecker C.; Saad Z.; Sauvage J.-P. Formation of Li+ and Cd2+ Catenates, a Reaction with a Negative Enthalpy of Activation. J. Chem. Soc., Chem. Commun. 1992, 280–282 10.1039/c39920000280. [DOI] [Google Scholar]
Armaroli N.; Decola L.; Balzani V.; Sauvage J.-P.; Dietrich-Buchecker C. O.; Kern J. M.; Bailal A. Absorption and Emission Properties of a 2-Catenand, Its Protonated Forms, and Its Complexes with Li⁺, Cu⁺, Ag⁺, Co²⁺, Ni²⁺, Zn²⁺, Pd²⁺ and Cd²⁺ - Tuning of the Luminescence over the Whole Visible Spectral Region. J. Chem. Soc., Dalton Trans. 1993, 3241–3247 10.1039/dt9930003241. [DOI] [Google Scholar]
Sauvage J.-P.; Weiss J. Synthesis of Dicopper(I) [3]Catenates - Multiring Interlocked Coordinating Systems. J. Am. Chem. Soc. 1985, 107, 6108–6110 10.1021/ja00307a049. [DOI] [PubMed] [Google Scholar]
Dietrich-Buchecker C. O.; Khemiss A.; Sauvage J.-P. High-Yield Synthesis of Multiring Copper(I) Catenates by Acetylenic Oxidative Coupling. J. Chem. Soc., Chem. Commun. 1986, 1376–1378 10.1039/c39860001376. [DOI] [Google Scholar]
Mohr B.; Weck M.; Sauvage J. P.; Grubbs R. H. High-yield synthesis of [2]catenanes by intramolecular ring-closing metathesis. Angew. Chem., Int. Ed. Engl. 1997, 36, 1308–1310 10.1002/anie.199713081. [DOI] [Google Scholar]
Koizumi M.; Dietrich-Buchecker C.; Sauvage J.-P. A [2]Catenane Containing 1,1′-Binaphthyl Units and 1,10-Phenanthroline Fragments: Synthesis and Intermolecular Energy Transfer Processes. Eur. J. Org. Chem. 2004, 2004, 770–775 10.1002/ejoc.200300572. [DOI] [Google Scholar]
Fuller A. M. L.; Leigh D. A.; Lusby P. J.; Slawin A. M. Z.; Walker D. B. Selecting Topology and Connectivity Through Metal-directed Macrocyclization Reactions: A Square Planar Palladium [2]Catenate and Two Noninterlocked Isomers. J. Am. Chem. Soc. 2005, 127, 12612–12619 10.1021/ja053005a. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Lusby P. J.; Slawin A. M. Z.; Walker D. B. Half-rotation in a [2] Catenane via Interconvertible Pd(II) Coordination Modes. Chem. Commun. 2005, 4919–4921 10.1039/b510663j. [DOI] [PubMed] [Google Scholar]
Mobian P.; Kern J. M.; Sauvage J.-P. Light-driven Machine Prototypes Based on Dissociative Excited States: Photoinduced Decoordination and Thermal Recoordination of a Ring in a Ruthenium(II)-containing [2]Catenane. Angew. Chem., Int. Ed. 2004, 43, 2392–2395 10.1002/anie.200352522. [DOI] [PubMed] [Google Scholar]
Baranoff E.; Collin J.-P.; Furusho Y.; Laemmel A. C.; Sauvage J.-P. A Photochromic System Based on Photochemical or Thermal Chelate Exchange on Ru(phen)₂L²⁺ (L = Diimine or Dinitrile Ligand). Chem. Commun. 2000, 1935–1936 10.1039/b004982o. [DOI] [PubMed] [Google Scholar]
Collin J.-P.; Laemmel A. C.; Sauvage J.-P. Photochemical Expulsion of a Ru(phen)₂ Unit From a Macrocyclic Receptor and its Thermal Reco-ordination. New J. Chem. 2001, 25, 22–24 10.1039/b007192g. [DOI] [Google Scholar]
Laemmel A. C.; Collin J.-P.; Sauvage J.-P.; Accorsi G.; Armaroli N. Macrocyclic complexes of [Ru(N-N)₂]²⁺ Units [N-N = 1,10 Phenanthroline or 4-(p-Anisyl)-1,10-Phenanthroline]: Synthesis and Photochemical Expulsion Studies. Eur. J. Inorg. Chem. 2003, 2003, 467–474 10.1002/ejic.200390066. [DOI] [Google Scholar]
Bonnet S.; Collin J.-P.; Sauvage J.-P. A Ru(terpy) (phen)-Incorporating Ring and its Light-induced Geometrical Changes. Chem. Commun. 2005, 3195–3197 10.1039/b503411f. [DOI] [PubMed] [Google Scholar]
Collin J.-P.; Jouvenot D.; Koizumi M.; Sauvage J.-P. Light-driven Expulsion of the Sterically Hindering Ligand L in Tris-diimine Ruthenium(II) Complexes of the Ru(phen)₂L²⁺ Family: A Pronounced Ring Effect. Inorg. Chem. 2005, 44, 4693–4698 10.1021/ic050246a. [DOI] [PubMed] [Google Scholar]
Arico F.; Mobian P.; Kern J. M.; Sauvage J.-P. Synthesis of a [2]Catenane Around a Ru(diimine)₃²⁺ Scaffold by Ring-closing Metathesis of olefins. Org. Lett. 2003, 5, 1887–1890 10.1021/ol0300367. [DOI] [PubMed] [Google Scholar]
Pomeranc D.; Jouvenot D.; Chambron J. C.; Collin J.-P.; Heitz V.; Sauvage J.-P. Templated Synthesis of a Rotaxane with a [Ru(diimine)₃]²⁺ Core. Chem. - Eur. J. 2003, 9, 4247–4254 10.1002/chem.200304716. [DOI] [PubMed] [Google Scholar]
Laemmel A. C.; Collin J.-P.; Sauvage J.-P. Efficient and Selective Photochemical Labilization of a Given Bidentate Ligand in Mixed Ruthenium(II) Complexes of the Ru(phen)₂L²⁺ and Ru(bipy)₂L²⁺ Family (L = Sterically Hindering Chelate). Eur. J. Inorg. Chem. 1999, 1999, 383–386. [DOI] [Google Scholar]
Vogtle F.; Muller W. M.; Muller U.; Bauer M.; Rissanen K. Photoswitchable Catenanes. Angew. Chem., Int. Ed. Engl. 1993, 32, 1295–1297 10.1002/anie.199312951. [DOI] [Google Scholar]
Ashton P. R.; Blower M.; Philp D.; Spencer N.; Stoddart J. F.; Tolley M. S.; Ballardini R.; Ciano M.; Balzani V.; Gandolfi M. T.; et al. The Control of Translational Isomerism in Catenated Structures. New J. Chem. 1993, 17, 689–695. [Google Scholar]
Raymo F. M.; Houk K. N.; Stoddart J. F. Origins of Selectivity in Molecular and Supramolecular Entities: Solvent and Electrostatic Control of the Translational Isomerism in [2]Catenanes. J. Org. Chem. 1998, 63, 6523–6528 10.1021/jo980543f. [DOI] [Google Scholar]
Ballardini R.; Balzani V.; Gandolfi M. T.; Gillard R. E.; Stoddart J. F.; Tabellini E. The Synthesis and Spectroscopic Properties of Macrocyclic Polyethers Containing Two Different Aromatic Moieties and Their [2]Catenanes Incorporating Cyclobis(paraquat-p-phenylene). Chem. - Eur. J. 1998, 4, 449–459. [DOI] [Google Scholar]
Leigh D. A.; Wong J. K. Y.; Dehez F.; Zerbetto F. Unidirectional Rotation in a Mechanically Interlocked Molecular Rotor. Nature 2003, 424, 174–179 10.1038/nature01758. [DOI] [PubMed] [Google Scholar]
Baranoff E. D.; Voignier J.; Yasuda T.; Heitz V.; Sauvage J.-P.; Kato T. A Liquid-Crystalline [2]Catenane and Its Copper(I) Complex. Angew. Chem., Int. Ed. 2007, 46, 4680–4683 10.1002/anie.200700308. [DOI] [PubMed] [Google Scholar]
Hernandez J. V.; Kay E. R.; Leigh D. A. A Reversible Synthetic Rotary Molecular Motor. Science 2004, 306, 1532–1537 10.1126/science.1103949. [DOI] [PubMed] [Google Scholar]
Karczmarek J.; Wright J.; Corkum P.; Ivanov M. Optical Centrifuge for Molecules. Phys. Rev. Lett. 1999, 82, 3420–3423 10.1103/PhysRevLett.82.3420. [DOI] [Google Scholar]
Villeneuve D. M.; Aseyev S. A.; Dietrich P.; Spanner M.; Ivanov M. Y.; Corkum P. B. Forced Molecular Rotation in an Optical Centrifuge. Phys. Rev. Lett. 2000, 85, 542–545 10.1103/PhysRevLett.85.542. [DOI] [PubMed] [Google Scholar]
Charlier J. C.; Michenaud J.-P. Energetics of Multilayered Carbon Tubules. Phys. Rev. Lett. 1993, 70, 1858–1861 10.1103/PhysRevLett.70.1858. [DOI] [PubMed] [Google Scholar]
Merkle R. C. A Proof About Molecular Bearings. Nanotechnology 1993, 4, 86–90 10.1088/0957-4484/4/2/004. [DOI] [Google Scholar]
Tuzun R. E.; Noid D. W.; Sumpter B. G. The Dynamics of Molecular Bearings. Nanotechnology 1995, 6, 64–74 10.1088/0957-4484/6/2/005. [DOI] [Google Scholar]
Han J.; Globus A.; Jaffe R.; Deardorff G. Molecular Dynamics Simulations of Carbon Nanotube-based Gears. Nanotechnology 1997, 8, 95–102 10.1088/0957-4484/8/3/001. [DOI] [Google Scholar]
Sohlberg K.; Tuzun R. E.; Sumpter B. G.; Noid D. W. Application of Rigid-body dynamics and Semiclassical Mechanics to Molecular Bearings. Nanotechnology 1997, 8, 103–111 10.1088/0957-4484/8/3/002. [DOI] [Google Scholar]
Globus A.; Bauschlicher C. W. Jr.; Han J.; Jaffe R. L.; Levit C.; Srivastava D. Machine Phase Fullerene Nanotechnology. Nanotechnology 1998, 9, 192–199 10.1088/0957-4484/9/3/008. [DOI] [Google Scholar]
Kwon Y.-K.; Tomanek D.. Electronic and Structural Properties of Multiwall Carbon Nanotubes. Phys. Rev. B: Condens. Matter Mater. Phys. 1998, 58, R16001, 10.1103/PhysRevB.58.R16001. [DOI] [Google Scholar]
Tuzun R. E.; Sohlberg K.; Noid D. W.; Sumpter B. G. Docking Envelopes for the Assembly of Molecular Bearings. Nanotechnology 1998, 9, 37–48 10.1088/0957-4484/9/1/005. [DOI] [Google Scholar]
Palser A. H. R. Interlayer Interactions in Graphite and Carbon Nanotubes. Phys. Chem. Chem. Phys. 1999, 1, 4459–4464 10.1039/a905154f. [DOI] [Google Scholar]
Cumings J. Low-Friction Nanoscale Linear Bearing Realized from Multiwall Carbon Nanotubes. Science 2000, 289, 602–604 10.1126/science.289.5479.602. [DOI] [PubMed] [Google Scholar]
Kolmogorov A. N.; Crespi V. H. The Smoothest Bearings: Interlayer Sliding in Multiwalled Carbon Nanotubes. Phys. Rev. Lett. 2000, 85, 4727–4730 10.1103/PhysRevLett.85.4727. [DOI] [PubMed] [Google Scholar]
Yu M.-F.; Yakobson B. I.; Ruoff R. S. Controlled Sliding and Pullout of Nested Shells in Individual Multiwalled Carbon Nanotubes. J. Phys. Chem. B 2000, 104, 8764–8767 10.1021/jp002828d. [DOI] [Google Scholar]
Saito R.; Matsuo R.; Kimura T.; Dresselhaus G.; Dresselhaus M. S. Anomalous Potential Barrier of Double-wall Carbon Nanotubes. Chem. Phys. Lett. 2001, 348, 187–193 10.1016/S0009-2614(01)01127-7. [DOI] [Google Scholar]
Damnjanović M.; Vuković T.; Milošević I. Super-slippery Carbon Nanotubes. Eur. Phys. J. B 2002, 25, 131–134 10.1140/epjb/e20020014. [DOI] [Google Scholar]
Zheng Q.; Jiang Q. Multiwalled Carbon Nanotubes as Gigahertz Oscillators. Phys. Rev. Lett. 2002, 88, 045503. 10.1103/PhysRevLett.88.045503. [DOI] [PubMed] [Google Scholar]
Zheng Q.; Liu J.; Jiang Q. Excess van der Waals Interaction Energy of a Multiwalled Carbon Nanotube with an Extruded Core and the Induced Core Oscillation. Phys. Rev. B: Condens. Matter Mater. Phys. 2002, 65, 245409.1–245409.6 10.1103/PhysRevB.65.245409. [DOI] [Google Scholar]
Damnjanović M.; Dobardzic E.; Milosevic I.; Vukovic T.; Nikolic B. Lattice Dynamics and Symmetry of Double Wall Carbon Nanotubes. New J. Phys. 2003, 5, 148. 10.1088/1367-2630/5/1/148. [DOI] [Google Scholar]
Guo W.; Guo Y.; Gao H.; Zheng Q.; Zhong W. Energy Dissipation in Gigahertz Oscillators from Multiwalled Carbon Nanotubes. Phys. Rev. Lett. 2003, 91, 125501. 10.1103/PhysRevLett.91.125501. [DOI] [PubMed] [Google Scholar]
Legoas S.; Coluci V.; Braga S.; Coura P.; Dantas S.; Galvão D. Molecular-Dynamics Simulations of Carbon Nanotubes as Gigahertz Oscillators. Phys. Rev. Lett. 2003, 90, 055504. 10.1103/PhysRevLett.90.055504. [DOI] [PubMed] [Google Scholar]
Lozovik Y. E.; Minogin A. V.; Popov A. M. Nanomachines Based on Carbon Nanotubes. Phys. Lett. A 2003, 313, 112–121 10.1016/S0375-9601(03)00649-2. [DOI] [Google Scholar]
Lozovik Y. E.; Minogin A. V.; Popov A. M. Possible Nanomachines: Nanotube Walls as Movable Elements. JETP Lett. 2003, 77, 631–635 10.1134/1.1600820. [DOI] [Google Scholar]
Servantie J.; Gaspard P. Methods of Calculation of a Friction Coefficient: Application to Nanotubes. Phys. Rev. Lett. 2003, 91, 185503. 10.1103/PhysRevLett.91.185503. [DOI] [PubMed] [Google Scholar]
Vukovic T.; Damnjanovic M.; Milosevic I. Interaction Between Layers of the Multi-wall Carbon Nanotubes. Phys. E 2003, 16, 259–268 10.1016/S1386-9477(02)00685-9. [DOI] [Google Scholar]
Lin J.-S.; Lin J.-H.; Chang C.-C. Molecular Dynamics Simulations of the Rotary Motor F₀ Under External Electric Fields Across the Membrane. Biophys. J. 2010, 98, 1009–1017 10.1016/j.bpj.2009.11.025. [DOI] [PMC free article] [PubMed] [Google Scholar]
Williams P. A.; Papadakis S. J.; Patel A. M.; Falvo M. R.; Washburn S.; Superfine R. Fabrication of Nanometer-scale Mechanical Devices Incorporating Individual Multiwalled Carbon Nanotubes as Torsional Springs. Appl. Phys. Lett. 2003, 82, 805–907 10.1063/1.1538346. [DOI] [Google Scholar]
Zhao Y.; Ma C.-C.; Chen G.; Jiang Q. Energy Dissipation Mechanisms in Carbon Nanotube Oscillators. Phys. Rev. Lett. 2003, 91, 175504. 10.1103/PhysRevLett.91.175504. [DOI] [PubMed] [Google Scholar]
Belikov A. V.; Lozovik Y. E.; Nikolaev A. G.; Popov A. M. Double-wall Nanotubes: Classification and Barriers to Walls Relative Rotation, Sliding and Screwlike Motion. Chem. Phys. Lett. 2004, 385, 72–78 10.1016/j.cplett.2003.12.049. [DOI] [Google Scholar]
Bourlon B.; Glattli D. C.; Miko C.; Forro L.; Bachtold A. Carbon Nanotube Based Bearing for Rotational Motions. Nano Lett. 2004, 4, 709–712 10.1021/nl035217g. [DOI] [Google Scholar]
Kang J. W.; Hwang H. J. Gigahertz Actuator of Multiwall Marbon Nanotube Encapsulating Metallic Ions: Molecular Dynamics Simulations. J. Appl. Phys. 2004, 96, 3900–3905 10.1063/1.1785837. [DOI] [Google Scholar]
Kang J. W.; Hwang H. J. Nanoscale Carbon Nanotube Motor Schematics and Simulations for Micro-electro-mechanical Machines. Nanotechnology 2004, 15, 1633–1638 10.1088/0957-4484/15/11/045. [DOI] [Google Scholar]
Legoas S. B.; Coluci V. R.; Braga S. F.; Coura P. Z.; Dantas S. O.; Galvão D. S. Gigahertz Nanomechanical Oscillators Based on Carbon Nanotubes. Nanotechnology 2004, 15, S184–S189 10.1088/0957-4484/15/4/012. [DOI] [Google Scholar]
Papadakis S.; Hall A.; Williams P.; Vicci L.; Falvo M.; Superfine R.; Washburn S. Resonant Oscillators with Carbon-Nanotube Torsion Springs. Phys. Rev. Lett. 2004, 93, 146101. 10.1103/PhysRevLett.93.146101. [DOI] [PubMed] [Google Scholar]
Regan B. C.; Aloni S.; Ritchie R. O.; Dahmen U.; Zettl A. Carbon Nanotubes as Nanoscale Mass Conveyors. Nature 2004, 428, 924–927 10.1038/nature02496. [DOI] [PubMed] [Google Scholar]
Tangney P.; Louie S.; Cohen M. Dynamic Sliding Friction between Concentric Carbon Nanotubes. Phys. Rev. Lett. 2004, 93, 065530. 10.1103/PhysRevLett.93.065503. [DOI] [PubMed] [Google Scholar]
Tu Z. C.; Ou-Yang Z. C. A Molecular Motor Constructed from a Double-walled Carbon Nanotube Driven by Temperature Variation. J. Phys.: Condens. Matter 2004, 16, 1287–1292 10.1088/0953-8984/16/8/012. [DOI] [Google Scholar]
Bichoutskaia E.; Popov A.; El-Barbary A.; Heggie M.; Lozovik Y. Ab initio Study of Relative Motion of Walls in Carbon Nanotubes. Phys. Rev. B: Condens. Matter Mater. Phys. 2005, 71, 113403. 10.1103/PhysRevB.71.113403. [DOI] [Google Scholar]
Kang J. W.; Song K. O.; Kwon O. K.; Hwang H. J. Carbon Nanotube Oscillator Operated by Thermal Expansion of Encapsulated Gases. Nanotechnology 2005, 16, 2670–2676 10.1088/0957-4484/16/11/034. [DOI] [Google Scholar]
Meyer J. C.; Paillet M.; Roth S. Single-molecule Torsional Pendulum. Science 2005, 309, 1539–1541 10.1126/science.1115067. [DOI] [PubMed] [Google Scholar]
Regan B. C.; Aloni S.; Jensen K.; Ritchie R. O.; Zettl A. Nanocrystal-Powered Nanomotor. Nano Lett. 2005, 5, 1730–1733 10.1021/nl0510659. [DOI] [PubMed] [Google Scholar]
Tu Z.; Hu X. Molecular Motor Constructed From a Double-walled Carbon Nanotube Driven by Axially Varying Voltage. Phys. Rev. B: Condens. Matter Mater. Phys. 2005, 72, 033404. 10.1103/PhysRevB.72.033404. [DOI] [Google Scholar]
Tasis D.; Tagmatarchis N.; Bianco A.; Prato M. Chemistry of Carbon Nanotubes. Chem. Rev. 2006, 106, 1105–1136 10.1021/cr050569o. [DOI] [PubMed] [Google Scholar]
Yuzvinsky T. D.; Fennimore A. M.; Kis A.; Zettl A. Controlled Placement of Highly Aligned Carbon Nanotubes for the Manufacture of Arrays of Nanoscale Torsional Actuators. Nanotechnology 2006, 17, 434–438 10.1088/0957-4484/17/2/015. [DOI] [Google Scholar]
Li R.; Sun D.; Zhang B. Motion and Energy Dissipation of Single-walled Carbon Nanotube on Graphite by Molecular Dynamics Simulation. Mater. Res. Express 2014, 1, 025046. 10.1088/2053-1591/1/2/025046. [DOI] [Google Scholar]
Bedard T. C.; Moore J. S. Design and Synthesis of Molecular Turnstiles. J. Am. Chem. Soc. 1995, 117, 10662–10671 10.1021/ja00148a008. [DOI] [Google Scholar]
Hsu L. Y.; Li E. Y.; Rabitz H. Single-molecule Electric Revolving Door. Nano Lett. 2013, 13, 5020–5025 10.1021/nl401340c. [DOI] [PubMed] [Google Scholar]
Troisi A.; Ratner M. Molecular Rectification Through Electric Field Induced Conformational Changes. J. Am. Chem. Soc. 2002, 124, 14528–14529 10.1021/ja028281t. [DOI] [PubMed] [Google Scholar]
Troisi A.; Ratner M. A. Conformational Molecular Rectifiers. Nano Lett. 2004, 4, 591–595 10.1021/nl0352088. [DOI] [Google Scholar]
Goychuk I.; Haenggi P. Quantum Rectifiers From Harmonic Mixing. Europhys. Lett. 1998, 43, 503–509 10.1209/epl/i1998-00389-2. [DOI] [Google Scholar]
Kornilovitch P.; Bratkovsky A.; Williams R. Bistable Molecular Conductors with a Field-switchable Dipole Group. Phys. Rev. B: Condens. Matter Mater. Phys. 2002, 66, 245413. 10.1103/PhysRevB.66.245413. [DOI] [Google Scholar]
Ghosh A. W.; Rakshit T.; Datta S. Gating of a Molecular Transistor: Electrostatic and Conformational. Nano Lett. 2004, 4, 565–568 10.1021/nl035109u. [DOI] [Google Scholar]
Tuzun R. E.; Noid D. W.; Sumpter B. G. Dynamics of a Laser Driven Molecular Motor. Nanotechnology 1995, 6, 52–63 10.1088/0957-4484/6/2/004. [DOI] [Google Scholar]
Hoki K.; Gonzalez L.; Fujimura Y. Control of Molecular Handedness Using Pump-dump Laser Pulses. J. Chem. Phys. 2002, 116, 2433–2438 10.1063/1.1432996. [DOI] [Google Scholar]
Hoki K.; Yamaki M.; Fujimura Y. Chiral Molecular Motors Driven by a Nonhelical Laser Pulse. Angew. Chem., Int. Ed. 2003, 42, 2976–2978 10.1002/anie.200250872. [DOI] [PubMed] [Google Scholar]
Hoki K.; Yamaki M.; Koseki S.; Fujimura Y. Mechanism of Unidirectional Motions of Chiral Molecular Motors Driven by Linearly Polarized Pulses. J. Chem. Phys. 2003, 119, 12393–12398 10.1063/1.1621622. [DOI] [Google Scholar]
Hoki K.; Yamaki M.; Koseki S.; Fujimura Y. Molecular Motors Driven by Laser Pulses: Role of Molecular Chirality and Photon Helicity. J. Chem. Phys. 2003, 118, 497–504 10.1063/1.1526834. [DOI] [Google Scholar]
Hoki K.; Sato M.; Yamaki M.; Sahnoun R.; Gonzalez L.; Koseki S.; Fujimura Y. Chiral Molecular Motors Ignited by Femtosecond Pump-dump Laser Pulses. J. Phys. Chem. B 2004, 108, 4916–4921 10.1021/jp036437l. [DOI] [Google Scholar]
Kono H.; Sato Y.; Tanaka N.; Kato T.; Nakai K.; Koseki S.; Fujimura Y. Quantum Mechanical Study of Electronic and Nuclear Dynamics of Molecules in Intense Laser Fields. Chem. Phys. 2004, 304, 203–226 10.1016/j.chemphys.2004.04.017. [DOI] [Google Scholar]
Hoki K.; Sato M.; Yamaki M.; Sahnoun R.; Gonzalez L.; Koseki S.; Fujimura Y. Chiral Molecular Motors Ignited by Femtosecond Pump–Dump Laser Pulses. J. Phys. Chem. B 2004, 108, 4916–4921 10.1021/jp036437l. [DOI] [Google Scholar]
Yamaki M.; Hoki K.; Ohtsuki Y.; Kono H.; Fujimura Y. Quantum Control of Unidirectional Rotations of a Chiral Molecular Motor. Phys. Chem. Chem. Phys. 2005, 7, 900–904 10.1039/b418231f. [DOI] [PubMed] [Google Scholar]
Yamaki M.; Hoki K.; Ohtsuki Y.; Kono H.; Fujimura Y. Quantum Control of a Chiral Molecular Motor Driven by Laser Pulses. J. Am. Chem. Soc. 2005, 127, 7300–7301 10.1021/ja0437757. [DOI] [PubMed] [Google Scholar]
Yamaki M.; Hoki K.; Kono H.; Fujimura Y. Quantum Control of a Chiral Molecular Motor Driven by Femtosecond Laser Pulses: Mechanisms of Regular and Reverse Rotations. Chem. Phys. 2008, 347, 272–274 10.1016/j.chemphys.2007.11.016. [DOI] [Google Scholar]
Yamaki M.; Hoki K.; Teranishi T.; Chung W.; Pichierri F.; Kono H.; Fujimura Y. Theoretical Design of an Aromatic Hydrocarbon Rotor Driven by a Circularly Polarized Electric Field. J. Phys. Chem. A 2007, 111, 9374–9378 10.1021/jp073953t. [DOI] [PubMed] [Google Scholar]
Yamaki M.; Nakayama S.; Hoki K.; Kono H.; Fujimura Y. Quantum Dynamics of Light-driven Chiral Molecular Motors. Phys. Chem. Chem. Phys. 2009, 11, 1662–1678 10.1039/b815047h. [DOI] [PubMed] [Google Scholar]
Fujimura Y.; González L.; Kröner D.; Manz J.; Mehdaoui I.; Schmidt B. Quantum Ignition of Intramolecular Rotation by Means of IR+UV Laser Pulses. Chem. Phys. Lett. 2004, 386, 248–253 10.1016/j.cplett.2004.01.070. [DOI] [Google Scholar]
Jian H.; Tour J. En Route to Surface-bound Electric Field-driven Molecular Motors. J. Org. Chem. 2003, 68, 5091–5103 10.1021/jo034169h. [DOI] [PubMed] [Google Scholar]
Caskey D.; Shoemaker R.; Michl J. Toward Self-assembled Surface-mounted Prismatic Altitudinal Rotors. A Test Case: Molecular Rectangle. Org. Lett. 2004, 6, 2093–2096 10.1021/ol049539i. [DOI] [PubMed] [Google Scholar]
Zheng X.; Mulcahy M.; Horinek D.; Galeotti F.; Magnera T.; Michl J. Dipolar and Nonpolar Altitudinal Molecular Rotors Mounted on an Au(111) Surface. J. Am. Chem. Soc. 2004, 126, 4540–4542 10.1021/ja039482f. [DOI] [PubMed] [Google Scholar]
Magnera T.; Michl J.; Kelly T. Altitudinal Surface-mounted Molecular Rotors. Molecular Machines 2005, 262, 63–97 10.1007/128_014. [DOI] [Google Scholar]
Caskey D.; Michl J. Toward Self-assembled Surface-mounted Prismatic Altitudinal Rotors. A Test Case: Trigonal and Tetragonal Prisms. J. Org. Chem. 2005, 70, 5442–5448 10.1021/jo050409c. [DOI] [PubMed] [Google Scholar]
Kottas G.; Clarke L.; Horinek D.; Michl J. Artificial Molecular Rotors. Chem. Rev. 2005, 105, 1281–1376 10.1021/cr0300993. [DOI] [PubMed] [Google Scholar]
Mulcahy M.; Magnera T.; Michl J. Molecular Rotors on Au(111): Rotator Orientation from IR Spectroscopy. J. Phys. Chem. C 2009, 113, 20698–20704 10.1021/jp906809b. [DOI] [Google Scholar]
Mulcahy M.; Bastl Z.; Stensrud K.; Magnera T.; Michl J. Mercury-Mediated Attachment of Metal-Sandwich-Based Altitudinal Molecular Rotors to Gold Surfaces. J. Phys. Chem. C 2010, 114, 14050–14060 10.1021/jp100923f. [DOI] [Google Scholar]
Kobr L.; Zhao K.; Shen Y.; Comotti A.; Bracco S.; Shoemaker R.; Sozzani P.; Clark N.; Price J.; Rogers C.; et al. Inclusion Compound Based Approach to Arrays of Artificial Dipolar Molecular Rotors. A Surface Inclusion. J. Am. Chem. Soc. 2012, 134, 10122–10131 10.1021/ja302173y. [DOI] [PubMed] [Google Scholar]
Casher D. L.; Kobr L.; Michl J. Average Orientation of a Molecular Rotor Embedded in a Langmuir-Blodgett Monolayer. Langmuir 2012, 28, 1625–1637 10.1021/la2037789. [DOI] [PubMed] [Google Scholar]
Kobr L.; Zhao K.; Shen Y.; Polivkova K.; Shoemaker R.; Clark N.; Price J.; Rogers C.; Michl J. Inclusion Compound Based Approach to Arrays of Artificial Dipolar Molecular Rotors: Bulk Inclusions. J. Org. Chem. 2013, 78, 1768–1777 10.1021/jo3009897. [DOI] [PubMed] [Google Scholar]
Clarke L. I.; Horinek D.; Kottas G. S.; Varaksa N.; Magnera T. F.; Hinderer T. P.; Horansky R. D.; Michl J.; Price J. C. The Dielectric Response of Chloromethylsilyl and Dichloromethylsilyl Dipolar Rotors on Fused Silica Surfaces. Nanotechnology 2002, 13, 533–540 10.1088/0957-4484/13/4/317. [DOI] [Google Scholar]
Michl J.; Magnera T. F. Two-dimensional Supramolecular Chemistry with Molecular Tinkertoys. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4788–4792 10.1073/pnas.052016299. [DOI] [PMC free article] [PubMed] [Google Scholar]
Horinek D.; Michl J. Molecular Dynamics Simulation of an Electric Field Driven Dipolar Molecular Rotor Attached to a Quartz Glass Surface. J. Am. Chem. Soc. 2003, 125, 11900–11910 10.1021/ja0348851. [DOI] [PubMed] [Google Scholar]
Horinek D.; Michl J. Surface-mounted Altitudinal Molecular Rotors in Alternating Electric Field: Single-molecule Parametric Oscillator Molecular Dynamics. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 14175–14180 10.1073/pnas.0506183102. [DOI] [PMC free article] [PubMed] [Google Scholar]
Vacek J.; Michl J. Molecular Dynamics of a Grid-mounted Molecular Dipolar Rotor in a Rotating Electric Field. Proc. Natl. Acad. Sci. U. S. A. 2001, 98, 5481–5486 10.1073/pnas.091100598. [DOI] [PMC free article] [PubMed] [Google Scholar]
Vacek J.; Michl J. Artificial Surface-mounted Molecular Rotors: Molecular Dynamics Simulations. Adv. Funct. Mater. 2007, 17, 730–739 10.1002/adfm.200601225. [DOI] [Google Scholar]
Prokop A.; Vacek J.; Michl J. Friction in Carborane-Based Molecular Rotors Driven by Gas Flow or Electric Field: Classical Molecular Dynamics. ACS Nano 2012, 6, 1901–1914 10.1021/nn300003x. [DOI] [PubMed] [Google Scholar]
Dunitz J. D.; Maverick E. F.; Trueblood K. N. Atomic Motions in Molecular Crystals from Diffraction Measurements. Angew. Chem., Int. Ed. Engl. 1988, 27, 880–895 10.1002/anie.198808801. [DOI] [Google Scholar]
Akutagawa T.; Shitagami K.; Nishihara S.; Takeda S.; T H.; Nakamura T.; Hosokoshi Y.; Inoue K.; Ikeuchi S.; Miyazaki Y.; Saito K. Molecular Rotor of Cs₂([18]crown-6)₃ in the Solid State Coupled with the Magnetism of [Ni(dmit)₂]. J. Am. Chem. Soc. 2005, 127, 4397–4402 10.1021/ja043527a. [DOI] [PubMed] [Google Scholar]
Khuong T.; Nunez J.; Godinez C.; Garcia-Garibay M. Crystalline Molecular Machines: A Quest Toward Solid-state Dynamics and Function. Acc. Chem. Res. 2006, 39, 413–422 10.1021/ar0680217. [DOI] [PubMed] [Google Scholar]
Karlen S.; Reyes H.; Taylor R.; Khan S.; Hawthorne M.; Garcia-Garibay M. Symmetry and Dynamics of Molecular Rotors in Amphidynamic Molecular Cystals. Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 14973–14977 10.1073/pnas.1008213107. [DOI] [PMC free article] [PubMed] [Google Scholar]
Lemouchi C.; Iliopoulos K.; Zorina L.; Simonov S.; Wzietek P.; Cauchy T.; Rodríguez-Fortea A.; Canadell E.; Kaleta J.; Michl J.; et al. Crystalline Arrays of Pairs of Molecular Rotors: Correlated Motion, Rotational Barriers, and Space-Inversion Symmetry Breaking Due to Conformational Mutations. J. Am. Chem. Soc. 2013, 135, 9366–9376 10.1021/ja4044517. [DOI] [PubMed] [Google Scholar]
Zhang Q.-C.; Wu F.-T.; Hao H.-M.; Xu H.; Zhao H.-X.; Long L.-S.; Huang R.-B.; Zheng L.-S. Modulating the Rotation of a Molecular Rotor through Hydrogen-Bonding Interactions between the Rotator and Stator. Angew. Chem., Int. Ed. 2013, 52, 12602–12605 10.1002/anie.201306193. [DOI] [PubMed] [Google Scholar]
Karlen S. D.; Garcia-Garibay M. A. Amphidynamic Crystals: Structural Blueprints for Molecular Machines 2005, 262, 179–227 10.1007/128_012. [DOI] [Google Scholar]
Shima T.; Hampel F.; Gladysz J. A. Molecular gyroscopes: [Fe(CO)₃] and [Fe(CO)₂(NO)]⁺ rotators encased in three-spoke stators; facile assembly by alkene metatheses. Angew. Chem., Int. Ed. 2004, 43, 5537–5540 10.1002/anie.200460534. [DOI] [PubMed] [Google Scholar]
Skopek K.; Hershberger M.; Gladysz J. Gyroscopes and the chemical literature: 1852–2002. Coord. Chem. Rev. 2007, 251, 1723–1733 10.1016/j.ccr.2006.12.015. [DOI] [Google Scholar]
Commins P.; Nunez J.; Garcia-Garibay M. Synthesis of Bridged Molecular Gyroscopes with Closed Topologies: Triple One-Pot Macrocyclization. J. Org. Chem. 2011, 76, 8355–8363 10.1021/jo201513y. [DOI] [PubMed] [Google Scholar]
Karlen S. D.; Godinez C. E.; Garcia-Garibay M. A. Improved physical properties and rotational dynamics in a molecular gyroscope with an asymmetric stator structure. Org. Lett. 2006, 8, 3417–3420 10.1021/ol060894d. [DOI] [PubMed] [Google Scholar]
Horansky R.; Clarke L.; Winston E.; Price J.; Karlen S.; Jarowski P.; Santillan R.; Garcia-Garibay M. Dipolar rotor-rotor interactions in a difluorobenzene molecular rotor crystal. Phys. Rev. B: Condens. Matter Mater. Phys. 2006, 74, 054306. 10.1103/PhysRevB.74.054306. [DOI] [Google Scholar]
Setaka W.; Yamaguchi K. Order-disorder transition of dipolar rotor in a crystalline molecular gyrotop and its optical change. J. Am. Chem. Soc. 2013, 135, 14560–14563 10.1021/ja408405f. [DOI] [PubMed] [Google Scholar]
Shima T.; Hampel F.; Gladysz J. Molecular gyroscopes: {Fe(CO)₃} and {Fe(CO)₂(NO)}⁺ rotators encased in three-spoke stators; facile assembly by alkene metatheses. Angew. Chem., Int. Ed. 2004, 43, 5537–5540 10.1002/anie.200460534. [DOI] [PubMed] [Google Scholar]
Zeits P.; Rachiero G.; Harnpel F.; Reibenspies J.; Gladysz J. Gyroscope-Like Platinum and Palladium Complexes with Trans-Spanning Bis(pyridine) Ligands. Organometallics 2012, 31, 2854–2877 10.1021/om201145x. [DOI] [Google Scholar]
Dominguez Z.; Dang H.; Strouse M. J.; Garcia-Garibay M. A. Molecular “Compasses” and “Gyroscopes.” III. Dynamics of a Phenylene Rotor and Clathrated Benzene in a Slipping-Gear Crystal Lattice. J. Am. Chem. Soc. 2002, 124, 7719–7727 10.1021/ja025753v. [DOI] [PubMed] [Google Scholar]
Dominguez Z.; Dang H.; Strouse M.; Garcia-Garibay M. Molecular ″compasses″ and ″gyroscopes″. I. Expedient synthesis and solid state dynamics of an open rotor with a bis(triarylmethyl) frame. J. Am. Chem. Soc. 2002, 124, 2398–2399 10.1021/ja0119447. [DOI] [PubMed] [Google Scholar]
Marahatta A. B.; Kanno M.; Hoki K.; Setaka W.; Irle S. II; Kono H. Theoretical Investigation of the Structures and Dynamics of Crystalline Molecular Gyroscopes. J. Phys. Chem. C 2012, 116, 24845–24854 10.1021/jp308974j. [DOI] [Google Scholar]
Dominguez Z.; Khuong T.; Dang H.; Sanrame C.; Nunez J.; Garcia-Garibay M. Molecular compasses and gyroscopes with polar rotors: Synthesis and characterization of crystalline forms. J. Am. Chem. Soc. 2003, 125, 8827–8837 10.1021/ja035274b. [DOI] [PubMed] [Google Scholar]
Godinez C.; Zepeda G.; Mortko C.; Dang H.; Garcia-Garibay M. Molecular crystals with moving parts: Synthesis, characterization, and crystal packing of molecular gyroscopes with methyl-substituted triptycyl frames. J. Org. Chem. 2004, 69, 1652–1662 10.1021/jo035517i. [DOI] [PubMed] [Google Scholar]
Khuong T.; Zepeda G.; Ruiz R.; Khan S.; Garcia-Garibay M. Molecular compasses and gyroscopes: Engineering molecular crystals with fast internal rotation. Cryst. Growth Des. 2004, 4, 15–18 10.1021/cg034144b. [DOI] [Google Scholar]
Binhi V. N.; Savin A. V. Molecular Gyroscopes and Biological Effects of Weak Extremely Low-Frequency Magnetic Fields. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 2002, 65, 051912. 10.1103/PhysRevE.65.051912. [DOI] [PubMed] [Google Scholar]
Karlen S.; Ortiz R.; Chapman O.; Garcia-Garibay M. Effects of rotational symmetry order on the solid state dynamics of phenylene and diamantane rotators. J. Am. Chem. Soc. 2005, 127, 6554–6555 10.1021/ja042512+. [DOI] [PubMed] [Google Scholar]
Gardinier J. R.; Pellechia P. J.; Smith M. D. Ionic rotors. preparation, structure, and dynamic solid-state 2D NMR study of the 1,4-diethynylbenzenebis(triphenylborate) dianion. J. Am. Chem. Soc. 2005, 127, 12448–12449 10.1021/ja053256j. [DOI] [PubMed] [Google Scholar]
Karlen S. D.; Garcia-Garibay M. A. Highlighting gyroscopic motion in crystals in 13C CPMAS spectra by specific isotopic substitution and restricted cross polarization. Chem. Commun. 2005, 189–191 10.1039/b409744k. [DOI] [PubMed] [Google Scholar]
Karlen S. D.; Khan S. I.; Garcia-Garibay M. A. Removal of Conflicting Molecular Symmetries Restores a HexagonalArray of Six-Fold Phenyl Embraces in a bis(Trityl)-Containing Compound. I. Crystals of 1,1,1,6,6,6-Hexaphenyl-2,4-hexadiyne. Cryst. Growth Des. 2005, 5, 53–55 10.1021/cg049898k. [DOI] [Google Scholar]
Karlen S.; Khan S.; Garcia-Garibay M. Crystalline molecular gyroscopes: The effects of subtle molecular differences on the crystal packing of triphenylmethyl and triphenylsilyl stators. Mol. Cryst. Liq. Cryst. 2006, 456, 221–230 10.1080/15421400600788757. [DOI] [Google Scholar]
Nunez J.; Khuong T.; Campos L.; Farfan N.; Dang H.; Karlen S.; Garcia-Garibay M. Crystal phases and phase transitions in a highly polymorphogenic solid-state molecular gyroscope with meta-methoxytrityl frames. Cryst. Growth Des. 2006, 6, 866–873 10.1021/cg050155o. [DOI] [Google Scholar]
Garcia-Garibay M.; Godinez C. Engineering Crystal Packing and Internal Dynamics in Molecular Gyroscopes by Refining their Components. Fast Exchange of a Phenylene Rotator by H-2 NMR. Cryst. Growth Des. 2009, 9, 3124–3128 10.1021/cg801065a. [DOI] [Google Scholar]
Rodriguez-Molina B.; Ochoa M.; Farfan N.; Santillan R.; Garcia-Garibay M. Synthesis, Characterization, and Rotational Dynamics of Crystalline Molecular Compasses with N-Heterocyclic Rotators. J. Org. Chem. 2009, 74, 8554–8565 10.1021/jo901261j. [DOI] [PubMed] [Google Scholar]
O’Brien Z.; Natarajan A.; Khan S.; Garcia-Garibay M. Synthesis and Solid-State Rotational Dynamics of Molecular Gyroscopes with a Robust and Low Density Structure Built with a Phenylene Rotator and a Tri(meta-terphenyl)methyl Stator. Cryst. Growth Des. 2011, 11, 2654–2659 10.1021/cg200373g. [DOI] [Google Scholar]
O’Brien Z.; Karlen S.; Khan S.; Garcia-Garibay M. Solid-State Molecular Rotors with Perdeuterated Stators: Mechanistic Insights from Biphenylene Rotational Dynamics in Ordered and Disordered Crystal Forms. J. Org. Chem. 2010, 75, 2482–2491 10.1021/jo9025176. [DOI] [PubMed] [Google Scholar]
Escalante-Sanchez E.; Rodriguez-Molina B.; Garcia-Garibay M. Toward Crystalline Molecular Rotors with Linearly Conjugated Diethynyl-Phenylene Rotators and Pentiptycene Stators. J. Org. Chem. 2012, 77, 7428–7434 10.1021/jo301223q. [DOI] [PubMed] [Google Scholar]
Horansky R.; Clarke L.; Price J.; Khuong T.; Jarowski P.; Garcia-Garibay M.. Dielectric response of a dipolar molecular rotor crystal. Phys. Rev. B: Condens. Matter Mater. Phys. 2005, 72, 10.1103/PhysRevB.72.014302. [DOI] [Google Scholar]
Ozin G. A.; Manners I.; Fournier-Bidoz S.; Arsenault A. Dream Nanomachines. Adv. Mater. 2005, 17, 3011–3018 10.1002/adma.200501767. [DOI] [Google Scholar]
Ebbens S. J.; Howse J. R. In pursuit of propulsion at the nanoscale. Soft Matter 2010, 6, 726–738 10.1039/b918598d. [DOI] [Google Scholar]
Young N. O.; G J. S.; Block M. J. The motion of bubbles in a vertical temperature gradient. J. Fluid Mech. 1959, 6, 350–356 10.1017/S0022112059000684. [DOI] [Google Scholar]
Scriven L. E.; Sternling C. V. The Marangoni Effects. Nature 1960, 187, 186–188 10.1038/187186a0. [DOI] [Google Scholar]
Cazabat A. M.; Heslot F.; Troian S. M.; Carles P. Fingering instability of thin spreading films driven by temperature gradients. Nature 1990, 346, 824–826 10.1038/346824a0. [DOI] [Google Scholar]
Barton K. D.; Shankar Subramanian R. The migration of liquid drops in a vertical temperature gradient. J. Colloid Interface Sci. 1989, 133, 211–222 10.1016/0021-9797(89)90294-4. [DOI] [Google Scholar]
Burns M. A.; Mastrangelo C. H.; Sammarco T. S.; Man F. P.; Webster J. R.; Johnsons B. N.; Foerster B.; Jones D.; Fields Y.; Kaiser A. R.; Burke D. T. Microfabricated structures for integrated DNA analysis. Proc. Natl. Acad. Sci. U. S. A. 1996, 93, 5556–5561 10.1073/pnas.93.11.5556. [DOI] [PMC free article] [PubMed] [Google Scholar]
Kataoka D. E.; Troian S. M. Patterning liquid flow on the microscopic scale. Nature 1999, 402, 794–797 10.1038/45521. [DOI] [Google Scholar]
Kumar G.; Prabhu K. N. Review of non-reactive and reactive wetting of liquids on surfaces. Adv. Colloid Interface Sci. 2007, 133, 61–89 10.1016/j.cis.2007.04.009. [DOI] [PubMed] [Google Scholar]
Gennes P. G. d. Forced wetting by a reactive fluid. Europhys. Lett. 1997, 39, 407–412 10.1209/epl/i1997-00369-6. [DOI] [Google Scholar]
de Gennes P. G. The dynamics of reactive wetting on solid surfaces. Phys. A 1998, 249, 196–205 10.1016/S0378-4371(97)00466-4. [DOI] [Google Scholar]
Bain C. D.; Burnett-Hall G. D.; Montgomerie R. R. Rapid motion of liquid drops. Nature 1994, 372, 414–415 10.1038/372414a0. [DOI] [Google Scholar]
Dos Santos F. D.; Ondarçuhu T. Free-Running Droplets. Phys. Rev. Lett. 1995, 75, 2972–2975 10.1103/PhysRevLett.75.2972. [DOI] [PubMed] [Google Scholar]
Lee S.-W.; Laibinis P. E. Directed Movement of Liquids on Patterned Surfaces Using Noncovalent Molecular Adsorption. J. Am. Chem. Soc. 2000, 122, 5395–5396 10.1021/ja994076a. [DOI] [Google Scholar]
Mitsumata T.; Ikeda K.; Gong J. P.; Osada Y. Solvent-driven chemical motor. Appl. Phys. Lett. 1998, 73, 2366–2368 10.1063/1.122505. [DOI] [Google Scholar]
Ismagilov R. F.; Schwartz A.; Bowden N.; Whitesides G. M. Autonomous Movement and Self-Assembly. Angew. Chem., Int. Ed. 2002, 41, 652–654. [DOI] [Google Scholar]
Paxton W. F.; Kistler K. C.; Olmeda C. C.; Sen A.; St. Angelo S. K.; Cao Y.; Mallouk T. E.; Lammert P. E.; Crespi V. H. Catalytic Nanomotors: Autonomous Movement of Striped Nanorods. J. Am. Chem. Soc. 2004, 126, 13424–13431 10.1021/ja047697z. [DOI] [PubMed] [Google Scholar]
Golestanian R.; Liverpool T. B.; Ajdari A. Propulsion of a Molecular Machine by Asymmetric Distribution of Reaction Products. Phys. Rev. Lett. 2005, 94, 220801. 10.1103/PhysRevLett.94.220801. [DOI] [PubMed] [Google Scholar]
Dhar P.; Fischer T. M.; Wang Y.; Mallouk T. E.; Paxton W. F.; Sen A. Autonomously Moving Nanorods at a Viscous Interface. Nano Lett. 2006, 6, 66–72 10.1021/nl052027s. [DOI] [PubMed] [Google Scholar]
Paxton W. F.; Sen A.; Mallouk T. E. Motility of Catalytic Nanoparticles through Self-Generated Forces. Chem. - Eur. J. 2005, 11, 6462–6470 10.1002/chem.200500167. [DOI] [PubMed] [Google Scholar]
Kline T. R.; Paxton W. F.; Wang Y.; Velegol D.; Mallouk T. E.; Sen A. Catalytic Micropumps: Microscopic Convective Fluid Flow and Pattern Formation. J. Am. Chem. Soc. 2005, 127, 17150–17151 10.1021/ja056069u. [DOI] [PubMed] [Google Scholar]
Mano N.; Heller A. Bioelectrochemical Propulsion. J. Am. Chem. Soc. 2005, 127, 11574–11575 10.1021/ja053937e. [DOI] [PubMed] [Google Scholar]
Catchmark J. M.; Subramanian S.; Sen A. Directed Rotational Motion of Microscale Objects Using Interfacial Tension Gradients Continually Generated via Catalytic Reactions. Small 2005, 1, 202–206 10.1002/smll.200400061. [DOI] [PubMed] [Google Scholar]
Fournier-Bidoz S.; Arsenault A. C.; Manners I.; Ozin G. A. Synthetic self-propeled nanorotors. Chem. Commun. 2005, 441–443 10.1039/b414896g. [DOI] [PubMed] [Google Scholar]
Valadares L. F.; Tao Y.-G.; Zacharia N. S.; Kitaev V.; Galembeck F.; Kapral R.; Ozin G. A. Catalytic Nanomotors: Self-Propeled Sphere Dimers. Small 2010, 6, 565–572 10.1002/smll.200901976. [DOI] [PubMed] [Google Scholar]
Qin L.; Banholzer M. J.; Xu X.; Huang L.; Mirkin C. A. Rational Design and Synthesis of Catalytically Driven Nanorotors. J. Am. Chem. Soc. 2007, 129, 14870–14871 10.1021/ja0772391. [DOI] [PubMed] [Google Scholar]
Wang Y.; Fei S.-t.; Byun Y.-M.; Lammert P. E.; Crespi V. H.; Sen A.; Mallouk T. E. Dynamic Interactions between Fast Microscale Rotors. J. Am. Chem. Soc. 2009, 131, 9926–9927 10.1021/ja904827j. [DOI] [PubMed] [Google Scholar]
Vicario J.; Eelkema R.; Browne W. R.; Meetsma A.; La Crois R. M.; Feringa B. L. Catalytic molecular motors: fuelling autonomous movement by a surface bound synthetic manganese catalase. Chem. Commun. 2005, 3936–3938 10.1039/b505092h. [DOI] [PubMed] [Google Scholar]
Lee T.-C.; Alarcón-Correa M.; Miksch C.; Hahn K.; Gibbs J. G.; Fischer P. Self-Propeling Nanomotors in the Presence of Strong Brownian Forces. Nano Lett. 2014, 14, 2407–2412 10.1021/nl500068n. [DOI] [PMC free article] [PubMed] [Google Scholar]
Pantarotto D.; Browne W. R.; Feringa B. L. Autonomous propulsion of carbon nanotubes powered by a multienzyme ensemble. Chem. Commun. 2008, 1533–1535 10.1039/B715310D. [DOI] [PubMed] [Google Scholar]
Gao W.; Feng X.; Pei A.; Gu Y.; Li J.; Wang J. Seawater-driven magnesium based Janus micromotors for environmental remediation. Nanoscale 2013, 5, 4696–4700 10.1039/c3nr01458d. [DOI] [PubMed] [Google Scholar]
Pavlick R. A.; Sengupta S.; McFadden T.; Zhang H.; Sen A. A Polymerization-Powered Motor. Angew. Chem., Int. Ed. 2011, 50, 9374–9377 10.1002/anie.201103565. [DOI] [PubMed] [Google Scholar]
Taylor G. Analysis of the Swimming of Microscopic Organisms. Proc. R. Soc. London, Ser. A 1951, 209, 447–461 10.1098/rspa.1951.0218. [DOI] [Google Scholar]
Shapere A.; Wilczek F. Self-Propulsion at Low Reynolds Number. Phys. Rev. Lett. 1987, 58, 2051–2054 10.1103/PhysRevLett.58.2051. [DOI] [PubMed] [Google Scholar]
Alfred Shapere F. W. Geometry of self-propulsion at low Reynolds number. J. Fluid Mech. 1989, 198, 557–585 10.1017/S002211208900025X. [DOI] [Google Scholar]
Stone H. A.; Samuel A. D. T. Propulsion of Microorganisms by Surface Distortions. Phys. Rev. Lett. 1996, 77, 4102–4104 10.1103/PhysRevLett.77.4102. [DOI] [PubMed] [Google Scholar]
Ajdari A.; Stone H. A. A note on swimming using internally generated traveling waves. Phys. Fluids 1999, 11, 1275–1277 10.1063/1.869991. [DOI] [Google Scholar]
Dreyfus R.; Baudry J.; Stone H. A. Purcell’s “rotator”: mechanical rotation at low Reynolds number. Eur. Phys. J. B 2005, 47, 161–164 10.1140/epjb/e2005-00302-5. [DOI] [Google Scholar]
Purcell E. M. The efficiency of propulsion by a rotating flagellum. Proc. Natl. Acad. Sci. U. S. A. 1997, 94, 11307–11311 10.1073/pnas.94.21.11307. [DOI] [PMC free article] [PubMed] [Google Scholar]
Wiggins C. H.; Goldstein R. E. Flexive and Propulsive Dynamics of Elastica at Low Reynolds Number. Phys. Rev. Lett. 1998, 80, 3879–3882 10.1103/PhysRevLett.80.3879. [DOI] [Google Scholar]
Camalet S.; Jülicher F.; Prost J. Self-Organized Beating and Swimming of Internally Driven Filaments. Phys. Rev. Lett. 1999, 82, 1590–1593 10.1103/PhysRevLett.82.1590. [DOI] [Google Scholar]
Becker L. E.; Koehler S. A.; Stone H. A. On self-propulsion of micro-machines at low Reynolds number: Purcell’s three-link swimmer. J. Fluid Mech. 2003, 490, 15–35 10.1017/S0022112003005184. [DOI] [Google Scholar]
Najafi A.; Golestanian R. Simple swimmer at low Reynolds number: Three linked spheres. Phys. Rev. E 2004, 69, 062901. 10.1103/PhysRevE.69.062901. [DOI] [PubMed] [Google Scholar]
Avron J. E.; Gat O.; Kenneth O. Optimal Swimming at Low Reynolds Numbers. Phys. Rev. Lett. 2004, 93, 186001. 10.1103/PhysRevLett.93.186001. [DOI] [PubMed] [Google Scholar]
Avron J. E.; Kenneth O.; Oaknin D. H. Pushmepullyou: an efficient micro-swimmer. New J. Phys. 2005, 7, 234. 10.1088/1367-2630/7/1/234. [DOI] [Google Scholar]
Porto M.; Urbakh M.; Klafter J. Atomic Scale Engines: Cars and Wheels. Phys. Rev. Lett. 2000, 84, 6058–6061 10.1103/PhysRevLett.84.6058. [DOI] [PubMed] [Google Scholar]
Wang Z. Bioinspired laser-operated molecular locomotive. Phys. Rev. E 2004, 70, 031903. 10.1103/PhysRevE.70.031903. [DOI] [PubMed] [Google Scholar]
Dreyfus R.; Baudry J.; Roper M. L.; Fermigier M.; Stone H. A.; Bibette J. Microscopic artificial swimmers. Nature 2005, 437, 862–865 10.1038/nature04090. [DOI] [PubMed] [Google Scholar]
Baranova N. B.; Zel’dovich B. Y. Separation of mirror isomeric molecules by radio-frequency electric field of rotating polarization. Chem. Phys. Lett. 1978, 57, 435–437 10.1016/0009-2614(78)85543-2. [DOI] [Google Scholar]
Space B.; Rabitz H.; Lörincz A.; Moore P. Feasibility of using photophoresis to create a concentration gradient of solvated molecules. J. Chem. Phys. 1996, 105, 9515–9524 10.1063/1.472785. [DOI] [Google Scholar]
Arai Y.; Yasuda R.; Akashi K.; Harada Y.; Miyata H.; Kinosita K.; Itoh H. Tying a molecular knot with optical tweezers. Nature 1999, 399, 446–448 10.1038/20894. [DOI] [PubMed] [Google Scholar]
Neuman K. C.; Block S. M. Optical trapping. Rev. Sci. Instrum. 2004, 75, 2787–2809 10.1063/1.1785844. [DOI] [PMC free article] [PubMed] [Google Scholar]
Zhuang X. W. Unraveling DNA condensation with optical tweezers. Science 2004, 305, 188–190 10.1126/science.1100603. [DOI] [PubMed] [Google Scholar]
Allemand J. F.; Bensimon D.; Croquette V. Stretching DNA and RNA to probe their interactions with proteins. Curr. Opin. Struct. Biol. 2003, 13, 266–274 10.1016/S0959-440X(03)00067-8. [DOI] [PubMed] [Google Scholar]
Bustamante C.; Macosko J. C.; Wuite G. J. Grabbing the cat by the tail: manipulating molecules one by one. Nat. Rev. Mol. Cell Biol. 2000, 1, 130–136 10.1038/35040072. [DOI] [PubMed] [Google Scholar]
Mehta A. D.; Rief M.; Spudich J. A.; Smith D. A.; Simmons R. M. Single-molecule biomechanics with optical methods. Science 1999, 283, 1689–1695 10.1126/science.283.5408.1689. [DOI] [PubMed] [Google Scholar]
Yanagida T.; Harada Y.; Ishijima A. Nano-manipulation of actomyosin molecular motors in vitro: a new working principle. Trends Biochem. Sci. 1993, 18, 319–324 10.1016/0968-0004(93)90064-T. [DOI] [PubMed] [Google Scholar]
Lensen D.; Elemans J. A. A. W. Artificial molecular rotors and motors on surfaces: STM reveals and triggers. Soft Matter 2012, 8, 9053–9063 10.1039/c2sm26235e. [DOI] [Google Scholar]
Binning G.; Rohrer H.; Gerber C.; Weibel E. Surface Studies by Scanning Tunneling Microscopy. Phys. Rev. Lett. 1982, 49, 57–61 10.1103/PhysRevLett.49.57. [DOI] [Google Scholar]
Binnig G.; Rohrer H. Scanning Tunneling Microscopy - from Birth to Adolescence. Usp. Fiz. Nauk 1988, 154, 261–278 10.3367/UFNr.0154.198802d.0261. [DOI] [Google Scholar]
Binnig G.; Rohrer H. Scanning Tunneling Microscopy - from Birth to Adolescence. Angew. Chem., Int. Ed. Engl. 1987, 26, 606–614 10.1002/anie.198706061. [DOI] [Google Scholar]
Binnig G.; Rohrer H. Scanning Tunneling Microscopy - from Birth to Adolescence. Rev. Mod. Phys. 1987, 59, 615–625 10.1103/RevModPhys.59.615. [DOI] [Google Scholar]
Block S. M. Making light work with optical tweezers. Nature 1992, 360, 493–495 10.1038/360493a0. [DOI] [PubMed] [Google Scholar]
Kuo S. C.; Sheetz M. P. Optical tweezers in cell biology. Trends Cell Biol. 1992, 2, 116–118 10.1016/0962-8924(92)90016-G. [DOI] [PubMed] [Google Scholar]
Iancu V.; Hla S.-W. Realization of a four-step molecular switch in scanning tunneling microscope manipulation of single chlorophyll-a molecules. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 13718–13721 10.1073/pnas.0603643103. [DOI] [PMC free article] [PubMed] [Google Scholar]
Chiang S. Introduction: Force and Tunneling Microscopy. Chem. Rev. 1997, 97, 1015–1016 10.1021/cr970041m. [DOI] [PubMed] [Google Scholar]
Gimzewski J. K.; Joachim C. Nanoscale science of single molecules using local probes. Science 1999, 283, 1683–1688 10.1126/science.283.5408.1683. [DOI] [PubMed] [Google Scholar]
Stroscio J. A.; Eigler D. M. Atomic and molecular manipulation with the scanning tunneling microscope. Science 1991, 254, 1319–1326 10.1126/science.254.5036.1319. [DOI] [PubMed] [Google Scholar]
Avouris P. Manipulation of Matter at the Atomic and Molecular-Levels. Acc. Chem. Res. 1995, 28, 95–102 10.1021/ar00051a002. [DOI] [Google Scholar]
Gimzewski J. K.; Jung T. A.; Cuberes M. T.; Schlittler R. R. Scanning tunneling microscopy of individual molecules: beyond imaging. Surf. Sci. 1997, 386, 101–114 10.1016/S0039-6028(97)00301-4. [DOI] [Google Scholar]
Rosei F.; Schunack M.; Naitoh Y.; Jiang P.; Gourdon A.; Laegsgaard E.; Stensgaard I.; Joachim C.; Besenbacher F. Properties of large organic molecules on metal surfaces. Prog. Surf. Sci. 2003, 71, 95–146 10.1016/S0079-6816(03)00004-2. [DOI] [Google Scholar]
Takano H.; Kenseth J. R.; Wong S. S.; O’Brien J. C.; Porter M. D. Chemical and biochemical analysis using scanning force microscopy. Chem. Rev. 1999, 99, 2845–2890 10.1021/cr9801317. [DOI] [PubMed] [Google Scholar]
Guthold M.; Falvo M.; Matthews W. G.; Paulson S.; Mullin J.; Lord S.; Erie D.; Washburn S.; Superfine R.; Brooks F. P. Jr.; Taylor R. M. 2nd Investigation and modification of molecular structures with the nanoManipulator. J. Mol. Graphics Modell. 1999, 17, 187–197 10.1016/S1093-3263(99)00030-3. [DOI] [PubMed] [Google Scholar]
Kawakami M.; Taniguchi Y. Recent Advances in Single-Molecule Biophysics with the Use of Atomic Force Microscopy. Adv. Chem. Phys. 2012, 146, 89–132. [Google Scholar]
Giessibl F. J. Advances in atomic force microscopy. Rev. Mod. Phys. 2003, 75, 949–983 10.1103/RevModPhys.75.949. [DOI] [Google Scholar]
Hansma P. K.; Elings V. B.; Marti O.; Bracker C. E. Scanning tunneling microscopy and atomic force microscopy: application to biology and technology. Science 1988, 242, 209–216 10.1126/science.3051380. [DOI] [PubMed] [Google Scholar]
Engel A.; Gaub H. E.; Muller D. J. Atomic force microscopy: a forceful way with single molecules. Curr. Biol. 1999, 9, R133–R136 10.1016/S0960-9822(99)80081-5. [DOI] [PubMed] [Google Scholar]
Clausen-Schaumann H.; Seitz M.; Krautbauer R.; Gaub H. E. Force spectroscopy with single bio-molecules. Curr. Opin. Chem. Biol. 2000, 4, 524–530 10.1016/S1367-5931(00)00126-5. [DOI] [PubMed] [Google Scholar]
Samori B. Stretching single molecules along unbinding and unfolding pathways with the scanning force microscope. Chem. - Eur. J. 2000, 6, 4249–4255. [DOI] [PubMed] [Google Scholar]
Janshoff A.; Neitzert M.; Oberdorfer Y.; Fuchs H. Force Spectroscopy of Molecular Systems-Single Molecule Spectroscopy of Polymers and Biomolecules. Angew. Chem., Int. Ed. 2000, 39, 3212–3237. [DOI] [PubMed] [Google Scholar]
Rief M.; Grubmuller H. Force spectroscopy of single biomolecules. ChemPhysChem 2002, 3, 255–261. [DOI] [PubMed] [Google Scholar]
Best R. B.; Clarke J. What can atomic force microscopy tell us about protein folding?. Chem. Commun. 2002, 183–192 10.1039/b108159b. [DOI] [PubMed] [Google Scholar]
Hla S. W.; Meyer G.; Rieder K. H. Inducing single-molecule chemical reactions with a UHV-STM: a new dimension for nano-science and technology. ChemPhysChem 2001, 2, 361–366. [DOI] [PubMed] [Google Scholar]
Joachim C.; Gimzewski J. K. A nanoscale single-molecule amplifier and its consequences. Proc. IEEE 1998, 86, 184–190 10.1109/5.658770. [DOI] [Google Scholar]
Joachim C.; Gimzewski J. K.; Aviram A. Electronics using hybrid-molecular and mono-molecular devices. Nature 2000, 408, 541–548 10.1038/35046000. [DOI] [PubMed] [Google Scholar]
Moresco F. Manipulation of large molecules by low-temperature STM: model systems for molecular electronics. Phys. Rep. 2004, 399, 175–225 10.1016/j.physrep.2004.08.001. [DOI] [Google Scholar]
Bhushan B.; Israelachvili J. N.; Landman U. Nanotribology - Friction, Wear and Lubrication at the Atomic-Scale. Nature 1995, 374, 607–616 10.1038/374607a0. [DOI] [Google Scholar]
Luan B. Q.; Robbins M. O. The breakdown of continuum models for mechanical contacts. Nature 2005, 435, 929–932 10.1038/nature03700. [DOI] [PubMed] [Google Scholar]
Buldum A.; Lu J. P. Atomic scale sliding and rolling of carbon nanotubes. Phys. Rev. Lett. 1999, 83, 5050–5053 10.1103/PhysRevLett.83.5050. [DOI] [Google Scholar]
Kang J. W.; Hwang H. J. Fullerene nano ball bearings: an atomistic study. Nanotechnology 2004, 15, 614–621 10.1088/0957-4484/15/5/036. [DOI] [Google Scholar]
Sasaki N.; Miura K. Key issues of nanotribology for successful nanofabrication - From basis to C-60 molecular bearings. Jpn. J. Appl. Phys. 1 2004, 43, 4486–4491 10.1143/JJAP.43.4486. [DOI] [Google Scholar]
Falvo M. R.; Taylor R. M. 2nd; Helser A.; Chi V.; Brooks F. P. Jr.; Washburn S.; Superfine R. Nanometre-scale rolling and sliding of carbon nanotubes. Nature 1999, 397, 236–238 10.1038/16662. [DOI] [PubMed] [Google Scholar]
Falvo M. R.; Steele J.; Taylor R. M. Superfine, R. Gearlike rolling motion mediated by commensurate contact: Carbon nanotubes on HOPG. Phys. Rev. B: Condens. Matter Mater. Phys. 2000, 62, 10665–10667 10.1103/PhysRevB.62.R10665. [DOI] [Google Scholar]
Miura K.; Takagi T.; Kamiya S.; Sahashi T.; Yamauchi M. Natural rolling of zigzag multiwalled carbon nanotubes on graphite. Nano Lett. 2001, 1, 161–163 10.1021/nl015513y. [DOI] [Google Scholar]
Moriarty P.; Ma Y. R.; Upward M. D.; Beton P. H. Translation, rotation and removal of C-60 on Si(100)-2 × 1 using anisotropic molecular manipulation. Surf. Sci. 1998, 407, 27–35 10.1016/S0039-6028(98)00082-X. [DOI] [Google Scholar]
Miura K.; Kamiya S.; Sasaki N.. C-60 molecular bearings. Phys. Rev. Lett. 2003, 90, 10.1103/PhysRevLett.90.055509. [DOI] [PubMed] [Google Scholar]
Keeling D. L.; Humphry M. J.; Fawcett R. H. J.; Beton P. H.; Hobbs C.; Kantorovich L. Bond breaking coupled with translation in rolling of covalently bound molecules. Phys. Rev. Lett. 2005, 94, 94. 10.1103/PhysRevLett.94.146104. [DOI] [PubMed] [Google Scholar]
Otero R.; Hummelink F.; Sato F.; Legoas S. B.; Thostrup P.; Laegsgaard E.; Stensgaard I.; Galvao D. S.; Besenbacher F. Lock-and-key effect in the surface diffusion of large organic molecules probed by STM. Nat. Mater. 2004, 3, 779–782 10.1038/nmat1243. [DOI] [PubMed] [Google Scholar]
Eigler D. M.; Lutz C. P.; Rudge W. E. An Atomic Switch Realized with the Scanning Tunneling Microscope. Nature 1991, 352, 600–603 10.1038/352600a0. [DOI] [Google Scholar]
Stipe B. C.; Rezaei M. A.; Ho W. Inducing and viewing the rotational motion of a single molecule. Science 1998, 279, 1907–1909 10.1126/science.279.5358.1907. [DOI] [PubMed] [Google Scholar]
Stipe B. C.; Rezaei M. A.; Ho W. Coupling of vibrational excitation to the rotational motion of a single adsorbed molecule. Phys. Rev. Lett. 1998, 81, 1263–1266 10.1103/PhysRevLett.81.1263. [DOI] [Google Scholar]
Wintjes N.; Bonifazi D.; Cheng F.; Kiebele A.; Stöhr M.; Jung T.; Spillmann H.; Diederich F. A Supramolecular Multiposition Rotary Device. Angew. Chem., Int. Ed. 2007, 46, 4089–4092 10.1002/anie.200700285. [DOI] [PubMed] [Google Scholar]
Jung T. A.; Schlittler R. R.; Gimzewski J. K.; Tang H.; Joachim C. Controlled room-temperature positioning of individual molecules: Molecular flexure and motion. Science 1996, 271, 181–184 10.1126/science.271.5246.181. [DOI] [Google Scholar]
Jung T. A.; Schlittler R. R.; Gimzewski J. K. Conformational identification of individual adsorbed molecules with the STM. Nature 1997, 386, 696–698 10.1038/386696a0. [DOI] [Google Scholar]
Moresco F.; Meyer G.; Rieder K. H.; Ping H.; Tang H.; Joachim C. TBPP molecules on copper surfaces: a low temperature scanning tunneling microscope investigation. Surf. Sci. 2002, 499, 94–102 10.1016/S0039-6028(01)01803-9. [DOI] [Google Scholar]
Moresco F.; Meyer G.; Rieder K. H.; Tang H.; Gourdon A.; Joachim C. Low temperature manipulation of big molecules in constant height mode. Appl. Phys. Lett. 2001, 78, 306–308 10.1063/1.1339251. [DOI] [Google Scholar]
Moresco F.; Meyer G.; Rieder K. H.; Tang H.; Gourdon A.; Joachim C. Conformational changes of single molecules induced by scanning tunneling microscopy manipulation: A route to molecular switching. Phys. Rev. Lett. 2001, 86, 672–675 10.1103/PhysRevLett.86.672. [DOI] [PubMed] [Google Scholar]
Moresco F.; Meyer G.; Rieder K. H.; Tang H.; Gourdon A.; Joachim C.. Recording intramolecular mechanics during the manipulation of a large molecule. Phys. Rev. Lett. 2001, 87, 10.1103/PhysRevLett.87.088302. [DOI] [PubMed] [Google Scholar]
Cuberes M. T.; Schlittler R. R.; Gimzewski J. K. Room-temperature repositioning of individual C-60 molecules at Cu steps: Operation of a molecular counting device. Appl. Phys. Lett. 1996, 69, 3016–3018 10.1063/1.116824. [DOI] [Google Scholar]
Gimzewski J. K.; Joachim C.; Schlittler R. R.; Langlais V.; Tang H.; Johannsen I. Rotation of a single molecule within a supramolecular bearing. Science 1998, 281, 531–533 10.1126/science.281.5376.531. [DOI] [PubMed] [Google Scholar]
Griessl S. J. H.; Lackinger M.; Jamitzky F.; Markert T.; Hietschold M.; Heckl W. A. Incorporation and manipulation of coronene in an organic template structure. Langmuir 2004, 20, 9403–9407 10.1021/la049441c. [DOI] [PubMed] [Google Scholar]
Joachim C.; Gimzewski J. K. Single molecular rotor at the nanoscale. Struct. Bonding (Berlin) 2001, 99, 1–18. [Google Scholar]
Stranick S. J.; Kamna M. M.; Weiss P. S. Atomic-scale dynamics of a two-dimensional gas-solid interface. Science 1994, 266, 99–102 10.1126/science.266.5182.99. [DOI] [PubMed] [Google Scholar]
Kwon K. Y.; Wong K. L.; Pawin G.; Bartels L.; Stolbov S.; Rahman T. S.. Unidirectional adsorbate motion on a high-symmetry surface: “Walking” molecules can stay the course. Phys. Rev. Lett. 2005, 95, 10.1103/PhysRevLett.95.166101. [DOI] [PubMed] [Google Scholar]
Das B.; Sebastian K. L. Adsorbed hypostrophene: can it roll on a surface by rearrangement of bonds?. Chem. Phys. Lett. 2000, 330, 433–439 10.1016/S0009-2614(00)01100-3. [DOI] [Google Scholar]
Das B.; Sebastian K. L. Molecular wheels on surfaces. Chem. Phys. Lett. 2002, 357, 25–31 10.1016/S0009-2614(02)00435-9. [DOI] [Google Scholar]
Fujikawa Y.; Sadowski J. T.; Kelly K. F.; Nakayama K. S.; Mickelson E. T.; Hauge R. H.; Margrave J. L.; Sakurai T. Adsorption of fluorinated C-60 on the Si(111)-(7 × 7) surface studied by scanning tunneling microscopy and high-resolution electron energy loss spectroscopy. Jpn. J. Appl. Phys. 1 2002, 41, 245–249 10.1143/JJAP.41.245. [DOI] [Google Scholar]
Joachim C.; Tang H.; Moresco F.; Rapenne G.; Meyer G. The design of a nanoscale molecular barrow. Nanotechnology 2002, 13, 330–335 10.1088/0957-4484/13/3/318. [DOI] [Google Scholar]
Jimenez-Bueno G.; Rapenne G. Technomimetic molecules: synthesis of a molecular wheelbarrow. Tetrahedron Lett. 2003, 44, 6261–6263 10.1016/S0040-4039(03)01519-3. [DOI] [Google Scholar]
Rapenne G. Synthesis of technomimetic molecules: towards rotation control in single-molecular machines and motors. Org. Biomol. Chem. 2005, 3, 1165–1169 10.1039/b419282f. [DOI] [PubMed] [Google Scholar]
Grill L.; Rieder K. H.; Moresco F.; Jimenez-Bueno G.; Wang C.; Rapenne G.; Joachim C. Imaging of a molecular wheelbarrow by scanning tunneling microscopy. Surf. Sci. 2005, 584, L153–L158 10.1016/j.susc.2005.03.062. [DOI] [Google Scholar]
Grill L.; Rieder K. H.; Moresco F.; Rapenne G.; Stojkovic S.; Bouju X.; Joachim C. Rolling a single molecular wheel at the atomic scale. Nat. Nanotechnol. 2007, 2, 95–98 10.1038/nnano.2006.210. [DOI] [PubMed] [Google Scholar]
Vaughan O. P.; Williams F. J.; Bampos N.; Lambert R. M. A chemically switchable molecular pinwheel. Angew. Chem., Int. Ed. 2006, 45, 3779–3781 10.1002/anie.200600683. [DOI] [PubMed] [Google Scholar]
Wong K. L.; Pawin G.; Kwon K. Y.; Lin X.; Jiao T.; Solanki U.; Fawcett R. H. J.; Bartels L.; Stolbov S.; Rahman T. S. A molecule carrier. Science 2007, 315, 1391–1393 10.1126/science.1135302. [DOI] [PubMed] [Google Scholar]
Chiaravalloti F.; Gross L.; Rieder K. H.; Stojkovic S. M.; Gourdon A.; Joachim C.; Moresco F. A rack-and-pinion device at the molecular scale. Nat. Mater. 2007, 6, 30–33 10.1038/nmat1802. [DOI] [PubMed] [Google Scholar]
Shirai Y.; Osgood A. J.; Zhao Y.; Kelly K. F.; Tour J. M. Directional control in Thermally Driven Single-molecule Nanocars. Nano Lett. 2005, 5, 2330–2334 10.1021/nl051915k. [DOI] [PubMed] [Google Scholar]
Chu P. L. E.; Wang L. Y.; Khatua S.; Kolomeisky A. B.; Link S.; Tour J. M. Synthesis and Single-Molecule Imaging of Highly Mobile Adamantane-Wheeled Nanocars. ACS Nano 2013, 7, 35–41 10.1021/nn304584a. [DOI] [PubMed] [Google Scholar]
Khatua S.; Guerrero J. M.; Claytor K.; Vives G.; Kolomeisky A. B.; Tour J. M.; Link S. Micrometer-Scale Translation and Monitoring of Individual Nanocars on Glass. ACS Nano 2009, 3, 351–356 10.1021/nn800798a. [DOI] [PubMed] [Google Scholar]
Morin J. F.; Shirai Y.; Tour J. M. En route to a motorized nanocar. Org. Lett. 2006, 8, 1713–1716 10.1021/ol060445d. [DOI] [PubMed] [Google Scholar]
Tierney H. L.; Murphy C. J.; Jewell A. D.; Baber A. E.; Iski E. V.; Khodaverdian H. Y.; McGuire A. F.; Klebanov N.; Sykes E. C. H. Experimental demonstration of a single-molecule electric motor. Nat. Nanotechnol. 2011, 6, 625–629 10.1038/nnano.2011.142. [DOI] [PubMed] [Google Scholar]
Tanaka H.; Ikeda T.; Takeuchi M.; Sada K.; Shinkai S.; Kawai T. Molecular Rotation in Self-Assembled Multidecker Porphyrin Complexes. ACS Nano 2011, 5, 9575–9582 10.1021/nn203773p. [DOI] [PubMed] [Google Scholar]
Kudernac T.; Ruangsupapichat N.; Parschau M.; Macia B.; Katsonis N.; Harutyunyan S. R.; Ernst K. H.; Feringa B. L. Electrically driven directional motion of a four-wheeled molecule on a metal surface. Nature 2011, 479, 208–211 10.1038/nature10587. [DOI] [PubMed] [Google Scholar]
Hao X.; Zhu N.; Gschneidtner T.; Jonsson E. O.; Zhang J. D.; Moth-Poulsen K.; Wang H. D.; Thygesen K. S.; Jacobsen K. W.; Ulstrup J.; et al. Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex. Nat. Commun. 2013, 4, 2121. 10.1038/ncomms3121. [DOI] [PubMed] [Google Scholar]
Biscarini F.; Gebauer W.; Di Domenico D.; Zamboni R.; Pascual J. I.; Leigh D. A.; Murphy A.; Tetard D. STM investigation of flexible supramolecules: Benzylic amide [2] catenanes. Synth. Met. 1999, 102, 1466–1467 10.1016/S0379-6779(98)00539-6. [DOI] [Google Scholar]
Samori P.; Jackel F.; Unsal O.; Godt A.; Rabe J. P. Ordered nanostructures of a [2]catenane through self-assembly at surfaces - An STM study with sub-molecular resolution. ChemPhysChem 2001, 2, 461–464. [DOI] [PubMed] [Google Scholar]
Shigekawa H.; Miyake K.; Sumaoka J.; Harada A.; Komiyama M. The molecular abacus: STM manipulation of cyclodextrin necklace. J. Am. Chem. Soc. 2000, 122, 5411–5412 10.1021/ja000037j. [DOI] [PubMed] [Google Scholar]
Feng M.; Guo X. F.; Lin X.; He X. B.; Ji W.; Du S. X.; Zhang D. Q.; Zhu D. B.; Gao H. J. Stable, reproducible nanorecording on rotaxane thin films. J. Am. Chem. Soc. 2005, 127, 15338–15339 10.1021/ja054836j. [DOI] [PubMed] [Google Scholar]
Cavallini M.; Biscarini F.; Leon S.; Zerbetto F.; Bottari G.; Leigh D. A. Information storage using supramolecular surface patterns. Science 2003, 299, 531–531 10.1126/science.1078012. [DOI] [PubMed] [Google Scholar]
Brough B.; Northrop B. H.; Schmidt J. J.; Tseng H. R.; Houk K. N.; Stoddart J. F.; Ho C. M. Evaluation of synthetic linear motor-molecule actuation energetics. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 8583–8588 10.1073/pnas.0509645103. [DOI] [PMC free article] [PubMed] [Google Scholar]
Lussis P.; Svaldo-Lanero T.; Bertocco A.; Fustin C. A.; Leigh D. A.; Duwez A. S. A single synthetic small molecule that generates force against a load. Nat. Nanotechnol. 2011, 6, 553–557 10.1038/nnano.2011.132. [DOI] [PubMed] [Google Scholar]
Luo Y.; Collier C. P.; Jeppesen J. O.; Nielsen K. A.; DeIonno E.; Ho G.; Perkins J.; Tseng H. R.; Yamamoto T.; Stoddart J. F.; Heath J. R. Two-dimensional molecular electronics circuits. ChemPhysChem 2002, 3, 519–525. [DOI] [PubMed] [Google Scholar]
Huang T. J.; Flood A.; Chu C. W.; Kang S.; Guo T. F.; Yamamoto T.; Tseng H. R.; Yu B. D.; Yang Y.; Stoddart J. F.; Ho C. M. In situ infrared spectroscopic studies of molecular behavior in nanoelectronic devices. IEEE-NANO 2003, 2, 698–701 10.1109/NANO.2003.1231008. [DOI] [Google Scholar]
Collier C. P.; Wong E. W.; Belohradsky M.; Raymo F. M.; Stoddart J. F.; Kuekes P. J.; Williams R. S.; Heath J. R. Electronically configurable molecular-based logic gates. Science 1999, 285, 391–394 10.1126/science.285.5426.391. [DOI] [PubMed] [Google Scholar]
Kitagawa K.; Morita T.; Kimura S. A helical molecule that exhibits two lengths in response to an applied potential. Angew. Chem., Int. Ed. 2005, 44, 6330–6333 10.1002/anie.200502240. [DOI] [PubMed] [Google Scholar]
Carella A.; Rapenne G.; Launay J. P. Design and synthesis of the active part of a potential molecular motor. New J. Chem. 2005, 29, 288–290 10.1039/b415214j. [DOI] [Google Scholar]
Carella A.; Jaud J.; Rapenne G.; Launay J. P. Technomimetic molecules: synthesis of ruthenium(II) 1,2,3,4,5-penta(p-bromophenyl)cyclopentadienyl hydrotris(indazolyl)borate, an organometallic molecular turnstile. Chem. Commun. 2003, 2434–2435 10.1039/b307577j. [DOI] [PubMed] [Google Scholar]
DeIonno E.; Tseng H. R.; Harvey D. D.; Stoddart J. F.; Heath J. R. Infrared spectroscopic characterization of [2]rotaxane molecular switch tunnel junction devices. J. Phys. Chem. B 2006, 110, 7609–7612 10.1021/jp0607723. [DOI] [PubMed] [Google Scholar]
Flood A. H.; Wong E. W.; Stoddart J. F. Models of charge transport and transfer in molecular switch tunnel junctions of bistable catenanes and rotaxanes. Chem. Phys. 2006, 324, 280–290 10.1016/j.chemphys.2005.12.031. [DOI] [Google Scholar]
Flood A. H.; Nygaard S.; Laursen B. W.; Jeppesen J. O.; Stoddart J. F. Locking down the electronic structure of (monopyrrolo)tetrathiafulvalene in [2]rotaxanes. Org. Lett. 2006, 8, 2205–2208 10.1021/ol060319+. [DOI] [PubMed] [Google Scholar]
Loppacher C.; Guggisberg M.; Pfeiffer O.; Meyer E.; Bammerlin M.; Luthi R.; Schlittler R.; Gimzewski J. K.; Tang H.; Joachim C.. Direct determination of the energy required to operate a single molecule switch. Phys. Rev. Lett. 2003, 90, 10.1103/PhysRevLett.90.066107. [DOI] [PubMed] [Google Scholar]
Viala C.; Secchi A.; Gourdon A. Synthesis of polyaromatic hydrocarbons with a central rotor. Eur. J. Org. Chem. 2002, 2002, 4185–4189. [DOI] [Google Scholar]
Gourdon A. Synthesis of ″molecular landers″. Eur. J. Org. Chem. 1998, 1998, 2797–2801. [DOI] [Google Scholar]
Langlais V. J.; Schlittler R. R.; Tang H.; Gourdon A.; Joachim C.; Gimzewski J. K. Spatially resolved tunneling along a molecular wire. Phys. Rev. Lett. 1999, 83, 2809–2812 10.1103/PhysRevLett.83.2809. [DOI] [Google Scholar]
Moresco F.; Gross L.; Grill L.; Alemani M.; Gourdon A.; Joachim C.; Rieder K. H. Contacting a single molecular wire by STM manipulation. Appl. Phys. A: Mater. Sci. Process. 2005, 80, 913–920 10.1007/s00339-004-3116-x. [DOI] [Google Scholar]
Moresco F.; Gourdon A. Scanning tunneling microscopy experiments on single molecular landers. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 8809–8814 10.1073/pnas.0500915102. [DOI] [PMC free article] [PubMed] [Google Scholar]
Soukiassian L.; Mayne A. J.; Comtet G.; Hellner L.; Dujardin G.; Gourdon A. Selective internal manipulation of a single molecule by scanning tunneling microscopy. J. Chem. Phys. 2005, 122, 134704. 10.1063/1.1874972. [DOI] [PubMed] [Google Scholar]
Lastapis M.; Martin M.; Riedel D.; Hellner L.; Comtet G.; Dujardin G. Picometer-scale electronic control of molecular dynamics inside a single molecule. Science 2005, 308, 1000–1003 10.1126/science.1108048. [DOI] [PubMed] [Google Scholar]
Metiu H. Special topic: Single-molecule physics and chemistry - Preface. J. Chem. Phys. 2002, 117, 10923–10923. [Google Scholar]
Barbara P. F. Single-molecule spectroscopy. Acc. Chem. Res. 2005, 38, 503–503 10.1021/ar050120h. [DOI] [PubMed] [Google Scholar]
Chiou P. Y.; Ohta A. T.; Wu M. C. Massively parallel manipulation of single cells and microparticles using optical images. Nature 2005, 436, 370–372 10.1038/nature03831. [DOI] [PubMed] [Google Scholar]
Dholakia K. Micromanipulation - Optoelectronic tweezers. Nat. Mater. 2005, 4, 579–580 10.1038/nmat1436. [DOI] [PubMed] [Google Scholar]
Moerner W. E.; Basche T. Optical Spectroscopy of Single Impurity Molecules in Solids. Angew. Chem., Int. Ed. Engl. 1993, 32, 457–476 10.1002/anie.199304573. [DOI] [Google Scholar]
Moerner W. E. Examining Nanoenvironments in Solids on the Scale of a Single, Isolated Impurity Molecule. Science 1994, 265, 46–53 10.1126/science.265.5168.46. [DOI] [PubMed] [Google Scholar]
Moerner W. E. High-resolution optical spectroscopy of single molecules in solids. Acc. Chem. Res. 1996, 29, 563–571 10.1021/ar950245u. [DOI] [Google Scholar]
Xie X. S. Single-molecule spectroscopy and dynamics at room temperature. Acc. Chem. Res. 1996, 29, 598–606 10.1021/ar950246m. [DOI] [Google Scholar]
Goodwin P. M.; Ambrose W. P.; Keller R. A. Single-molecule detection in liquids by laser-induced fluorescence. Acc. Chem. Res. 1996, 29, 607–613 10.1021/ar950250y. [DOI] [Google Scholar]
Nie S. M.; Zare R. N. Optical detection of single molecules. Annu. Rev. Biophys. Biomol. Struct. 1997, 26, 567–596 10.1146/annurev.biophys.26.1.567. [DOI] [PubMed] [Google Scholar]
Plakhotnik T.; Donley E. A.; Wild U. P. Single-molecule spectroscopy. Annu. Rev. Phys. Chem. 1997, 48, 181–212 10.1146/annurev.physchem.48.1.181. [DOI] [PubMed] [Google Scholar]
Xie X. S.; Trautman J. K. Optical studies of single molecules at room temperature. Annu. Rev. Phys. Chem. 1998, 49, 441–480 10.1146/annurev.physchem.49.1.441. [DOI] [PubMed] [Google Scholar]
Moerner W. E.; Orrit M. Illuminating single molecules in condensed matter. Science 1999, 283, 1670–1676 10.1126/science.283.5408.1670. [DOI] [PubMed] [Google Scholar]
Weiss S. Fluorescence spectroscopy of single biomolecules. Science 1999, 283, 1676–1683 10.1126/science.283.5408.1676. [DOI] [PubMed] [Google Scholar]
Ambrose W. P.; Goodwin P. M.; Jett J. H.; Van Orden A.; Werner J. H.; Keller R. A. Single molecule fluorescence spectroscopy at ambient temperature. Chem. Rev. 1999, 99, 2929–2956 10.1021/cr980132z. [DOI] [PubMed] [Google Scholar]
Deniz A. A.; Laurence T. A.; Dahan M.; Chemla D. S.; Schultz P. G.; Weiss S. Ratiometric single-molecule studies of freely diffusing biomolecules. Annu. Rev. Phys. Chem. 2001, 52, 233–253 10.1146/annurev.physchem.52.1.233. [DOI] [PubMed] [Google Scholar]
Moerner W. E. A dozen years of single-molecule spectroscopy in physics, chemistry, and biophysics. J. Phys. Chem. B 2002, 106, 910–927 10.1021/jp012992g. [DOI] [Google Scholar]
Keller R. A.; Ambrose W. P.; Arias A. A.; Gai H.; Emory S. R.; Goodwin P. M.; Jett J. H. Analytical applications of single-molecule detection. Anal. Chem. 2002, 74, 316a–324a 10.1021/ac022035i. [DOI] [PubMed] [Google Scholar]
Bohmer M.; Enderlein J. Fluorescence spectroscopy of single molecules under ambient conditions: Methodology and technology. ChemPhysChem 2003, 4, 793–808 10.1002/cphc.200200565. [DOI] [PubMed] [Google Scholar]
Moerner W. E.; Fromm D. P. Methods of single-molecule fluorescence spectroscopy and microscopy. Rev. Sci. Instrum. 2003, 74, 3597–3619 10.1063/1.1589587. [DOI] [Google Scholar]
Tinnefeld P.; Sauer M. Branching out of single-molecule fluorescence spectroscopy: Challenges for chemistry and influence on biology. Angew. Chem., Int. Ed. 2005, 44, 2642–2671 10.1002/anie.200300647. [DOI] [PubMed] [Google Scholar]
Fang N.; Lee H.; Sun C.; Zhang X. Sub-diffraction-limited optical imaging with a silver superlens. Science 2005, 308, 534–537 10.1126/science.1108759. [DOI] [PubMed] [Google Scholar]
Nishimura D.; Takashima Y.; Aoki H.; Takahashi T.; Yamaguchi H.; Ito S.; Harada A. Single-Molecule Imaging of Rotaxanes Immobilized on Glass Substrates: Observation of Rotary Movement. Angew. Chem., Int. Ed. 2008, 47, 6077–6079 10.1002/anie.200801431. [DOI] [PubMed] [Google Scholar]
Crooks R. M.; Ricco A. J. New organic materials suitable for use in chemical sensor arrays. Acc. Chem. Res. 1998, 31, 219–227 10.1021/ar970246h. [DOI] [Google Scholar]
Goldenberg L. M.; Bryce M. R.; Petty M. C. Chemosensor devices: voltammetric molecular recognition at solid interfaces. J. Mater. Chem. 1999, 9, 1957–1974 10.1039/a901825e. [DOI] [Google Scholar]
Flink S.; van Veggel F. C. J. M.; Reinhoudt D. N. Sensor functionalities in self-assembled monolayers. Adv. Mater. 2000, 12, 1315–1328. [DOI] [Google Scholar]
Shipway A. N.; Katz E.; Willner I. Nanoparticle arrays on surfaces for electronic, optical, and sensor applications. ChemPhysChem 2000, 1, 18–52. [DOI] [PubMed] [Google Scholar]
Katz E.; Willner I. Probing biomolecular interactions at conductive and semiconductive surfaces by impedance spectroscopy: Routes to impedimetric immunosensors, DNA-Sensors, and enzyme biosensors. Electroanalysis 2003, 15, 913–947 10.1002/elan.200390114. [DOI] [Google Scholar]
Cooke G. Electrochemical and photochemical control of host-guest complexation at surfaces. Angew. Chem., Int. Ed. 2003, 42, 4860–4870 10.1002/anie.200301636. [DOI] [PubMed] [Google Scholar]
Astruc D.; Daniel M. C.; Ruiz J. Dendrimers and gold nanoparticles as exo-receptors sensing biologically important anions. Chem. Commun. 2004, 2637–2649 10.1039/b410399h. [DOI] [PubMed] [Google Scholar]
Drechsler U.; Erdogan B.; Rotello V. M. Nanoparticles: Scaffolds for molecular recognition. Chem. - Eur. J. 2004, 10, 5570–5579 10.1002/chem.200306076. [DOI] [PubMed] [Google Scholar]
Mallouk T. E.; Gavin J. A. Molecular recognition in lamellar solids and thin films. Acc. Chem. Res. 1998, 31, 209–217 10.1021/ar970038p. [DOI] [Google Scholar]
Chia S. Y.; Cao J. G.; Stoddart J. F.; Zink J. I. Working supramolecular machines trapped in glass and mounted on a film surface. Angew. Chem., Int. Ed. 2001, 40, 2447–2451. [DOI] [PubMed] [Google Scholar]
Gase T.; Grando D.; Chollet P. A.; Kajzar F.; Murphy A.; Leigh D. A. Linear and unanticipated second-order nonlinear optical properties of benzylic amide [2]Catenane thin films: Evidence of partial rotation of the interlocked molecular rings in the solid state. Adv. Mater. 1999, 11, 1303–1306. [DOI] [Google Scholar]
Deleuze M. S. Can benzylic amide [2]catenane rings rotate on graphite?. J. Am. Chem. Soc. 2000, 122, 1130–1143 10.1021/ja992458a. [DOI] [Google Scholar]
Bidan G.; Billon M.; Divisia-Blohorn B.; Kern J. M.; Raehm L.; Sauvage J.-P. Electrode-deposited films of polyrotaxanes: electrochemically induced gliding motion. New J. Chem. 1998, 22, 1139–1141 10.1039/a804969f. [DOI] [Google Scholar]
Raehm L.; Kern J. M.; Sauvage J.-P.; Hamann C.; Palacin S.; Bourgoin J. P. Disulfide- and thiol-incorporating copper catenanes: Synthesis deposition onto gold, and surface studies. Chem. - Eur. J. 2002, 8, 2153–2162. [DOI] [PubMed] [Google Scholar]
Tseng H. R.; Wu D. M.; Fang N. X. L.; Zhang X.; Stoddart J. F. The metastability of an electrochemically controlled nanoscale machine on gold surfaces. ChemPhysChem 2004, 5, 111–116 10.1002/cphc.200300992. [DOI] [PubMed] [Google Scholar]
Huang T. J.; Tseng H. R.; Sha L.; Lu W. X.; Brough B.; Flood A. H.; Yu B. D.; Celestre P. C.; Chang J. P.; Stoddart J. F.; Ho C. M. Mechanical shuttling of linear motor-molecules in condensed phases on solid substrates. Nano Lett. 2004, 4, 2065–2071 10.1021/nl035099x. [DOI] [Google Scholar]
Long B.; Nikitin K.; Fitzmaurice D. Assembly of an electronically switchable rotaxane on the surface of a titanium dioxide nanoparticle. J. Am. Chem. Soc. 2003, 125, 15490–15498 10.1021/ja037592g. [DOI] [PubMed] [Google Scholar]
Nikitin K.; Fitzmaurice D. The oxidation-state dependent structural conformation and supramolecular function of a redox-active [2]rotaxane in solution. J. Am. Chem. Soc. 2005, 127, 8067–8076 10.1021/ja050694h. [DOI] [PubMed] [Google Scholar]
van Delden R. A.; ter Wiel M. K. J.; Pollard M. M.; Vicario J.; Koumura N.; Feringa B. L. Unidirectional molecular motor on a gold surface. Nature 2005, 437, 1337–1340 10.1038/nature04127. [DOI] [PubMed] [Google Scholar]
Hou S. M.; Sagara T.; Xu D. C.; Kelly T. R.; Ganz E. Investigation of triptycene-based surface-mounted rotors. Nanotechnology 2003, 14, 566–570 10.1088/0957-4484/14/5/316. [DOI] [Google Scholar]
Jensen K.; Girit Ç.; Mickelson W.; Zettl A. Tunable Nanoresonators Constructed from Telescoping Nanotubes. Phys. Rev. Lett. 2006, 96, 215503. 10.1103/PhysRevLett.96.215503. [DOI] [PubMed] [Google Scholar]
Deshpande V. V.; Chiu H. Y.; Postma H. W. C.; Mikó C.; Forró L.; Bockrath M. Carbon Nanotube Linear Bearing Nanoswitches. Nano Lett. 2006, 6, 1092–1095 10.1021/nl052513f. [DOI] [PubMed] [Google Scholar]
Ebron V. H.; Yang Z.; Seyer D. J.; Kozlov M. E.; Oh J.; Xie H.; Razal J.; Hall L. J.; Ferraris J. P.; MacDiarmid A. G.; Baughman R. H. Fuel-Powered Artificial Muscles. Science 2006, 311, 1580–1583 10.1126/science.1120182. [DOI] [PubMed] [Google Scholar]
Huang T. J.; Flood A. H.; Brough B.; Liu Y.; Bonvallet P. A.; Kang S. S.; Chu C. W.; Guo T. F.; Lu W. X.; Yang Y.; et al. Understanding and harnessing biomimetic molecular machines for NEMS actuation materials. IEEE Trans. Autom. Sci. Eng. 2006, 3, 254–259 10.1109/TASE.2006.875543. [DOI] [Google Scholar]
Yamaguchi H.; Kobayashi Y.; Kobayashi R.; Takashima Y.; Hashidzume A.; Harada A. Photoswitchable gel assembly based on molecular recognition. Nat. Commun. 2012, 3, 603. 10.1038/ncomms1617. [DOI] [PMC free article] [PubMed] [Google Scholar]
Zheng Y.; Hashidzume A.; Takashima Y.; Yamaguchi H.; Harada A. Switching of macroscopic molecular recognition selectivity using a mixed solvent system. Nat. Commun. 2012, 3, 831. 10.1038/ncomms1841. [DOI] [PubMed] [Google Scholar]
Abelow A. E.; Zharov I. Reversible nanovalves in inorganic materials. J. Mater. Chem. 2012, 22, 21810–21818 10.1039/c2jm33437b. [DOI] [Google Scholar]
Adiga S. P.; Brenner D. W. Toward designing smart nanovalves: Modeling of flow control through nanopores via the helix-coil transition of grafted polypeptide chains. Macromolecules 2007, 40, 1342–1348 10.1021/ma0617522. [DOI] [Google Scholar]
Angelos S.; Yang Y. W.; Patel K.; Stoddart J. F.; Zink J. I. pH-responsive supramolecular nanovalves based on cucurbit[6]uril pseudorotaxanes. Angew. Chem., Int. Ed. 2008, 47, 2222–2226 10.1002/anie.200705211. [DOI] [PubMed] [Google Scholar]
Chen T.; Fu J. J. pH-responsive nanovalves based on hollow mesoporous silica spheres for controlled release of corrosion inhibitor. Nanotechnology 2012, 23, 235605. 10.1088/0957-4484/23/23/235605. [DOI] [PubMed] [Google Scholar]
Croissant J.; Chaix A.; Mongin O.; Wang M.; Clement S.; Raehm L.; Durand J. O.; Hugues V.; Blanchard-Desce M.; Maynadier M.; et al. Two-Photon-Triggered Drug Delivery via Fluorescent Nanovalves. Small 2014, 10, 1752–1755 10.1002/smll.201400042. [DOI] [PubMed] [Google Scholar]
Hwang A. A.; Lu J.; Tamanoi F.; Zink J. I. Functional Nanovalves on Protein-Coated Nanoparticles for In vitro and In vivo Controlled Drug Delivery. Small 2015, 11, 319–328 10.1002/smll.201400765. [DOI] [PMC free article] [PubMed] [Google Scholar]
Dong J. Y.; Xue M.; Zink J. I. Functioning of nanovalves on polymer coated mesoporous silica Nanoparticles. Nanoscale 2013, 5, 10300–10306 10.1039/c3nr03442a. [DOI] [PMC free article] [PubMed] [Google Scholar]
Lau Y. A.; Ferris D. P.; Zink J. I.. Photo-driven nano-impellers and nanovalves for on-command drug release. Proc. SPIE 2010, 7574, 75740P, 10.1117/12.841175. [DOI] [Google Scholar]
Li Q. L.; Wang L.; Qiu X. L.; Sun Y. L.; Wang P. X.; Liu Y.; Li F.; Qi A. D.; Gao H.; Yang Y. W. Stimuli-responsive biocompatible nanovalves based on beta-cyclodextrin modified poly(glycidyl methacrylate). Polym. Chem. 2014, 5, 3389–3395 10.1039/c4py00041b. [DOI] [Google Scholar]
Liu J. S.; Du X. Z. pH- and competitor-driven nanovalves of cucurbit[7]uril pseudorotaxanes based on mesoporous silica supports for controlled release. J. Mater. Chem. 2010, 20, 3642–3649 10.1039/b915510d. [DOI] [Google Scholar]
Liu J. S.; Du X. Z.; Zhang X. F. Enzyme-Inspired Controlled Release of Cucurbit[7]uril Nanovalves by Using Magnetic Mesoporous Silica. Chem. - Eur. J. 2011, 17, 810–815 10.1002/chem.201002899. [DOI] [PubMed] [Google Scholar]
Luo G. F.; Chen W. H.; Liu Y.; Zhang J.; Cheng S. X.; Zhuo R. X.; Zhang X. Z. Charge-reversal plug gate nanovalves on peptide-functionalized mesoporous silica nanoparticles for targeted drug delivery. J. Mater. Chem. B 2013, 1, 5723–5732 10.1039/c3tb20792g. [DOI] [PubMed] [Google Scholar]
Meng H. A.; Xue M.; Xia T. A.; Zhao Y. L.; Tamanoi F.; Stoddart J. F.; Zink J. I.; Nel A. E. Autonomous in Vitro Anticancer Drug Release from Mesoporous Silica Nanoparticles by pH-Sensitive Nanovalves. J. Am. Chem. Soc. 2010, 132, 12690–12697 10.1021/ja104501a. [DOI] [PMC free article] [PubMed] [Google Scholar]
Saha S.; Leung K. C. F.; Nguyen T. D.; Stoddart J. F.; Zink J. I. Nanovalves. Adv. Funct. Mater. 2007, 17, 685–693 10.1002/adfm.200600989. [DOI] [Google Scholar]
Yang Y. W. Towards biocompatible nanovalves based on mesoporous silica nanoparticles. MedChemComm 2011, 2, 1033–1049 10.1039/c1md00158b. [DOI] [Google Scholar]
Zhou Y.; Tan L. L.; Li Q. L.; Qiu X. L.; Qi A. D.; Tao Y. C.; Yang Y. W. Acetylcholine-Triggered Cargo Release from Supramolecular Nanovalves Based on Different Macrocyclic Receptors. Chem. - Eur. J. 2014, 20, 2998–3004 10.1002/chem.201304864. [DOI] [PubMed] [Google Scholar]
Hernandez R.; Tseng H. R.; Wong J. W.; Stoddart J. F.; Zink J. I. An operational supramolecular nanovalve. J. Am. Chem. Soc. 2004, 126, 3370–3371 10.1021/ja039424u. [DOI] [PubMed] [Google Scholar]
Unimolecular and Supramolecular Electronics II: Chemistry and Physics Meet at Metal-Molecule Interfaces; 2012; Vol. 313, pp 1–272. [Google Scholar]
Joachim C. Molecular wires and logic circuits integration in a single molecule?. Nanotechnology 2003, 2, 80–81. [Google Scholar]
Joachim C. Molecular and intramolecular electronics. Superlattices Microstruct. 2000, 28, 305–315 10.1006/spmi.2000.0918. [DOI] [Google Scholar]
Joachim C.; Ratner M. A. Molecular electronics. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 8800–8800 10.1073/pnas.0504046102. [DOI] [PMC free article] [PubMed] [Google Scholar]
Schenning A. P. H. J.; Jonkheijm P.; Hoeben F. J. M.; van Herrikhuyzen J.; Meskers S. C. J.; Meijer E. W.; Herz L. M.; Daniel C.; Silva C.; Phillips R. T.; et al. Towards supramolecular electronics. Synth. Met. 2004, 147, 43–48 10.1016/j.synthmet.2004.06.038. [DOI] [Google Scholar]
Weiss J. Supramolecular approaches to nano and molecular electronics. Coord. Chem. Rev. 2010, 254, 2247–2248 10.1016/j.ccr.2010.06.002. [DOI] [Google Scholar]
Flood A. H.; Stoddart J. F.; Steuerman D. W.; Heath J. R. Chemistry. Whence molecular electronics?. Science 2004, 306, 2055–2056 10.1126/science.1106195. [DOI] [PubMed] [Google Scholar]
Blanco M. J.; Jimenez M. C.; Chambron J. C.; Heitz V.; Linke M.; Sauvage J.-P. Rotaxanes as new architectures for photoinduced electron transfer and molecular motions. Chem. Soc. Rev. 1999, 28, 293–305 10.1039/a901205b. [DOI] [Google Scholar]
Huang T. J. Towards artificial molecular motor-based electroactive/photoactive biomimetic muscles - art. no. 65240H. P. Soc. Photo. Opt. Ins. 2007, 6524, H5240–H5240 10.1117/12.718483. [DOI] [Google Scholar]
Juluri B. K.; Kumar A. S.; Liu Y.; Ye T.; Yang Y. W.; Flood A. H.; Fang L.; Stoddart J. F.; Weiss P. S.; Huang T. J. A Mechanical Actuator Driven Electrochemically by Artificial Molecular Muscles. ACS Nano 2009, 3, 291–300 10.1021/nn8002373. [DOI] [PubMed] [Google Scholar]
Li D. B.; Paxton W. F.; Baughman R. H.; Huang T. J.; Stoddart J. F.; Weiss P. S. Molecular, Supramolecular, and Macromolecular Motors and Artificial Muscles. MRS Bull. 2009, 34, 671–681 10.1557/mrs2009.179. [DOI] [Google Scholar]
Liu Y.; Flood A. H.; Bonvallett P. A.; Vignon S. A.; Northrop B. H.; Tseng H. R.; Jeppesen J. O.; Huang T. J.; Brough B.; Baller M.; Magonov S.; Solares S. D.; Goddard W. A. III; Ho C. M.; Stoddart J. F. Linear artificial molecular muscles. J. Am. Chem. Soc. 2005, 127, 9745–9759 10.1021/ja051088p. [DOI] [PubMed] [Google Scholar]
Park J. K.; Carr J.; Calhoun B.; Moore R. B. Enhanced actuation in artificial muscles through supra-molecular orientation of ionic domains. Polym. Prepr. 2006, 47, 484–485. [Google Scholar]
Otero T. F.; Grande H.; Rodriguez J. Reversible electrochemical reactions in conducting polymers: A molecular approach to artificial muscles. J. Phys. Org. Chem. 1996, 9, 381–386. [DOI] [Google Scholar]
Valero L.; Arias-Pardilla J.; Cauich-Rodriguez J.; Smit M. A.; Otero T. F. Characterization of the movement of polypyrrole-dodecylbenzenesulfonate-perchlorate/tape artificial muscles. Faradaic control of reactive artificial molecular motors and muscles. Electrochim. Acta 2011, 56, 3721–3726 10.1016/j.electacta.2010.11.058. [DOI] [Google Scholar]
Takashima Y.; Hatanaka S.; Otsubo M.; Nakahata M.; Kakuta T.; Hashidzume A.; Yamaguchi H.; Harada A. Expansion-contraction of photoresponsive artificial muscle regulated by host-guest interactions. Nat. Commun. 2012, 3, 1270. 10.1038/ncomms2280. [DOI] [PMC free article] [PubMed] [Google Scholar]
Ceroni P.; Credi A.; Venturi M. Light to investigate (read) and operate (write) molecular devices and machines. Chem. Soc. Rev. 2014, 43, 4068–4083 10.1039/c3cs60400d. [DOI] [PubMed] [Google Scholar]
Hutchison K. A.; Parakka J. P.; Kesler B. S.; Schumaker R. R. Chiropticenes: Molecular chiroptical dipole switches for optical data storage. Micro-Nano-Photonic Mater. Dev. 2000, 3937, 64–72 10.1117/12.382795. [DOI] [Google Scholar]
Berna J.; Leigh D. A.; Lubomska M.; Mendoza S. M.; Perez E. M.; Rudolf P.; Teobaldi G.; Zerbetto F. Macroscopic transport by synthetic molecular machines. Nat. Mater. 2005, 4, 704–710 10.1038/nmat1455. [DOI] [PubMed] [Google Scholar]
Silvi S.; Arduini A.; Pochini A.; Secchi A.; Tomasulo M.; Raymo F. M.; Baroncini M.; Credi A. A simple molecular machine operated by photoinduced proton transfer. J. Am. Chem. Soc. 2007, 129, 13378–13379 10.1021/ja0753851. [DOI] [PubMed] [Google Scholar]
Silvi S.; Constable E. C.; Housecroft C. E.; Beves J. E.; Dunphy E. L.; Tomasulo M.; Raymo F. M.; Credi A. Photochemical switching of luminescence and singlet oxygen generation by chemical signal communication. Chem. Commun. 2009, 1484–1486 10.1039/b900712a. [DOI] [PubMed] [Google Scholar]
Tatum L. A.; Foy J. T.; Aprahamian I. Waste Management of Chemically Activated Switches: Using a Photoacid To Eliminate Accumulation of Side Products. J. Am. Chem. Soc. 2014, 136, 17438–17441 10.1021/ja511135k. [DOI] [PubMed] [Google Scholar]
Jousselme B.; Blanchard P.; Levillain E.; Delaunay J.; Allain M.; Richomme P.; Rondeau D.; Gallego-Planas N.; Roncali J. Crown-annelated oligothiophenes as model compounds for molecular actuation. J. Am. Chem. Soc. 2003, 125, 1363–1370 10.1021/ja026819p. [DOI] [PubMed] [Google Scholar]
Roncali J.; Garreau R.; Delabouglise D.; Garnier F.; Lemaire M. Modification of the Structure and Electrochemical Properties of Poly(Thiophene) by Ether Groups. J. Chem. Soc., Chem. Commun. 1989, 679–681 10.1039/c39890000679. [DOI] [Google Scholar]
Roncali J.; Shi L. H.; Garnier F. Effects of Environmental-Factors on the Electrooptical Properties of Conjugated Polymers Containing Oligo(Oxyethylene) Substituents. J. Phys. Chem. 1991, 95, 8983–8989 10.1021/j100175a102. [DOI] [Google Scholar]
Marsella M. J.; Swager T. M. Designing Conducting Polymer-Based Sensors - Selective Ionochromic Response in Crown-Ether Containing Polythiophenes. J. Am. Chem. Soc. 1993, 115, 12214–12215 10.1021/ja00078a090. [DOI] [Google Scholar]
Wang B.; Wasielewski M. R. Design and synthesis of metal ion-recognition-induced conjugated polymers: An approach to metal ion sensory materials. J. Am. Chem. Soc. 1997, 119, 12–21 10.1021/ja962229d. [DOI] [Google Scholar]
Marsella M. J.; Newland R. J.; Carroll P. J.; Swager T. M. Ionoresistivity as a Highly Sensitive Sensory Probe - Investigations of Polythiophenes Functionalized with Calix[4]Arene-Based Ion Receptors. J. Am. Chem. Soc. 1995, 117, 9842–9848 10.1021/ja00144a009. [DOI] [Google Scholar]
Roncali J. Electrogenerated functional conjugated polymers as advanced electrode materials. J. Mater. Chem. 1999, 9, 1875–1893 10.1039/a902747e. [DOI] [Google Scholar]
McQuade D. T.; Pullen A. E.; Swager T. M. Conjugated polymer-based chemical sensors. Chem. Rev. 2000, 100, 2537–2574 10.1021/cr9801014. [DOI] [PubMed] [Google Scholar]
Barbarella G.; Melucci M.; Sotgiu G. The versatile thiophene: An overview of recent research on thiophene-based materials. Adv. Mater. 2005, 17, 1581–1593 10.1002/adma.200402020. [DOI] [Google Scholar]
Jousselme B.; Blanchard P.; Gallego-Planas N.; Delaunay J.; Allain M.; Richomme P.; Levillain E.; Roncali J. Photomechanical actuation and manipulation of the electronic properties of linear π-conjugated systems. J. Am. Chem. Soc. 2003, 125, 2888–2889 10.1021/ja029754z. [DOI] [PubMed] [Google Scholar]
Jousselme B.; Blanchard P.; Gallego-Planas N.; Levillain E.; Delaunay J.; Allain M.; Richomme P.; Roncali J. Photomechanical control of the electronic properties of linear π-conjugated systems. Chem. - Eur. J. 2003, 9, 5297–5306 10.1002/chem.200305010. [DOI] [PubMed] [Google Scholar]
Clayden J.; Lund A.; Vallverdu L. S.; Helliwell M. Ultra-remote stereocontrol by conformational communication of information along a carbon chain. Nature 2004, 431, 966–971 10.1038/nature02933. [DOI] [PubMed] [Google Scholar]
Barton D. H. R.; Cookson R. C. The Principles of Conformational Analysis. Q. Rev., Chem. Soc. 1956, 10, 44–82 10.1039/qr9561000044. [DOI] [Google Scholar]
Browne W. R.; Pollard M. M.; de Lange B.; Meetsma A.; Feringa B. L. Reversible three-state switching of luminescence: a new twist to electro- and photochromic behavior. J. Am. Chem. Soc. 2006, 128, 12412–12413 10.1021/ja064423y. [DOI] [PubMed] [Google Scholar]
Nilsson J. R.; O’Sullivan M. C.; Li S.; Anderson H. L.; Andreasson J. A photoswitchable supramolecular complex with release-and-report capabilities. Chem. Commun. 2015, 51, 847–850 10.1039/C4CC08513B. [DOI] [PubMed] [Google Scholar]
Zigon N.; Larpent P.; Jouaiti A.; Kyritsakas N.; Hosseini M. W. Optical reading of the open and closed states of a molecular turnstile. Chem. Commun. 2014, 50, 5040–5042 10.1039/c4cc01071j. [DOI] [PubMed] [Google Scholar]
Dube H.; Ams M. R.; Rebek J. Supramolecular Control of Fluorescence through Reversible Encapsulation. J. Am. Chem. Soc. 2010, 132, 9984–9985 10.1021/ja103912a. [DOI] [PubMed] [Google Scholar]
Tzeli D.; Theodorakopoulos G.; Petsalakis I. D.; Ajami D.; Rebek J. Conformations and Fluorescence of Encapsulated Stilbene. J. Am. Chem. Soc. 2012, 134, 4346–4354 10.1021/ja211164b. [DOI] [PubMed] [Google Scholar]
Masar M. S.; Gianneschi N. C.; Oliveri C. G.; Stern C. L.; Nguyen S. T.; Mirkin C. A. Allosterically regulated supramolecular catalysis of acyl transfer reactions for signal amplification and detection of small molecules. J. Am. Chem. Soc. 2007, 129, 10149–10158 10.1021/ja0711516. [DOI] [PubMed] [Google Scholar]
Riddle J. A.; Jiang X.; Huffman J.; Lee D. Signal-amplifying resonance energy transfer: A dynamic multichromophore array for allosteric switching. Angew. Chem., Int. Ed. 2007, 46, 7019–7022 10.1002/anie.200701410. [DOI] [PubMed] [Google Scholar]
Jiang X.; Bollinger J. C.; Lee D. Two-dimensional electronic conjugation: Cooperative folding and fluorescence switching. J. Am. Chem. Soc. 2006, 128, 11732–11733 10.1021/ja063413u. [DOI] [PubMed] [Google Scholar]
Riddle J. A.; Jiang X.; Lee D. W. Conformational dynamics for chemical sensing: simplicity and diversity. Analyst 2008, 133, 417–422 10.1039/b715673c. [DOI] [PubMed] [Google Scholar]
Opsitnick E.; Lee D. Two-dimensional electronic conjugation: Statics and dynamics at structural domains beyond molecular wires. Chem. - Eur. J. 2007, 13, 7041–7049 10.1002/chem.200700813. [DOI] [PubMed] [Google Scholar]
Onagi H.; Rebek J. Fluorescence resonance energy transfer across a mechanical bond of a rotaxane. Chem. Commun. 2005, 4604–4606 10.1039/b506177f. [DOI] [PubMed] [Google Scholar]
Azov V. A.; Schlegel A.; Diederich F. Geometrically precisely defined multinanometer expansion/contraction motions in a resorcin[4]arene cavitand based molecular switch. Angew. Chem., Int. Ed. 2005, 44, 4635–4638 10.1002/anie.200500970. [DOI] [PubMed] [Google Scholar]
Li Y. J.; Li H.; Li Y. L.; Liu H. B.; Wang S.; He X. R.; Wang N.; Zhu D. B. Energy transfer switching in a bistable molecular machine. Org. Lett. 2005, 7, 4835–4838 10.1021/ol051567t. [DOI] [PubMed] [Google Scholar]
Raker J.; Glass T. E. Cooperative ratiometric chemosensors: Pinwheel receptors with an integrated fluorescence system. J. Org. Chem. 2001, 66, 6505–6512 10.1021/jo001775t. [DOI] [PubMed] [Google Scholar]
Barboiu M.; Prodi L.; Montalti M.; Zaccheroni N.; Kyritsakas N.; Lehn J.-M. Dynamic chemical devices: Modulation of photophysical properties by reversible, ion-triggered, and proton-fueled nanomechanical shape-flipping molecular motions. Chem. - Eur. J. 2004, 10, 2953–2959 10.1002/chem.200306045. [DOI] [PubMed] [Google Scholar]
Zhong Z.; Zhao Y. Cholate-glutamic acid hybrid foldamer and its fluorescent detection of Zn²⁺. Org. Lett. 2007, 9, 2891–2894 10.1021/ol071130g. [DOI] [PubMed] [Google Scholar]
Kim U. I.; Suk J. M.; Naidu V. R.; Jeong K. S. Folding and anion-binding properties of fluorescent oligoindole foldamers. Chem. - Eur. J. 2008, 14, 11406–11414 10.1002/chem.200801713. [DOI] [PubMed] [Google Scholar]
Yuasa H.; Miyagawa N.; Izumi T.; Nakatani M.; Izumi M.; Hashimoto H. Hinge sugar as a movable component of an excimer fluorescence sensor. Org. Lett. 2004, 6, 1489–1492 10.1021/ol049628v. [DOI] [PubMed] [Google Scholar]
Monahan C.; Bien J. T.; Smith B. D. Fluorescence sensing due to allosteric switching of pyrene functionalized cis-cyclohexane-1,3-dicarboxylate. Chem. Commun. 1998, 431–432 10.1039/a705445i. [DOI] [Google Scholar]
Krauss R.; Weinig H. G.; Seydack M.; Bendig J.; Koert U. Molecular signal transduction through conformational transmission of a perhydroanthracene transducer. Angew. Chem., Int. Ed. 2000, 39, 1835–1837. [DOI] [PubMed] [Google Scholar]
Koert U.; Krauss R.; Weinig H. G.; Heumann C.; Ziemer B.; Mugge C.; Seydack M.; Bendig J. 2,3,6,7-tetrasubstituted decalins: Biconformational transducers for molecular signal transduction. Eur. J. Org. Chem. 2001, 2001, 575–586. [DOI] [Google Scholar]
Berna J.; Franco-Pujante C.; Alajarin M. Competitive binding for triggering a fluorescence response in a hydrazodicarboxamide-based [2]rotaxane. Org. Biomol. Chem. 2014, 12, 474–478 10.1039/C3OB41807C. [DOI] [PubMed] [Google Scholar]
Zhou W.; Wu Y.; Zhai B. Q.; Wang Q. C.; Qu D. H. An anthracene-containing bistable [2]rotaxane featuring color and fluorescence changes. RSC Adv. 2014, 4, 5148–5151 10.1039/c3ra46517a. [DOI] [Google Scholar]
Perez E. M.; Dryden D. T. F.; Leigh D. A.; Teobaldi G.; Zerbetto F. A generic basis for some simple light-operated mechanical molecular machines. J. Am. Chem. Soc. 2004, 126, 12210–12211 10.1021/ja0484193. [DOI] [PubMed] [Google Scholar]
Buschel M.; Helldobler M.; Daub J. Electronic coupling in 6,6″-donor-substituted terpyridines: tuning of the mixed valence state by proton and metal ion complexation. Chem. Commun. 2002, 1338–1339 10.1039/b110289c. [DOI] [Google Scholar]
Glass T. E. Cooperative chemical sensing with bis-tritylacetylenes: Pinwheel receptors with metal ion recognition properties. J. Am. Chem. Soc. 2000, 122, 4522–4523 10.1021/ja994398e. [DOI] [Google Scholar]
Raker J.; Glass T. E. Selectivity via cooperative interactions: Detection of dicarboxylates in water by a pinwheel chemosensor. J. Org. Chem. 2002, 67, 6113–6116 10.1021/jo025903k. [DOI] [PubMed] [Google Scholar]
Karle M.; Bockelmann D.; Schumann D.; Griesinger C.; Koert U. Conformative coupling of two conformational molecular switches. Angew. Chem., Int. Ed. 2003, 42, 4546–4549 10.1002/anie.200352130. [DOI] [PubMed] [Google Scholar]
Zhao Y.; Zhong Z. Detection of Hg²⁺ in aqueous solutions with a foldamer-based fluorescent sensor modulated by surfactant micelles. Org. Lett. 2006, 8, 4715–4717 10.1021/ol061735x. [DOI] [PubMed] [Google Scholar]
Qu D. H.; Wang Q. C.; Tian H. A half adder based on a photochemically driven [2]rotaxane. Angew. Chem., Int. Ed. 2005, 44, 5296–5299 10.1002/anie.200501215. [DOI] [PubMed] [Google Scholar]
Li H.; Zhang J. N.; Zhou W.; Zhang H.; Zhang Q.; Qu D. H.; Tian H. Dual-Mode Operation of a Bistable [1]Rotaxane with a Fluorescence Signal. Org. Lett. 2013, 15, 3070–3073 10.1021/ol401251u. [DOI] [PubMed] [Google Scholar]
Qu D. H.; Wang Q. C.; Tian H. Photodriven and thermal-driven shuttling of alpha-cyclodextrin on the molecular rotaxane containing azobenzene. Mol. Cryst. Liq. Cryst. 2005, 430, 59–65 10.1080/15421400590946172. [DOI] [Google Scholar]
Qu D. H.; Wang Q. C.; Ma X.; Tian H. A [3]Rotaxane with three stable states that responds to multiple-inputs and displays dual fluorescence addresses. Chem. - Eur. J. 2005, 11, 5929–5937 10.1002/chem.200401313. [DOI] [PubMed] [Google Scholar]
Lin Y. C.; Chen C. T. Alkaline Earth Metal Ion Induced CoilHelixCoil Transition of LysineCoumarinAzacrown Hybrid Foldamers with OFFOFFON Fluorescence Switching. Chem. - Eur. J. 2013, 19, 2531–2538 10.1002/chem.201202998. [DOI] [PubMed] [Google Scholar]
Coskun A.; Friedman D. C.; Li H.; Patel K.; Khatib H. A.; Stoddart J. F. A Light-Gated STOP–GO Molecular Shuttle. J. Am. Chem. Soc. 2009, 131, 2493–2495 10.1021/ja809225e. [DOI] [PubMed] [Google Scholar]
Cao J. J.; Ma X.; Min M. R.; Cao T. T.; Wu S. F.; Tian H. INHIBIT logic operations based on light-driven beta-cyclodextrin pseudo[1]rotaxane with room temperature phosphorescence addresses. Chem. Commun. 2014, 50, 3224–3226 10.1039/c3cc49820d. [DOI] [PubMed] [Google Scholar]
Brown R. A.; Diemer V.; Webb S. J.; Clayden J. End-to-end conformational communication through a synthetic purinergic receptor by ligand-induced helicity switching. Nat. Chem. 2013, 5, 853–860 10.1038/nchem.1747. [DOI] [PubMed] [Google Scholar]
Muraoka T.; Kinbara K.; Aida T. A self-locking molecule operative with a photoresponsive key. J. Am. Chem. Soc. 2006, 128, 11600–11605 10.1021/ja0632308. [DOI] [PubMed] [Google Scholar]
Clayden J.; Vassiliou N. Stereochemical relays: communication via conformation. Org. Biomol. Chem. 2006, 4, 2667–2678 10.1039/b604548k. [DOI] [PubMed] [Google Scholar]
Jiang X.; Lim Y. K.; Zhang B. J.; Opsitnick E. A.; Baik M. H.; Lee D. Dendritic molecular switch: chiral folding and helicity inversion. J. Am. Chem. Soc. 2008, 130, 16812–16822 10.1021/ja806723e. [DOI] [PubMed] [Google Scholar]
Clayden J.; Castellanos A.; Sola J.; Morris G. A. Quantifying End-to-End Conformational Communication of Chirality through an Achiral Peptide Chain. Angew. Chem., Int. Ed. 2009, 48, 5962–5965 10.1002/anie.200901892. [DOI] [PubMed] [Google Scholar]
Mathews M.; Tamaoki N. Reversibly tunable helicity induction and inversion in liquid crystal self-assembly by a planar chiroptic trigger molecule. Chem. Commun. 2009, 3609–3611 10.1039/b905305k. [DOI] [PubMed] [Google Scholar]
Akine S.; Hotate S.; Nabeshima T. A molecular leverage for helicity control and helix inversion. J. Am. Chem. Soc. 2011, 133, 13868–13871 10.1021/ja205570z. [DOI] [PubMed] [Google Scholar]
Wei K.; Ni J.; Min Y.; Chen S.; Liu Y. Unexpected helicity control and helix inversion: homochiral helical nanotubes consisting of an achiral ligand. Chem. Commun. 2013, 49, 8220–8222 10.1039/c3cc43898h. [DOI] [PubMed] [Google Scholar]
Sargsyan G.; Schatz A. A.; Kubelka J.; Balaz M. Formation and helicity control of ssDNA templated porphyrin nanoassemblies. Chem. Commun. 2013, 49, 1020–1022 10.1039/C2CC38150H. [DOI] [PubMed] [Google Scholar]
De Poli M.; Clayden J. Thionoglycine as a multifunctional spectroscopic reporter of screw-sense preference in helical foldamers. Org. Biomol. Chem. 2014, 12, 836–843 10.1039/C3OB42167H. [DOI] [PubMed] [Google Scholar]
Duan P.; Cao H.; Zhang L.; Liu M. Gelation induced supramolecular chirality: chirality transfer, amplification and application. Soft Matter 2014, 10, 5428–5448 10.1039/C4SM00507D. [DOI] [PubMed] [Google Scholar]
Nguyen B. T.; Anslyn E. V. Indicator-displacement assays. Coord. Chem. Rev. 2006, 250, 3118–3127 10.1016/j.ccr.2006.04.009. [DOI] [Google Scholar]
Gassensmith J. J.; Matthys S.; Lee J. J.; Wojcik A.; Kamat P. V.; Smith B. D. Squaraine Rotaxane as a Reversible Optical Chloride Sensor. Chem. - Eur. J. 2010, 16, 2916–2921 10.1002/chem.200902547. [DOI] [PubMed] [Google Scholar]
Langton M. J.; Beer P. D. Rotaxane and catenane host structures for sensing charged guest species. Acc. Chem. Res. 2014, 47, 1935–1949 10.1021/ar500012a. [DOI] [PubMed] [Google Scholar]
Hsueh S. Y.; Lai C. C.; Chiu S. H. Squaraine-Based [2]Rotaxanes that Function as Visibly Active Molecular Switches. Chem. - Eur. J. 2010, 16, 2997–3000 10.1002/chem.200903304. [DOI] [PubMed] [Google Scholar]
Klajn R.; Fang L.; Coskun A.; Olson M. A.; Wesson P. J.; Stoddart J. F.; Grzybowski B. A. Metal Nanoparticles Functionalized with Molecular and Supramolecular Switches. J. Am. Chem. Soc. 2009, 131, 4233–4235 10.1021/ja9001585. [DOI] [PubMed] [Google Scholar]
Cheng H. B.; Zhang H. Y.; Liu Y. Dual-Stimulus Luminescent Lanthanide Molecular Switch Based on an Unsymmetrical Diarylperfluorocyclopentene. J. Am. Chem. Soc. 2013, 135, 10190–10193 10.1021/ja4018804. [DOI] [PubMed] [Google Scholar]
Allenmark S. Induced circular dichroism by chiral molecular interaction. Chirality 2003, 15, 409–422 10.1002/chir.10220. [DOI] [PubMed] [Google Scholar]
Prins L. J.; Huskens J.; de Jong F.; Timmerman P.; Reinhoudt D. N. Complete asymmetric induction of supramolecular chirality in a hydrogen-bonded assembly. Nature 1999, 398, 498–502 10.1038/19053. [DOI] [Google Scholar]
Mineo P.; Villari V.; Scamporrino E.; Micali N. Supramolecular chirality induced by a weak thermal force. Soft Matter 2014, 10, 44–47 10.1039/C3SM52322E. [DOI] [PubMed] [Google Scholar]
Tachibana Y.; Kihara N.; Takata T. Asymmetric benzoin condensation catalyzed by chiral rotaxanes tethering a thiazolium salt moiety via the cooperation of the component: Can rotaxane be an effective reaction field?. J. Am. Chem. Soc. 2004, 126, 13560–13560 10.1021/ja0408202. [DOI] [PubMed] [Google Scholar]
Havinga E. Spontaneous Formation of Optically Active Substances. Biochim. Biophys. Acta 1954, 13, 171–174 10.1016/0006-3002(54)90300-5. [DOI] [PubMed] [Google Scholar]
Suarez M.; Branda N.; Lehn J.-M.; Decian A.; Fischer J. Supramolecular chirality: Chiral hydrogen-bonded supermolecules from achiral molecular components. Helv. Chim. Acta 1998, 81, 1–13 10.1002/hlca.19980810102. [DOI] [Google Scholar]
Evan-Salem T.; Baruch I.; Avram L.; Cohen Y.; Palmer L. C.; Rebek J. Resorcinarenes are hexameric capsules in solution. Proc. Natl. Acad. Sci. U. S. A. 2006, 103, 12296–12300 10.1073/pnas.0604757103. [DOI] [PMC free article] [PubMed] [Google Scholar]
Rivera J. M.; Martin T.; Rebek J. Chiral spaces: Dissymmetric capsules through self-assembly. Science 1998, 279, 1021–1023 10.1126/science.279.5353.1021. [DOI] [PubMed] [Google Scholar]
Woods C. R.; Benaglia M.; Cozzi F.; Siegel J. S. Enantioselective synthesis of copper(I) bipyridine based helicates by chiral templating of secondary structure: Transmission of stereochemistry on the nanometer scale. Angew. Chem., Int. Ed. Engl. 1996, 35, 1830–1833 10.1002/anie.199618301. [DOI] [Google Scholar]
Kaminker R.; de Hatten X.; Lahav M.; Lupo F.; Gulino A.; Evmenenko G.; Dutta P.; Browne C.; Nitschke J. R.; van der Boom M. E. Assembly of Surface-Confined Homochiral Helicates: Chiral Discrimination of DOPA and Unidirectional Charge Transfer. J. Am. Chem. Soc. 2013, 135, 17052–17059 10.1021/ja4077205. [DOI] [PubMed] [Google Scholar]
Miyake H.; Tsukube H. Coordination chemistry strategies for dynamic helicates: time-programmable chirality switching with labile and inert metal helicates. Chem. Soc. Rev. 2012, 41, 6977–6991 10.1039/c2cs35192g. [DOI] [PubMed] [Google Scholar]
Bottari G.; Leigh D. A.; Perez E. M. Chiroptical switching in a bistable molecular shuttle. J. Am. Chem. Soc. 2003, 125, 13360–13361 10.1021/ja036665t. [DOI] [PubMed] [Google Scholar]
Zhou W. D.; Xu J. L.; Zheng H. Y.; Yin X. D.; Zuo Z. C.; Liu H. B.; Li Y. L. Distinct Nanostructures from a Molecular Shuttle: Effects of Shuttling Movement on Nanostructural Morphologies. Adv. Funct. Mater. 2009, 19, 141–149 10.1002/adfm.200801149. [DOI] [Google Scholar]
Ji F. Y.; Zhu L. L.; Zhang D.; Chen Z. F.; Tian H. Coordination-driven self-organization of switchable [2]rotaxane. Tetrahedron 2009, 65, 9081–9085 10.1016/j.tet.2009.09.051. [DOI] [Google Scholar]
Hsueh S. Y.; Kuo C. T.; Lu T. W.; Lai C. C.; Liu Y. H.; Hsu H. F.; Peng S. M.; Chen C. H.; Chiu S. H. Acid/Base- and Anion-Controllable Organogels Formed From a Urea-Based Molecular Switch. Angew. Chem., Int. Ed. 2010, 49, 9170–9173 10.1002/anie.201004090. [DOI] [PubMed] [Google Scholar]
Gong H.-Y.; Rambo B. M.; Karnas E.; Lynch V. M.; Sessler J. L. A ‘Texas-sized’ molecular box that forms an anion-induced supramolecular necklace. Nat. Chem. 2010, 2, 406–409 10.1038/nchem.597. [DOI] [PubMed] [Google Scholar]
Fasano V.; Baroncini M.; Moffa M.; Iandolo D.; Camposeo A.; Credi A.; Pisignano D. Organic Nanofibers Embedding Stimuli-Responsive Threaded Molecular Components. J. Am. Chem. Soc. 2014, 136, 14245–14254 10.1021/ja5080322. [DOI] [PMC free article] [PubMed] [Google Scholar]
Jimenez M. C.; Dietrich-Buchecker C.; Sauvage J.-P. Towards synthetic molecular muscles: Contraction and stretching of a linear rotaxane dimer. Angew. Chem., Int. Ed. 2000, 39, 3284–3287. [DOI] [PubMed] [Google Scholar]
Gao L.; Zhang Z.; Zheng B.; Huang F. Construction of muscle-like metallo-supramolecular polymers from a pillar[5]arene-based [c2]daisy chain. Polym. Chem. 2014, 5, 5734–5739 10.1039/C4PY00733F. [DOI] [Google Scholar]
Yan X.; Zheng B.; Huang F. Integrated motion of molecular machines in supramolecular polymeric scaffolds. Polym. Chem. 2013, 4, 2395–2399 10.1039/c3py00060e. [DOI] [Google Scholar]
Bruns C. J.; Frasconi M.; Iehl J.; Hartlieb K. J.; Schneebeli S. T.; Cheng C.; Stupp S. I.; Stoddart J. F. Redox Switchable Daisy Chain Rotaxanes Driven by Radical–Radical Interactions. J. Am. Chem. Soc. 2014, 136, 4714–4723 10.1021/ja500675y. [DOI] [PubMed] [Google Scholar]
Silvi S.; Venturi M.; Credi A. Artificial molecular shuttles: from concepts to devices. J. Mater. Chem. 2009, 19, 2279–2294 10.1039/b818609j. [DOI] [Google Scholar]
Balzani V.; Credi A.; Silvi S.; Venturi M. Artificial nanomachines based on interlocked molecular species: recent advances. Chem. Soc. Rev. 2006, 35, 1135–1149 10.1039/b517102b. [DOI] [PubMed] [Google Scholar]
Romuald C.; Arda A.; Clavel C.; Jimenez-Barbero J.; Coutrot F. Tightening or loosening a pH-sensitive double-lasso molecular machine readily synthesized from an ends-activated [c2]daisy chain. Chem. Sci. 2012, 3, 1851–1857 10.1039/c2sc20072d. [DOI] [Google Scholar]
Fang L.; Hmadeh M.; Wu J.; Olson M. A.; Spruell J. M.; Trabolsi A.; Yang Y.-W.; Elhabiri M.; Albrecht-Gary A.-M.; Stoddart J. F. Acid–Base Actuation of [c2]Daisy Chains. J. Am. Chem. Soc. 2009, 131, 7126–7134 10.1021/ja900859d. [DOI] [PubMed] [Google Scholar]
Dawson R. E.; Lincoln S. F.; Easton C. J. The foundation of a light driven molecular muscle based on stilbene and alpha-cyclodextrin. Chem. Commun. 2008, 3980–3982 10.1039/b809014a. [DOI] [PubMed] [Google Scholar]
Huang T. J.; Brough B.; Ho C. M.; Liu Y.; Flood A. H.; Bonvallet P. A.; Tseng H. R.; Stoddart J. F.; Baller M.; Magonov S. A nanomechanical device based on linear molecular motors. Appl. Phys. Lett. 2004, 85, 5391–5393 10.1063/1.1826222. [DOI] [Google Scholar]
Ooya T.; Yui N. Synthesis of theophylline–polyrotaxane conjugates and their drug release via supramolecular dissociation. J. Controlled Release 1999, 58, 251–269 10.1016/S0168-3659(98)00163-1. [DOI] [PubMed] [Google Scholar]
Tooru O.; Atsushi Y.; Motoichi K.; Yuko S.; Atsushi M.; Nobuhiko Y. Effects of polyrotaxane structure on polyion complexation with DNA. Sci. Technol. Adv. Mater. 2004, 5, 363–369 10.1016/j.stam.2003.12.014. [DOI] [Google Scholar]
Ooya T.; Choi H. S.; Yamashita A.; Yui N.; Sugaya Y.; Kano A.; Maruyama A.; Akita H.; Ito R.; Kogure K.; Harashima H. Biocleavable Polyrotaxane–Plasmid DNA Polyplex for Enhanced Gene Delivery. J. Am. Chem. Soc. 2006, 128, 3852–3853 10.1021/ja055868+. [DOI] [PubMed] [Google Scholar]
Moon C.; Kwon Y. M.; Lee W. K.; Park Y. J.; Yang V. C. In vitro assessment of a novel polyrotaxane-based drug delivery system integrated with a cell-penetrating peptide. J. Controlled Release 2007, 124, 43–50 10.1016/j.jconrel.2007.08.029. [DOI] [PMC free article] [PubMed] [Google Scholar]
Zhang X.; Zhu X.; Ke F.; Ye L.; Chen E.-q.; Zhang A.-y.; Feng Z.-g. Preparation and self-assembly of amphiphilic triblock copolymers with polyrotaxane as a middle block and their application as carrier for the controlled release of Amphotericin B. Polymer 2009, 50, 4343–4351 10.1016/j.polymer.2009.07.006. [DOI] [Google Scholar]
Harada A. H. A.; Yamaguchi H.; Takashima Y. Polymeric Rotaxanes. Chem. Rev. 2009, 109, 5974–6023 10.1021/cr9000622. [DOI] [PubMed] [Google Scholar]
Li J. J.; Zhao F.; Li J. Polyrotaxanes for applications in life science and biotechnology. Appl. Microbiol. Biotechnol. 2011, 90, 427–443 10.1007/s00253-010-3037-x. [DOI] [PubMed] [Google Scholar]
Hashidzume A.; Yamaguchi H.; Harada A. Cyclodextrin-Based Molecular Machines. Topics Curr. Chem. 2014, 354, 71–110 10.1007/128_2014_547. [DOI] [PubMed] [Google Scholar]
Fernandes A.; Viterisi A.; Coutrot F.; Potok S.; Leigh D. A.; Aucagne V.; Papot S. Rotaxane-Based Propeptides: Protection and Enzymatic Release of a Bioactive Pentapeptide. Angew. Chem., Int. Ed. 2009, 48, 6443–6447 10.1002/anie.200903215. [DOI] [PubMed] [Google Scholar]
Fernandes A.; Viterisi A.; Aucagne V.; Leigh D. A.; Papot S. Second generation specific-enzyme-activated rotaxane propeptides. Chem. Commun. 2012, 48, 2083–2085 10.1039/c2cc17458h. [DOI] [PubMed] [Google Scholar]
Barat R.; Legigan T.; Tranoy-Opalinski I.; Renoux B.; Peraudeau E.; Clarhaut J.; Poinot P.; Fernandes A. E.; Aucagne V.; Leigh D. A.; Papot S. A mechanically interlocked molecular system programmed for the delivery of an anticancer drug. Chem. Sci. 2015, 6, 2608–2613 10.1039/C5SC00648A. [DOI] [PMC free article] [PubMed] [Google Scholar]
Singleton M. R.; Dillingham M. S.; Wigley D. B. Structure and mechanism of helicases and nucleic acid translocases. Annu. Rev. Biochem. 2007, 76, 23–50 10.1146/annurev.biochem.76.052305.115300. [DOI] [PubMed] [Google Scholar]
Virag L.; Szabo C. The therapeutic potential of poly(ADP-ribose) polymerase inhibitors. Pharmacol. Rev. 2002, 54, 375–429 10.1124/pr.54.3.375. [DOI] [PubMed] [Google Scholar]
Gore J.; Bryant Z.; Stone M. D.; Nollmann M. N.; Cozzarelli N. R.; Bustamante C. Mechanochemical analysis of DNA gyrase using rotor bead tracking. Nature 2006, 439, 100–104 10.1038/nature04319. [DOI] [PMC free article] [PubMed] [Google Scholar]
Reece R. J.; Maxwell A. DNA Gyrase - Structure and Function. Crit. Rev. Biochem. Mol. Biol. 1991, 26, 335–375 10.3109/10409239109114072. [DOI] [PubMed] [Google Scholar]
Chen S. H.; Chan N. L.; Hsieh T. S. New Mechanistic and Functional Insights into DNA Topoisomerases. Annu. Rev. Biochem. 2013, 82, 139–170 10.1146/annurev-biochem-061809-100002. [DOI] [PubMed] [Google Scholar]
Wang J. C. Cellular roles of DNA topoisomerases: A molecular perspective. Nat. Rev. Mol. Cell Biol. 2002, 3, 430–440 10.1038/nrm831. [DOI] [PubMed] [Google Scholar]
von Ballmoos C.; Cook G. M.; Dimroth P. Unique rotary ATP synthase and its biological diversity. Annu. Rev. Biophys. 2008, 37, 43–64 10.1146/annurev.biophys.37.032807.130018. [DOI] [PubMed] [Google Scholar]
Gadsby D. C. Ion channels versus ion pumps: the principal difference, in principle. Nat. Rev. Mol. Cell Biol. 2009, 10, 344–352 10.1038/nrm2668. [DOI] [PMC free article] [PubMed] [Google Scholar]
Yoneda Y. How proteins are transported from cytoplasm to the nucleus. J. Biochem. 1997, 121, 811–817 10.1093/oxfordjournals.jbchem.a021657. [DOI] [PubMed] [Google Scholar]
Sweeney H. L.; Houdusse A. Structural and Functional Insights into the Myosin Motor Mechanism. Annu. Rev. Biophys. 2010, 39, 539–557 10.1146/annurev.biophys.050708.133751. [DOI] [PubMed] [Google Scholar]
Koonce M. P.; Samso M. Of rings and levers: the dynein motor comes of age. Trends Cell Biol. 2004, 14, 612–619 10.1016/j.tcb.2004.09.013. [DOI] [PubMed] [Google Scholar]
Vale R. D. The molecular motor toolbox for intracellular transport. Cell 2003, 112, 467–480 10.1016/S0092-8674(03)00111-9. [DOI] [PubMed] [Google Scholar]
Schliwa M.; Woehlke G. Molecular motors. Nature 2003, 422, 759–765 10.1038/nature01601. [DOI] [PubMed] [Google Scholar]
Ptacin J. L.; Lee S. F.; Garner E. C.; Toro E.; Eckart M.; Comolli L. R.; Moerner W.; Shapiro L. A spindle-like apparatus guides bacterial chromosome segregation. Nat. Cell Biol. 2010, 12, 791–798 10.1038/ncb2083. [DOI] [PMC free article] [PubMed] [Google Scholar]
Saffarian S.; Collier I. E.; Marmer B. L.; Elson E. L.; Goldberg G. Interstitial collagenase is a Brownian ratchet driven by proteolysis of collagen. Science 2004, 306, 108–111 10.1126/science.1099179. [DOI] [PubMed] [Google Scholar]
Xie P. Molecular motors that digest their track to rectify Brownian motion: processive movement of exonuclease enzymes. J. Phys.: Condens. Matter 2009, 21, 375108. 10.1088/0953-8984/21/37/375108. [DOI] [PubMed] [Google Scholar]
von Delius M.; Leigh D. A. Walking molecules. Chem. Soc. Rev. 2011, 40, 3656–3676 10.1039/c1cs15005g. [DOI] [PubMed] [Google Scholar]
Vale R. D.; Reese T. S.; Sheetz M. P. Identification of a Novel Force-Generating Protein, Kinesin, Involved in Microtubule-Based Motility. Cell 1985, 42, 39–50 10.1016/S0092-8674(85)80099-4. [DOI] [PMC free article] [PubMed] [Google Scholar]
Block S. M. Kinesin motor mechanics: Binding, stepping, tracking, gating, and limping. Biophys. J. 2007, 92, 2986–2995 10.1529/biophysj.106.100677. [DOI] [PMC free article] [PubMed] [Google Scholar]
Asbury C. L.; Fehr A. N.; Block S. M. Kinesin moves by an asymmetric hand-over-hand mechanism. Science 2003, 302, 2130–2134 10.1126/science.1092985. [DOI] [PMC free article] [PubMed] [Google Scholar]
Yildiz A.; Tomishige M.; Vale R. D.; Selvin P. R. Kinesin walks hand-over-hand. Science 2004, 303, 676–678 10.1126/science.1093753. [DOI] [PubMed] [Google Scholar]
Howard J.; Hudspeth A. J.; Vale R. D. Movement of Microtubules by Single Kinesin Molecules. Nature 1989, 342, 154–158 10.1038/342154a0. [DOI] [PubMed] [Google Scholar]
Block S. M.; Goldstein L. S. B.; Schnapp B. J. Bead Movement by Single Kinesin Molecules Studied with Optical Tweezers. Nature 1990, 348, 348–352 10.1038/348348a0. [DOI] [PubMed] [Google Scholar]
Hackney D. D. Highly Processive Microtubule-Stimulated ATP Hydrolysis by Dimeric Kinesin Head Domains. Nature 1995, 377, 448–450 10.1038/377448a0. [DOI] [PubMed] [Google Scholar]
Vale R. D.; Funatsu T.; Pierce D. W.; Romberg L.; Harada Y.; Yanagida T. Direct observation of single kinesin molecules moving along microtubules. Nature 1996, 380, 451–453 10.1038/380451a0. [DOI] [PMC free article] [PubMed] [Google Scholar]
Hirokawa N.; Nitta R.; Okada Y. The mechanisms of kinesin motor motility: lessons from the monomeric motor KIF1A. Nat. Rev. Mol. Cell Biol. 2009, 10, 877–884 10.1038/nrm2807. [DOI] [PubMed] [Google Scholar]
Yin P.; Yan H.; Daniell X. G.; Turberfield A. J.; Reif J. H. A unidirectional DNA walker that moves autonomously along a track. Angew. Chem., Int. Ed. 2004, 43, 4906–4911 10.1002/anie.200460522. [DOI] [PubMed] [Google Scholar]
Tian Y.; He Y.; Chen Y.; Yin P.; Mao C. D. Molecular devices - A DNAzyme that walks processively and autonomously along a one-dimensional track. Angew. Chem., Int. Ed. 2005, 44, 4355–4358 10.1002/anie.200500703. [DOI] [PubMed] [Google Scholar]
Muscat R. A.; Bath J.; Turberfield A. J. Small Molecule Signals that Direct the Route of a Molecular Cargo. Small 2012, 8, 3593–3597 10.1002/smll.201201055. [DOI] [PubMed] [Google Scholar]
You M. X.; Chen Y.; Zhang X. B.; Liu H. P.; Wang R. W.; Wang K. L.; Williams K. R.; Tan W. H. An Autonomous and Controllable Light-Driven DNA Walking Device. Angew. Chem., Int. Ed. 2012, 51, 2457–2460 10.1002/anie.201107733. [DOI] [PMC free article] [PubMed] [Google Scholar]
You M. X.; Huang F. J.; Chen Z.; Wang R. W.; Tan W. H. Building a Nanostructure with Reversible Motions Using Photonic Energy. ACS Nano 2012, 6, 7935–7941 10.1021/nn302388e. [DOI] [PMC free article] [PubMed] [Google Scholar]
Perl A.; Gomez-Casado A.; Thompson D.; Dam H. H.; Jonkheijm P.; Reinhoudt D. N.; Huskens J. Gradient-driven motion of multivalent ligand molecules along a surface functionalized with multiple receptors. Nat. Chem. 2011, 3, 317–322 10.1038/nchem.1005. [DOI] [PubMed] [Google Scholar]
Weimann D. P.; Winkler H. D. F.; Falenski J. A.; Koksch B.; Schalley C. A. Highly dynamic motion of crown ethers along oligolysine peptide chains. Nat. Chem. 2009, 1, 668–668 10.1038/nchem.431. [DOI] [PubMed] [Google Scholar]
Strawser D.; Karton A.; Zenkina E. V.; Iron M. A.; Shimon L. J. W.; Martin J. M. L.; van der Boom M. E. Platinum stilbazoles: Ring-walking coupled with aryl-halide bond activation. J. Am. Chem. Soc. 2005, 127, 9322–9323 10.1021/ja050613h. [DOI] [PubMed] [Google Scholar]
Tkachov R.; Senkovskyy V.; Komber H.; Sommer J. U.; Kiriy A. Random Catalyst Walking along Polymerized Poly(3-hexylthlophene) Chains in Kumada Catalyst-Transfer Polycondensation. J. Am. Chem. Soc. 2010, 132, 7803–7810 10.1021/ja102210r. [DOI] [PubMed] [Google Scholar]
Claisen L.; Tietze E.; Über den Mechanismus der Umlagerung der Phenol-allyläther. Ber. Dtsch. Chem. Ges. B 1925, 58, 275–281 10.1002/cber.19250580207. [DOI] [Google Scholar]
Claisen L. The rearrangement of phenol-allyl-ather in C-allyl-phenole. Ber. Dtsch. Chem. Ges. 1912, 45, 3157–3166 10.1002/cber.19120450348. [DOI] [Google Scholar]
Cope A. C.; Hardy E. M. The introduction of substituted vinyl groups. VI. The regeneration of substituted vinyl malonic esters from their sodium enolates. J. Am. Chem. Soc. 1940, 62, 3319–3323 10.1021/ja01869a013. [DOI] [Google Scholar]
Cope A. C.; Hardy E. M. The introduction of substituted vinyl groups V A rearrangement involving the migration of an allyl group in a three-carbon system. J. Am. Chem. Soc. 1940, 62, 441–444 10.1021/ja01859a055. [DOI] [Google Scholar]
Cope A. C.; Hartung W. H.; Hancock E. M.; Crossley F. S. Substituted vinyl barbituric acids IV Derivatives containing a primary 1-alkenyl group. J. Am. Chem. Soc. 1940, 62, 1199–1201 10.1021/ja01862a060. [DOI] [Google Scholar]
Cope A. C.; Hartung W. H.; Hancock E. M.; Crossley F. S. The introduction of substituted vinyl groups IV (Primary 1-alkenyl) alkyl malonic esters. J. Am. Chem. Soc. 1940, 62, 314–316 10.1021/ja01859a020. [DOI] [Google Scholar]
Mitra S.; Lawton R. G. Reagents for the Cross-Linking of Proteins by Equilibrium Transfer Alkylation. J. Am. Chem. Soc. 1979, 101, 3097–3110 10.1021/ja00505a043. [DOI] [Google Scholar]
Kovaricek P.; Lehn J.-M. Merging Constitutional and Motional Covalent Dynamics in Reversible Imine Formation and Exchange Processes. J. Am. Chem. Soc. 2012, 134, 9446–9455 10.1021/ja302793c. [DOI] [PubMed] [Google Scholar]
Kovaricek P.; Lehn J.-M. Directional Dynamic Covalent Motion of a Carbonyl Walker on a Polyamine Track. Chem. - Eur. J. 2015, 21, 9380–9384 10.1002/chem.201500987. [DOI] [PubMed] [Google Scholar]
Campana A. G.; Carlone A.; Chen K.; Dryden D. T. F.; Leigh D. A.; Lewandowska U.; Mullen K. M. A Small Molecule that Walks Non-Directionally Along a Track Without External Intervention. Angew. Chem., Int. Ed. 2012, 51, 5480–5483 10.1002/anie.201200822. [DOI] [PubMed] [Google Scholar]
Campana A. G.; Leigh D. A.; Lewandowska U. One-Dimensional Random Walk of a Synthetic Small Molecule Toward a Thermodynamic Sink. J. Am. Chem. Soc. 2013, 135, 8639–8645 10.1021/ja402382n. [DOI] [PubMed] [Google Scholar]
von Delius M.; Geertsema E. M.; Leigh D. A. A synthetic small molecule that can walk down a track. Nat. Chem. 2010, 2, 96–101 10.1038/nchem.481. [DOI] [PubMed] [Google Scholar]
von Delius M.; Geertsema E. M.; Leigh D. A.; Tang D. T. D. Design, Synthesis, and Operation of Small Molecules That Walk along Tracks. J. Am. Chem. Soc. 2010, 132, 16134–16145 10.1021/ja106486b. [DOI] [PubMed] [Google Scholar]
Pulcu G. S.; Mikhailova E.; Choi L. S.; Bayley H. Continuous observation of the stochastic motion of an individual small-molecule walker. Nat. Nanotechnol. 2014, 10, 76–83 10.1038/nnano.2014.264. [DOI] [PMC free article] [PubMed] [Google Scholar]
Haq S.; Wit B.; Sang H.; Floris A.; Wang Y.; Wang J.; Pérez-García L.; Kantorovitch L.; Amabilino D. B.; Raval R. A Small Molecule Walks Along a Surface Between Porphyrin Fences That Are Assembled In Situ. Angew. Chem., Int. Ed. 2015, 54, 7101–7105 10.1002/anie.201502153. [DOI] [PubMed] [Google Scholar]
Beves J. E.; Blanco V.; Blight B. A.; Carrillo R.; D’Souza D. M.; Howgego D.; Leigh D. A.; Slawin A. M. Z.; Symes M. D. Toward Metal Complexes That Can Directionally Walk Along Tracks: Controlled Stepping of a Molecular Biped with a Palladium(II) Foot. J. Am. Chem. Soc. 2014, 136, 2094–2100 10.1021/ja4123973. [DOI] [PubMed] [Google Scholar]
Barrell M. J.; Campana A. G.; von Delius M.; Geertsema E. M.; Leigh D. A. Light-Driven Transport of a Molecular Walker in Either Direction along a Molecular Track. Angew. Chem., Int. Ed. 2011, 50, 285–290 10.1002/anie.201004779. [DOI] [PubMed] [Google Scholar]
Luning U. Switchable catalysis. Angew. Chem., Int. Ed. 2012, 51, 8163–8165 10.1002/anie.201204567. [DOI] [PubMed] [Google Scholar]
Kumagai N.; Shibasaki M. Catalytic chemical transformations with conformationally dynamic catalytic systems. Catal. Sci. Technol. 2013, 3, 41–57 10.1039/C2CY20257C. [DOI] [Google Scholar]
Neilson B. M.; Bielawski C. W. Illuminating Photoswitchable Catalysis. ACS Catal. 2013, 3, 1874–1885 10.1021/cs4003673. [DOI] [Google Scholar]
Leigh D. A.; Marcos V.; Wilson M. R. Rotaxane Catalysts. ACS Catal. 2014, 4, 4490–4497 10.1021/cs5013415. [DOI] [Google Scholar]
Blanco V.; Leigh D. A.; Marcos V. Artificial switchable catalysts. Chem. Soc. Rev. 2015, 44, 5341–5370 10.1039/C5CS00096C. [DOI] [PubMed] [Google Scholar]
Wiester M. J.; Ulmann P. A.; Mirkin C. A. Enzyme Mimics Based Upon Supramolecular Coordination Chemistry. Angew. Chem., Int. Ed. 2011, 50, 114–137 10.1002/anie.201000380. [DOI] [PubMed] [Google Scholar]
Yoon H. J.; Mirkin C. A. PCR-like cascade reactions in the context of an allosteric enzyme mimic. J. Am. Chem. Soc. 2008, 130, 11590–11591 10.1021/ja804076q. [DOI] [PMC free article] [PubMed] [Google Scholar]
Yoon H. J.; Heo J.; Mirkin C. A. Allosteric regulation of phosphate diester transesterification based upon a dinuclear zinc catalyst assembled via the weak-link approach. J. Am. Chem. Soc. 2007, 129, 14182–14183 10.1021/ja077467v. [DOI] [PubMed] [Google Scholar]
Vlatkovic M.; Bernardi L.; Otten E.; Feringa B. L. Dual stereocontrol over the Henry reaction using a light- and heat-triggered organocatalyst. Chem. Commun. 2014, 50, 7773–7775 10.1039/c4cc00794h. [DOI] [PubMed] [Google Scholar]
Stoll R. S.; Hecht S. Artificial Light-Gated Catalyst Systems. Angew. Chem., Int. Ed. 2010, 49, 5054–5075 10.1002/anie.201000146. [DOI] [PubMed] [Google Scholar]
Imahori T.; Kurihara S. Stimuli-responsive Cooperative Catalysts Based on Dynamic Conformational Changes toward Spatiotemporal Control of Chemical Reactions. Chem. Lett. 2014, 43, 1524–1531 10.1246/cl.140680. [DOI] [Google Scholar]
Frank Wuerthner; Julius Rebek J. Light-Switchable Catalysis in Synthetic Receptors. Angew. Chem., Int. Ed. Engl. 1995, 34, 446–448 10.1002/anie.199504461. [DOI] [Google Scholar]
Berryman O. B.; Sather A. C.; Lledo A.; Rebek J. Jr. Switchable catalysis with a light-responsive cavitand. Angew. Chem., Int. Ed. 2011, 50, 9400–9403 10.1002/anie.201105374. [DOI] [PMC free article] [PubMed] [Google Scholar]
Peters M. V.; Stoll R. S.; Kuhn A.; Hecht S. Photoswitching of basicity. Angew. Chem., Int. Ed. 2008, 47, 5968–5972 10.1002/anie.200802050. [DOI] [PubMed] [Google Scholar]
Osorio-Planes L.; Rodriguez-Escrich C.; Pericas M. A. Photoswitchable thioureas for the external manipulation of catalytic activity. Org. Lett. 2014, 16, 1704–1707 10.1021/ol500381c. [DOI] [PubMed] [Google Scholar]
Viehmann P.; Hecht S. Design and synthesis of a photoswitchable guanidine catalyst. Beilstein J. Org. Chem. 2012, 8, 1825–1830 10.3762/bjoc.8.209. [DOI] [PMC free article] [PubMed] [Google Scholar]
Neilson B. M.; Bielawski C. W. Photoswitchable Organocatalysis: Using Light To Modulate the Catalytic Activities of N-Heterocyclic Carbenes. J. Am. Chem. Soc. 2012, 134, 12693–12699 10.1021/ja304067k. [DOI] [PubMed] [Google Scholar]
Neilson B. M.; Bielawski C. W. Photoswitchable Metal-Mediated Catalysis: Remotely Tuned Alkene and Alkyne Hydroborations. Organometallics 2013, 32, 3121–3128 10.1021/om400348h. [DOI] [Google Scholar]
Wilson D.; Branda N. R. Turning ″on″ and ″off″ a pyridoxal 5′-phosphate mimic using light. Angew. Chem., Int. Ed. 2012, 51, 5431–5434 10.1002/anie.201201447. [DOI] [PubMed] [Google Scholar]
Wang J.; Feringa B. L. Dynamic control of chiral space in a catalytic asymmetric reaction using a molecular motor. Science 2011, 331, 1429–1432 10.1126/science.1199844. [DOI] [PubMed] [Google Scholar]
Zhao D.; Neubauer T. M.; Feringa B. L. Dynamic control of chirality in phosphine ligands for enantioselective catalysis. Nat. Commun. 2015, 6, 6652. 10.1038/ncomms7652. [DOI] [PMC free article] [PubMed] [Google Scholar]
Li Y.; Feng Y.; He Y. M.; Chen F.; Pan J.; Fan Q. H. Supramolecular chiral phosphorous ligands based on a [2]pseudorotaxane complex for asymmetric hydrogenation. Tetrahedron Lett. 2008, 49, 2878–2881 10.1016/j.tetlet.2008.03.039. [DOI] [Google Scholar]
Tachibana Y.; Kihara N.; Nakazono K.; Takata T. Thiazolium-Tethering Rotaxane-Catalyzed Asymmetric Benzoin Condensation: Unique Asymmetric Field Constructed by the Cooperation of Rotaxane Components. Phosphorus, Sulfur Silicon Relat. Elem. 2010, 185, 1182–1205 10.1080/10426501003773589. [DOI] [Google Scholar]
Suzaki Y.; Shimada K.; Chihara E.; Saito T.; Tsuchido Y.; Osakada K. [3]Rotaxane-Based Dinuclear Palladium Catalysts for Ring-closure Mizoroki-Heck Reaction. Org. Lett. 2011, 13, 3774–3777 10.1021/ol201357b. [DOI] [PubMed] [Google Scholar]
Caputo C. B.; Zhu K. L.; Vukotic V. N.; Loeb S. J.; Stephan D. W. Heterolytic Activation of H2 Using a Mechanically Interlocked Molecule as a Frustrated Lewis Base. Angew. Chem., Int. Ed. 2013, 52, 960–963 10.1002/anie.201207783. [DOI] [PubMed] [Google Scholar]
Miyagawa N.; Watanabe M.; Matsuyama T.; Koyama Y.; Moriuchi T.; Hirao T.; Furusho Y.; Takata T. Successive catalytic reactions specific to Pd-based rotaxane complexes as a result of wheel translation along the axle. Chem. Commun. 2010, 46, 1920–1922 10.1039/b917053g. [DOI] [PubMed] [Google Scholar]
Blanco V.; Carlone A.; Hanni K. D.; Leigh D. A.; Lewandowski B. A rotaxane-based switchable organocatalyst. Angew. Chem., Int. Ed. 2012, 51, 5166–5169 10.1002/anie.201201364. [DOI] [PubMed] [Google Scholar]
Blanco V.; Leigh D. A.; Lewandowska U.; Lewandowsld B.; Marcos V. Exploring the Activation Modes of a Rotaxane-Based Switchable Organocatalyst. J. Am. Chem. Soc. 2014, 136, 15775–15780 10.1021/ja509236u. [DOI] [PubMed] [Google Scholar]
Blanco V.; Leigh D. A.; Marcos V.; Morales-Serna J. A.; Nussbaumer A. L. A Switchable [2]Rotaxane Asymmetric Organocatalyst That Utilizes an Acyclic Chiral Secondary Amine. J. Am. Chem. Soc. 2014, 136, 4905–4908 10.1021/ja501561c. [DOI] [PubMed] [Google Scholar]
Beswick J.; Blanco V.; De Bo G.; Leigh D. A.; Lewandowska U.; Lewandowski B.; Mishiro K. Selecting reactions and reactants using a switchable rotaxane organocatalyst with two different active sites. Chem. Sci. 2015, 6, 140–143 10.1039/C4SC03279A. [DOI] [PMC free article] [PubMed] [Google Scholar]
Yoon H. J.; Kuwabara J.; Kim J. H.; Mirkin C. A. Allosteric supramolecular triple-layer catalysts. Science 2010, 330, 66–69 10.1126/science.1193928. [DOI] [PubMed] [Google Scholar]
Wiester M. J.; Braunschweig A. B.; Yoo H.; Mirkin C. A. Solvent and Temperature Induced Switching Between Structural Isomers of Rh-I Phosphinoalkyl Thioether (PS) Complexes. Inorg. Chem. 2010, 49, 7188–7196 10.1021/ic101021t. [DOI] [PMC free article] [PubMed] [Google Scholar]
McGuirk C. M.; Mendez-Arroyo J.; Lifschitz A. M.; Mirkin C. A. Allosteric Regulation of Supramolecular Oligomerization and Catalytic Activity via Coordination-Based Control of Competitive Hydrogen-Bonding Events. J. Am. Chem. Soc. 2014, 136, 16594–16601 10.1021/ja508804n. [DOI] [PubMed] [Google Scholar]
Lifschitz A. M.; Young R. M.; Mendez-Arroyo J.; Stern C. L.; McGuirk C. M.; Wasielewski M. R.; Mirkin C. A. An allosteric photoredox catalyst inspired by photosynthetic machinery. Nat. Commun. 2015, 6, 6541. 10.1038/ncomms7541. [DOI] [PMC free article] [PubMed] [Google Scholar]
Schmittel M.; De S.; Pramanik S. Reversible ON/OFF nanoswitch for organocatalysis: mimicking the locking and unlocking operation of CaMKII. Angew. Chem., Int. Ed. 2012, 51, 3832–3836 10.1002/anie.201108089. [DOI] [PubMed] [Google Scholar]
Schmittel M.; Pramanik S.; De S. A reversible nanoswitch as an ON-OFF photocatalyst. Chem. Commun. 2012, 48, 11730–11732 10.1039/c2cc36408e. [DOI] [PubMed] [Google Scholar]
Samanta S. K.; Schmittel M. Four-component supramolecular nanorotors. J. Am. Chem. Soc. 2013, 135, 18794–18797 10.1021/ja411011a. [DOI] [PubMed] [Google Scholar]
Zahn S. Electron-Induced Inversion of Helical Chirality in Copper Complexes of N,N-Dialkylmethionines. Science 2000, 288, 1404–1407 10.1126/science.288.5470.1404. [DOI] [PubMed] [Google Scholar]
Canary J. W.; Mortezaei S.; Liang J. Redox-reconfigurable tripodal coordination complexes: stereodynamic molecular switches. Chem. Commun. 2010, 46, 5850–5860 10.1039/c0cc00469c. [DOI] [PubMed] [Google Scholar]
Berova N.; Nakanishi K. o.; Woody R.. Circular Dichroism: Principles and Applications, 2nd ed.; Wiley-VCH: New York, 2000. [Google Scholar]
Mortezaei S.; Catarineu N. R.; Canary J. W. A redox-reconfigurable, ambidextrous asymmetric catalyst. J. Am. Chem. Soc. 2012, 134, 8054–8057 10.1021/ja302283s. [DOI] [PubMed] [Google Scholar]
Gartner Z. J.; Kanan M. W.; Liu D. R. Multistep Small-Molecule Synthesis Programmed by DNA Templates. J. Am. Chem. Soc. 2002, 124, 10304–10306 10.1021/ja027307d. [DOI] [PubMed] [Google Scholar]
He Y.; Liu D. R. Autonomous multistep organic synthesis in a single isothermal solution mediated by a DNA walker. Nat. Nanotechnol. 2010, 5, 778–782 10.1038/nnano.2010.190. [DOI] [PMC free article] [PubMed] [Google Scholar]
He Y.; Liu D. R. A Sequential Strand-Displacement Strategy Enables Efficient Six-Step DNA-Templated Synthesis. J. Am. Chem. Soc. 2011, 133, 9972–9975 10.1021/ja201361t. [DOI] [PMC free article] [PubMed] [Google Scholar]
McKee M. L.; Milnes P. J.; Bath J.; Stulz E.; O’Reilly R. K.; Turberfield A. J. Programmable One-Pot Multistep Organic Synthesis Using DNA Junctions. J. Am. Chem. Soc. 2012, 134, 1446–1449 10.1021/ja2101196. [DOI] [PubMed] [Google Scholar]
McKee M. L.; Milnes P. J.; Bath J.; Stulz E.; Turberfield A. J.; O’Reilly R. K. Multistep DNA-Templated Reactions for the Synthesis of Functional Sequence Controlled Oligomers. Angew. Chem., Int. Ed. 2010, 49, 7948–7951 10.1002/anie.201002721. [DOI] [PubMed] [Google Scholar]
Gartner Z. J.; Kanan M. W.; Liu D. R. Expanding the Reaction Scope of DNA-Templated Synthesis. Angew. Chem., Int. Ed. 2002, 41, 1796–1800. [DOI] [PubMed] [Google Scholar]
Gartner Z. J.; Liu D. R. The Generality of DNA-Templated Synthesis as a Basis for Evolving Non-Natural Small Molecules. J. Am. Chem. Soc. 2001, 123, 6961–6963 10.1021/ja015873n. [DOI] [PMC free article] [PubMed] [Google Scholar]
Li X.; Gartner Z. J.; Tse B. N.; Liu D. R. Translation of DNA into Synthetic N-Acyloxazolidines. J. Am. Chem. Soc. 2004, 126, 5090–5092 10.1021/ja049666+. [DOI] [PubMed] [Google Scholar]
Gartner Z. J.; Grubina R.; Calderone C. T.; Liu D. R. Two Enabling Architectures for DNA-Templated Organic Synthesis. Angew. Chem., Int. Ed. 2003, 42, 1370–1375 10.1002/anie.200390351. [DOI] [PubMed] [Google Scholar]
Gu H.; Chao J.; Xiao S. J.; Seeman N. C. A proximity-based programmable DNA nanoscale assembly line. Nature 2010, 465, 202–205 10.1038/nature09026. [DOI] [PMC free article] [PubMed] [Google Scholar]
Thordarson P.; Bijsterveld E. J. A.; Rowan A. E.; Nolte R. J. M. Epoxidation of polybutadiene by a topologically linked catalyst. Nature 2003, 424, 915–918 10.1038/nature01925. [DOI] [PubMed] [Google Scholar]
Elemans J. A. A. W.; Bijsterveld E. J. A.; Rowan A. E.; Nolte R. J. M. A host-guest epoxidation catalyst with enhanced activity and stability. Chem. Commun. 2000, 2443–2444 10.1039/b008567g. [DOI] [Google Scholar]
Monnereau C.; Ramos P. H.; Deutman A. B. C.; Elemans J. A. A. W.; Nolte R. J. M.; Rowan A. E. Porphyrin Macrocyclic Catalysts for the Processive Oxidation of Polymer Substrates. J. Am. Chem. Soc. 2010, 132, 1529–1531 10.1021/ja908524x. [DOI] [PubMed] [Google Scholar]
Deutman A. B. C.; Monnereau C.; Elemans J. A. A. W.; Ercolani G.; Nolte R. J. M.; Rowan A. E. Mechanism of Threading a Polymer Through a Macrocyclic Ring. Science 2008, 322, 1668–1671 10.1126/science.1164647. [DOI] [PubMed] [Google Scholar]
Takashima Y.; Osaki M.; Ishimaru Y.; Yamaguchi H.; Harada A. Artificial Molecular Clamp: A Novel Device for Synthetic Polymerases. Angew. Chem., Int. Ed. 2011, 50, 7524–7528 10.1002/anie.201102834. [DOI] [PubMed] [Google Scholar]
Dawson P.; Muir T.; Clark-Lewis I.; Kent S. Synthesis of proteins by native chemical ligation. Science 1994, 266, 776–779 10.1126/science.7973629. [DOI] [PubMed] [Google Scholar]
Hughs M.; Jimenez M.; Khan S.; Garcia-Garibay M. A. Synthesis, rotational dynamics, and photophysical characterization of a crystalline linearly conjugated phenyleneethynylene molecular dirotor. J. Org. Chem. 2013, 78, 5293–5302 10.1021/jo4004053. [DOI] [PubMed] [Google Scholar]
Garcia-Garibay M. A. Crystalline molecular machines: encoding supramolecular dynamics into molecular structure. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 10771–10776 10.1073/pnas.0502816102. [DOI] [PMC free article] [PubMed] [Google Scholar]
Rodriguez-Molina B.; Pozos A.; Cruz R.; Romero M.; Flores B.; Farfan N.; Santillan R.; Garcia-Garibay M. A. Synthesis and solid state characterization of molecular rotors with steroidal stators: ethisterone and norethisterone. Org. Biomol. Chem. 2010, 8, 2993–3000 10.1039/c003778h. [DOI] [PubMed] [Google Scholar]
Vogelsberg C. S.; Garcia-Garibay M. A. Crystalline molecular machines: function, phase order, dimensionality, and composition. Chem. Soc. Rev. 2012, 41, 1892–1910 10.1039/C1CS15197E. [DOI] [PubMed] [Google Scholar]
Rodriguez-Molina B.; Perez-Estrada S.; Garcia-Garibay M. A. Amphidynamic crystals of a steroidal bicyclo[2.2.2]octane rotor: a high symmetry group that rotates faster than smaller methyl and methoxy groups. J. Am. Chem. Soc. 2013, 135, 10388–10395 10.1021/ja4024463. [DOI] [PMC free article] [PubMed] [Google Scholar]
Staehle I. O.; Rodríguez-Molina B.; Khan S. I.; Garcia-Garibay M. A. Engineered Photochromism in Crystalline Salicylidene Anilines by Facilitating Rotation to Reach the Colored trans-Keto Form. Cryst. Growth Des. 2014, 14, 3667–3673 10.1021/cg500762a. [DOI] [Google Scholar]
Jiang X.; Rodriguez-Molina B.; Nazarian N.; Garcia-Garibay M. A. Rotation of a bulky triptycene in the solid state: toward engineered nanoscale artificial molecular machines. J. Am. Chem. Soc. 2014, 136, 8871–8874 10.1021/ja503467e. [DOI] [PubMed] [Google Scholar]
Commins P.; Garcia-Garibay M. A. Photochromic molecular gyroscope with solid state rotational states determined by an azobenzene bridge. J. Org. Chem. 2014, 79, 1611–1619 10.1021/jo402516n. [DOI] [PubMed] [Google Scholar]
Karlen S. D.; Ortiz R.; Chapman O. L.; Garcia-Garibay M. A. Effects of Rotational Symmetry Order on the Solid State Dynamics Phenylene and Diamantane Rotators. J. Am. Chem. Soc. 2005, 127, 6554–6555 10.1021/ja042512+. [DOI] [PubMed] [Google Scholar]
Comotti A.; Bracco S.; Valsesia P.; Beretta M.; Sozzani P. Fast molecular rotor dynamics modulated by guest inclusion in a highly organized nanoporous organosilica. Angew. Chem., Int. Ed. 2010, 49, 1760–1764 10.1002/anie.200906255. [DOI] [PubMed] [Google Scholar]
Vogelsberg C. S.; Bracco S.; Beretta M.; Comotti A.; Sozzani P.; Garcia-Garibay M. A. Dynamics of molecular rotors confined in two dimensions: transition from a 2D rotational glass to a 2D rotational fluid in a periodic mesoporous organosilica. J. Phys. Chem. B 2012, 116, 1623–1632 10.1021/jp2119263. [DOI] [PubMed] [Google Scholar]
Comotti A.; Bracco S.; Yamamoto A.; Beretta M.; Hirukawa T.; Tohnai N.; Miyata M.; Sozzani P. Engineering switchable rotors in molecular crystals with open porosity. J. Am. Chem. Soc. 2014, 136, 618–621 10.1021/ja411233p. [DOI] [PubMed] [Google Scholar]
Comotti A.; Bracco S.; Ben T.; Qiu S.; Sozzani P. Molecular rotors in porous organic frameworks. Angew. Chem., Int. Ed. 2014, 53, 1043–1047 10.1002/anie.201309362. [DOI] [PubMed] [Google Scholar]
Vukotic V. N.; Kelong Zhu K. J. H.; Schurko R. W.; Loeb S. J. Metal–organic frameworks with dynamic interlocked components. Nat. Chem. 2012, 4, 456–460 10.1038/nchem.1354. [DOI] [PubMed] [Google Scholar]
Zhu K.; O’Keefe C. A.; Vukotic V. N.; Schurko R. W.; Loeb S. J. A molecular shuttle that operates inside a metal-organic framework. Nat. Chem. 2015, 7, 514–519 10.1038/nchem.2258. [DOI] [PubMed] [Google Scholar]
Ahuja R. C.; Caruso P. L.; Mobius D.; Wildburg G.; Ringsdorf H.; Philp D.; Preece J. A.; Stoddart J. F. Molecular-Organization Via Ionic Interactions at Interfaces 0.1. Monolayers and Lb Films of Cyclic Bisbipyridinium Tetracations and Dimyristoylphosphatidic Acid. Langmuir 1993, 9, 1534–1544 10.1021/la00030a019. [DOI] [Google Scholar]
Collier C. P.; Mattersteig G.; Wong E. W.; Luo Y.; Beverly K.; Sampaio J.; Raymo F. M.; Stoddart J. F.; Heath J. R. A [2]catenane-based solid state electronically reconfigurable switch. Science 2000, 289, 1172–1175 10.1126/science.289.5482.1172. [DOI] [PubMed] [Google Scholar]
Pease A. R.; Jeppesen J. O.; Stoddart J. F.; Luo Y.; Collier C. P.; Heath J. R. Switching devices based on interlocked molecules. Acc. Chem. Res. 2001, 34, 433–444 10.1021/ar000178q. [DOI] [PubMed] [Google Scholar]
Heath J. R.; Ratner M. A. Molecular electronics. Phys. Today 2003, 56, 43–49 10.1063/1.1583533. [DOI] [Google Scholar]
Heath J. R.; Stoddart J. F.; Williams R. S. More on molecular electronics. Science 2004, 303, 1136–1137 10.1126/science.303.5661.1136c. [DOI] [PubMed] [Google Scholar]
Flood A. H.; Ramirez R.; Deng W.; Muller R.; Goddard W. A. III; Stoddart J. F. Meccano on the nanoscale - A blueprint for making some of the world’s tiniest machines. Aust. J. Chem. 2004, 57, 301–322 10.1071/CH03307. [DOI] [Google Scholar]
Mendes P.; Flood A. H.; Stoddart J. F. Nanoelectronic devices from self-organized molecular switches. Appl. Phys. A: Mater. Sci. Process. 2005, 80, 1197–1209 10.1007/s00339-004-3172-2. [DOI] [Google Scholar]
Beckman R.; Beverly K.; Boukai A.; Bunimovich Y.; Choi J. W.; DeIonno E.; Green J.; Johnston-Halperin E.; Luo Y.; Sheriff B.; Stoddart J. F.; Heath J. R. Spiers Memorial Lecture Molecular mechanics and molecular electronics. Faraday Discuss. 2006, 131, 9–22 10.1039/B513148K. [DOI] [PubMed] [Google Scholar]
Coskun A.; Spruell J. M.; Barin G.; Dichtel W. R.; Flood A. H.; Botros Y. Y.; Stoddart J. F. High hopes: can molecular electronics realise its potential?. Chem. Soc. Rev. 2012, 41, 4827–4859 10.1039/c2cs35053j. [DOI] [PubMed] [Google Scholar]
Steuerman D. W.; Tseng H. R.; Peters A. J.; Flood A. H.; Jeppesen J. O.; Nielsen K. A.; Stoddart J. F.; Heath J. R. Molecular-mechanical switch-based solid-state electrochromic devices. Angew. Chem., Int. Ed. 2004, 43, 6486–6491 10.1002/anie.200461723. [DOI] [PubMed] [Google Scholar]
Deng W. Q.; Muller R. P.; Goddard W. A. III Mechanism of the Stoddart-Heath bistable rotaxane molecular switch. J. Am. Chem. Soc. 2004, 126, 13562–13563 10.1021/ja036498x. [DOI] [PubMed] [Google Scholar]
Norgaard K.; Laursen B.; Nygaard S.; Kjaer K.; Tseng H.; Flood A. H.; Stoddart J. F.; Bjornholm T. Structural evidence of mechanical shuttling in condensed monolayers of bistable rotaxane molecules. Angew. Chem., Int. Ed. 2005, 44, 7035–7039 10.1002/anie.200501538. [DOI] [PubMed] [Google Scholar]
Dichtel W.; Heath J. R.; Stoddart J. F. Designing bistable [2] rotaxanes for molecular electronic devices. Philos. Trans. R. Soc., A 2007, 365, 1607–1625 10.1098/rsta.2007.2034. [DOI] [PubMed] [Google Scholar]
Nygaard S.; Leung K. C. F.; Aprahamian I.; Ikeda T.; Saha S.; Laursen B. W.; Kim S. Y.; Hansen S. W.; Stein P. C.; Flood A. H.; Stoddart J. F.; Jeppesen J. O. Functionally rigid bistable [2]rotaxanes. J. Am. Chem. Soc. 2007, 129, 960–970 10.1021/ja0663529. [DOI] [PubMed] [Google Scholar]
Coskun A.; Saha S.; Aprahamian I.; Stoddart J. F. A reverse donor-acceptor bistable [2]Catenane. Org. Lett. 2008, 10, 3187–3190 10.1021/ol800931z. [DOI] [PubMed] [Google Scholar]
Dey S. K.; Coskun A.; Fahrenbach A. C.; Barin G.; Basuray A. N.; Trabolsi A.; Botros Y. Y.; Stoddart J. F. A redox-active reverse donor-acceptor bistable [2]rotaxane. Chem. Sci. 2011, 2, 1046–1053 10.1039/C0SC00586J. [DOI] [Google Scholar]
Wang C.; Cao D.; Fahrenbach A. C.; Grunder S.; Dey S. K.; Sarjeant A. A.; Stoddart J. F. The effects of conformation on the noncovalent bonding interactions in a bistable donor-acceptor [3]catenane. Chem. Commun. 2012, 48, 9245–9247 10.1039/c2cc34190e. [DOI] [PubMed] [Google Scholar]
Fahrenbach A. C.; Bruns C. J.; Li H.; Trabolsi A.; Coskun A.; Stoddart J. F. Ground-State Kinetics of Bistable Redox-Active Donor-Acceptor Mechanically Interlocked Molecules. Acc. Chem. Res. 2014, 47, 482–493 10.1021/ar400161z. [DOI] [PubMed] [Google Scholar]
Olson M. A.; Braunschweig A. B.; Fang L.; Ikeda T.; Klajn R.; Trabolsi A.; Wesson P. J.; Benitez D.; Mirkin C. A.; Grzybowski B. A.; et al. A Bistable Poly[2]catenane Forms Nanosuperstructures. Angew. Chem., Int. Ed. 2009, 48, 1792–1797 10.1002/anie.200804558. [DOI] [PMC free article] [PubMed] [Google Scholar]
Asakawa M.; Higuchi M.; Mattersteig G.; Nakamura T.; Pease A. R.; Raymo F. M.; Shimizu T.; Stoddart J. F. Current/Voltage Characteristics of Monolayers of Redox-Switchable [2]Catenanes on Gold. Adv. Mater. 2000, 12, 1099–1102. [DOI] [Google Scholar]
Deng W.-Q.; Flood A. H.; Stoddart J. F.; Goddard W. A. III An Electrochemical Color-Switchable RGB Dye: Tristable [2]Catenane. J. Am. Chem. Soc. 2005, 127, 15994–15995 10.1021/ja0431298. [DOI] [PubMed] [Google Scholar]
Kim Y.-H.; Jang S.; Jang Y.; Goddard W. A. III First-Principles Study of the Switching Mechanism of [2]Catenane Molecular Electronic Devices. Phys. Rev. Lett. 2005, 94, 156801. 10.1103/PhysRevLett.94.156801. [DOI] [PubMed] [Google Scholar]
Ahuja R. C.; Caruso P.-L.; Moebius D.; Philp D.; Preece J. A.; Ringsdorf H.; Stoddart J. F.; Wildburg G. Thin Solid Films 1996, 285, 671–677 10.1016/S0040-6090(95)08418-5. [DOI] [Google Scholar]
Brown C. L.; Jonas U.; Preece J. A.; Ringsdorf H.; Seitz M.; Stoddart J. F. Introduction of [2]Catenanes into Langmuir Films and Langmuir–Blodgett Multilayers. A Possible Strategy for Molecular Information Storage Materials. Langmuir 2000, 16, 1924–1930 10.1021/la990791m. [DOI] [Google Scholar]
Norgaard K.; Jeppesen J. O.; Laursen B. W.; Simonsen J. B.; Weygand M. J.; Kjaer K.; Stoddart J. F.; Bjornholm T. J. Phys. Chem. B 2005, 109, 1063–1066 10.1021/jp0448494. [DOI] [PubMed] [Google Scholar]
Heinrich T.; Traulsen C. H. H.; Holzweber M.; Richter S.; Kunz V.; Kastner S. K.; Krabbenborg S. O.; Huskens J.; Unger W. E. S.; Schalley C. A. Coupled Molecular Switching Processes in Ordered Mono- and Multilayers of Stimulus-Responsive Rotaxanes on Gold Surfaces. J. Am. Chem. Soc. 2015, 137, 4382–4390 10.1021/ja512654d. [DOI] [PMC free article] [PubMed] [Google Scholar]
Pace G.; Petitjean A.; Lalloz-Vogel M.-N.; Harrowfield J.; Lehn J.-M.; Samorì P. Subnanometer-Resolved Patterning of Bicomponent Self-Assembled Monolayers on Au(111). Angew. Chem., Int. Ed. 2008, 47, 2484–2488 10.1002/anie.200704731. [DOI] [PubMed] [Google Scholar]
Jang S. S.; Jang Y. H.; Kim Y.-H.; Goddard W. A. III; Flood A. H.; Laursen B. W.; Tseng H.-R.; Stoddart J. F.; Jeppesen J. O.; Choik J. W.; et al. Structures and Properties of Self-Assembled Monolayers of Bistable [2]Rotaxanes on Au (111) Surfaces from Molecular Dynamics Simulations Validated with Experiment. J. Am. Chem. Soc. 2005, 127, 1563–1575 10.1021/ja044530x. [DOI] [PubMed] [Google Scholar]
Jang Y. H.; Jang S. S.; Goddard W. A. III Molecular Dynamics Simulation Study on a Monolayer of Half [2]Rotaxane Self-Assembled on Au(111). J. Am. Chem. Soc. 2005, 127, 4959–4964 10.1021/ja044762w. [DOI] [PubMed] [Google Scholar]
Richter S.; Poppenberg J.; Traulsen C. H. H.; Darlatt E.; Sokolowski A.; Sattler D.; Unger W. E. S.; Schalley C. A. Deposition of Ordered Layers of Tetralactam Macrocycles and Ether Rotaxanes on Pyridine-Terminated Self-Assembled Monolayers on Gold. J. Am. Chem. Soc. 2012, 134, 16289–16297 10.1021/ja306212m. [DOI] [PubMed] [Google Scholar]
Wong E. W.; Collier C. P.; Behloradsky M.; Raymo F. M.; Stoddart J. F.; Heath J. R. Fabrication and transport properties of single-molecule-thick electrochemical junctions. J. Am. Chem. Soc. 2000, 122, 5831–5840 10.1021/ja993890v. [DOI] [Google Scholar]
Collier C. P.; Jeppesen J. O.; Luo Y.; Perkins J.; Wong E. W.; Heath J. R.; Stoddart J. F. Molecular-based electronically switchable tunnel junction devices. J. Am. Chem. Soc. 2001, 123, 12632–12641 10.1021/ja0114456. [DOI] [PubMed] [Google Scholar]
Lee I. C.; Frank C. W.; Yamamoto T.; Tseng H. R.; Flood A. H.; Stoddart J. F.; Jeppesen J. O. Langmuir and Langmuir-Blodgett films of amphiphilic bistable rotaxanes. Langmuir 2004, 20, 5809–5828 10.1021/la0361518. [DOI] [PubMed] [Google Scholar]
Jang S. S.; Jang Y. H.; Kim Y. H.; Goddard W. A. III; Choi J. W.; Heath J. R.; Laursen B. W.; Flood A. H.; Stoddart J. F.; Norgaard K.; et al. Molecular dynamics simulation of amphiphilic bistable [2]rotaxane Langmuir monolayers at the air/water interface. J. Am. Chem. Soc. 2005, 127, 14804–14816 10.1021/ja0531531. [DOI] [PubMed] [Google Scholar]
Mendes P. M.; Lu W.; Tseng H. R.; Shinder S.; Iijima T.; Miyaji M.; Knobler C. M.; Stoddart J. F. A soliton phenomenon in langmuir monolayers of amphiphilic bistable rotaxanes. J. Phys. Chem. B 2006, 110, 3845–3848 10.1021/jp058287f. [DOI] [PubMed] [Google Scholar]
Ferri V.; Elbing M.; Pace G.; Dickey M. D.; Zharnikov M.; Samori P.; Mayor M.; Rampi M. A. Light-powered electrical switch based on cargo-lifting azobenzene monolayers. Angew. Chem., Int. Ed. 2008, 47, 3407–3409 10.1002/anie.200705339. [DOI] [PubMed] [Google Scholar]
Green J. E.; Choi J. W.; Boukai A.; Bunimovich Y.; Johnston-Halperin E.; DeIonno E.; Luo Y.; Sheriff B. A.; Xu K.; Shin Y. S.; Tseng H. R.; Stoddart J. F.; Heath J. R. A 160-kilobit molecular electronic memory patterned at 10(11) bits per square centimetre. Nature 2007, 445, 414–417 10.1038/nature05462. [DOI] [PubMed] [Google Scholar]
Yu H.; Luo Y.; Beverly K.; Stoddart J. F.; Tseng H. R.; Heath J. R. The molecule-electrode interface in single-molecule transistors. Angew. Chem., Int. Ed. 2003, 42, 5706–5711 10.1002/anie.200352352. [DOI] [PubMed] [Google Scholar]
Lau C. N.; Stewart D. R.; Williams R. S.; Bockrath M. Direct Observation of Nanoscale Switching Centers in Metal/Molecule/Metal Structures. Nano Lett. 2004, 4, 569–572 10.1021/nl035117a. [DOI] [Google Scholar]
Avellini T.; Li H.; Coskun A.; Barin G.; Trabolsi A.; Basuray A. N.; Dey S. K.; Credi A.; Silvi S.; Stoddart J. F.; Venturi M. Photoinduced Memory Effect in a Redox Controllable Bistable Mechanical Molecular Switch. Angew. Chem., Int. Ed. 2012, 51, 1611–1615 10.1002/anie.201107618. [DOI] [PubMed] [Google Scholar]
Ichimura K. Photoalignment of Liquid-Crystal Systems. Chem. Rev. 2000, 100, 1847–1873 10.1021/cr980079e. [DOI] [PubMed] [Google Scholar]
Hoogboom J.; Rasing T.; Rowan A. E.; Nolte R. J. M. LCD alignment layers. Controlling nematic domain properties. J. Mater. Chem. 2006, 16, 1305–1314 10.1039/B510579J. [DOI] [Google Scholar]
Yu Y.; Ikeda T. Soft Actuators Based on Liquid-Crystalline Elastomers. Angew. Chem., Int. Ed. 2006, 45, 5416–5418 10.1002/anie.200601760. [DOI] [PubMed] [Google Scholar]
Geelhaar T.; Griesar K.; Reckmann B. 125Years of Liquid CrystalsA Scientific Revolution in the Home. Angew. Chem., Int. Ed. 2013, 52, 8798–8809 10.1002/anie.201301457. [DOI] [PubMed] [Google Scholar]
Feringa B. L.; Huck N. P. M.; van Doren H. A. Chiroptical Switching between Liquid Crystalline Phases. J. Am. Chem. Soc. 1995, 117, 9929–9930 10.1021/ja00144a027. [DOI] [Google Scholar]
Huck N. P. M.; Jager W. F.; de Lange B.; Feringa B. L. Dynamic Control and Amplification of Molecular Chirality by Circular Polarized Light. Science 1996, 273, 1686–1688 10.1126/science.273.5282.1686. [DOI] [Google Scholar]
Sagisaka T.; Yokoyama Y. Reversible Control of the Pitch of Cholesteric Liquid Crystals by Photochromism of Chiral Fulgide Derivatives. Bull. Chem. Soc. Jpn. 2000, 73, 191–196 10.1246/bcsj.73.191. [DOI] [Google Scholar]
Palffy-Muhoray P.; Kosa T.; Weinan E. Dynamics of a Light Driven Molecular Motor. Mol. Cryst. Liq. Cryst. 2002, 375, 577–591 10.1080/10587250210584. [DOI] [Google Scholar]
van Delden R. A.; Mecca T.; Rosini C.; Feringa B. L. A chiroptical molecular switch with distinct chiral and photochromic entities and its application in optical switching of a cholesteric liquid crystal. Chem. - Eur. J. 2004, 10, 61–70 10.1002/chem.200305276. [DOI] [PubMed] [Google Scholar]
Kosa T.; Palffy-Muhoray P. Brownian motors in the photoalignment of liquid crystals. Int. J. Eng. Sci. 2000, 38, 1077–1084 10.1016/S0020-7225(99)00107-X. [DOI] [Google Scholar]
Palffy-Muhoray P.; Kosa T.; E W. Brownian motors in the photoalignment of liquid crystals. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 293–300 10.1007/s003390201321. [DOI] [Google Scholar]
van Delden R. A.; Koumura N.; Harada N.; Feringa B. L. Unidirectional rotary motion in a liquid crystalline environment: color tuning by a molecular motor. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4945–4949 10.1073/pnas.062660699. [DOI] [PMC free article] [PubMed] [Google Scholar]
van Delden R. A.; van Gelder M. B.; Huck N. P. M.; Feringa B. L. Controlling the Color of Cholesteric Liquid-Crystalline Films by Photoirradiation of a Chiroptical Molecular Switch Used as Dopant. Adv. Funct. Mater. 2003, 13, 319–324 10.1002/adfm.200304313. [DOI] [Google Scholar]
Setaka W.; Yamaguchi K. Thermal modulation of birefringence observed in a crystalline molecular gyrotop. Proc. Natl. Acad. Sci. U. S. A. 2012, 109, 9271–9275 10.1073/pnas.1114733109. [DOI] [PMC free article] [PubMed] [Google Scholar]
Setaka W.; Yamaguchi K. A Molecular Balloon: Expansion of a Molecular Gyrotop Cage Due to Rotation of the Phenylene Rotor. J. Am. Chem. Soc. 2012, 134, 12458–12461 10.1021/ja305822e. [DOI] [PubMed] [Google Scholar]
Setaka W.; Higa S.; Yamaguchi K. Ring-closing metathesis for the synthesis of a molecular gyrotop. Org. Biomol. Chem. 2014, 12, 3354–3357 10.1039/c4ob00470a. [DOI] [PubMed] [Google Scholar]
Suzaki Y.; Taira T.; Osakada K.; Horie M. Rotaxanes and pseudorotaxanes with Fe-, Pd- and Pt-containing axles. Molecular motion in the solid state and aggregation in solution. Dalton Trans. 2008, 4823–4833 10.1039/b804125c. [DOI] [PubMed] [Google Scholar]
Horie M.; Suzaki Y.; Hashizume D.; Abe T.; Wu T.; Sassa T.; Hosokai T.; Osakada K. Thermally-induced phase transition of pseudorotaxane crystals: changes in conformation and interaction of the molecules and optical properties of the crystals. J. Am. Chem. Soc. 2012, 134, 17932–17944 10.1021/ja304406c. [DOI] [PubMed] [Google Scholar]
Horie M.; Sassa T.; Hashizume D.; Suzaki Y.; Osakada K.; Wada T. A Crystalline Supramolecular Switch: Controlling the Optical Anisotropy through the Collective Dynamic Motion of Molecules. Angew. Chem., Int. Ed. 2007, 46, 4983–4986 10.1002/anie.200700708. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Morales M. A.; Perez E. M.; Wong J. K.; Saiz C. G.; Slawin A. M.; Carmichael A. J.; Haddleton D. M.; Brouwer A. M.; Buma W. J.; Wurpel G. W.; Leon S.; Zerbetto F. Patterning through controlled submolecular motion: rotaxane-based switches and logic gates that function in solution and polymer films. Angew. Chem., Int. Ed. 2005, 44, 3062–3067 10.1002/anie.200500101. [DOI] [PubMed] [Google Scholar]
Yasushi Okumura K. I. The Polyrotaxane Gel: A Topological Gel by Figure-of-Eight Cross-links. Adv. Mater. 2001, 13, 485–487. [DOI] [Google Scholar]
Ito K. Novel Cross-Linking Concept of Polymer Network: Synthesis, Structure, and Properties of Slide-Ring Gels with Freely Movable Junctions. Polym. J. 2007, 39, 489–499 10.1295/polymj.PJ2006239. [DOI] [Google Scholar]
Ma X.; Wang Q.; Qu D.; Xu Y.; Ji F.; Tian H. A light-driven pseudo[4]rotaxane encoded by induced circular dichroism in a hydrogel. Adv. Funct. Mater. 2007, 17, 829–837 10.1002/adfm.200600981. [DOI] [Google Scholar]
Taira T.; Suzaki Y.; Osakada K. Thermosensitive hydrogels composed of cyclodextrin pseudorotaxanes. Role of [3]pseudorotaxane in the gel formation. Chem. Commun. 2009, 7027–7029 10.1039/b911667b. [DOI] [PubMed] [Google Scholar]
Suzaki Y.; Taira T.; Osakada K. Physical gels based on supramolecular gelators, including host-guest complexes and pseudorotaxanes. J. Mater. Chem. 2011, 21, 930–938 10.1039/C0JM02219E. [DOI] [Google Scholar]
Zhu L.; Ma X.; Ji F.; Wang Q.; Tian H. Effective enhancement of fluorescence signals in rotaxane-doped reversible hydrosol-gel systems. Chem. - Eur. J. 2007, 13, 9216–9222 10.1002/chem.200700860. [DOI] [PubMed] [Google Scholar]
Madden J. D. W.; Vandesteeg N. A.; Anquetil P. A.; Madden P. G. A.; Takshi A.; Pytel R. Z.; Lafontaine S. R.; Wieringa P. A.; Hunter I. W. Artificial muscle technology: physical principles and naval prospects. IEEE J. Oceanic Eng. 2004, 29, 706–728 10.1109/JOE.2004.833135. [DOI] [Google Scholar]
Baughman R. H. Playing Nature’s Game with Artificial Muscles. Science 2005, 308, 63–65 10.1126/science.1099010. [DOI] [PubMed] [Google Scholar]
Frank S.; Lauterbur P. C. Voltage-sensitive magnetic gels as magnetic resonance monitoring agents. Nature 1993, 363, 334–336 10.1038/363334a0. [DOI] [PubMed] [Google Scholar]
Osada Y.; Gong J. Stimuli-responsive polymer gels and their application to chemomechanical systems. Prog. Polym. Sci. 1993, 18, 187–226 10.1016/0079-6700(93)90025-8. [DOI] [Google Scholar]
Osada Y.; Gong J.-P. Soft and Wet Materials: Polymer Gels. Adv. Mater. 1998, 10, 827–837. [DOI] [Google Scholar]
Berndt I.; Popescu C.; Wortmann F.-J.; Richtering W. Mechanics versus Thermodynamics: Swelling in Multiple-Temperature-Sensitive Core–Shell Microgels. Angew. Chem., Int. Ed. 2006, 45, 1081–1085 10.1002/anie.200502893. [DOI] [PubMed] [Google Scholar]
Juodkazis S.; Mukai N.; Wakaki R.; Yamaguchi A.; Matsuo S.; Misawa H. Reversible phase transitions in polymer gels induced by radiation forces. Nature 2000, 408, 178–181 10.1038/35041522. [DOI] [PubMed] [Google Scholar]
Yoshida R.; Takahashi T.; Yamaguchi T.; Ichijo H. Self-Oscillating Gel. J. Am. Chem. Soc. 1996, 118, 5134–5135 10.1021/ja9602511. [DOI] [Google Scholar]
Berndt I.; Pedersen J. S.; Richtering W. Temperature-Sensitive Core–Shell Microgel Particles with Dense Shell. Angew. Chem., Int. Ed. 2006, 45, 1737–1741 10.1002/anie.200503888. [DOI] [PubMed] [Google Scholar]
Kiyonaka S.; Sugiyasu K.; Shinkai S.; Hamachi I. First Thermally Responsive Supramolecular Polymer Based on Glycosylated Amino Acid. J. Am. Chem. Soc. 2002, 124, 10954–10955 10.1021/ja027277e. [DOI] [PubMed] [Google Scholar]
You J.-O.; Almeda D.; Ye G.; Auguste D. Bioresponsive matrices in drug delivery. J. Biol. Eng. 2010, 4, 15. 10.1186/1754-1611-4-15. [DOI] [PMC free article] [PubMed] [Google Scholar]
Chaterji S.; Kwon I. K.; Park K. Smart polymeric gels: Redefining the limits of biomedical devices. Prog. Polym. Sci. 2007, 32, 1083–1122 10.1016/j.progpolymsci.2007.05.018. [DOI] [PMC free article] [PubMed] [Google Scholar]
Schild H. G. Poly(N-isopropylacrylamide): experiment, theory and application. Prog. Polym. Sci. 1992, 17, 163–249 10.1016/0079-6700(92)90023-R. [DOI] [Google Scholar]
Shahinpoor M.; Bar-Cohen Y.; Simpson J. O.; Smith J. Ionic polymer-metal composites (IPMCs) as biomimetic sensors, actuators and artificial muscles - a review. Smart Mater. Struct. 1998, 7, R15–R30 10.1088/0964-1726/7/6/001. [DOI] [Google Scholar]
Urry D. W. Physical Chemistry of Biological Free Energy Transduction As Demonstrated by Elastic Protein-Based Polymers. J. Phys. Chem. B 1997, 101, 11007–11028 10.1021/jp972167t. [DOI] [Google Scholar]
Urry D. W. Five axioms for the functional design of peptide-based polymers as molecular machines and materials: Principle for macromolecular assemblies. Biopolymers 1998, 47, 167–178. [DOI] [Google Scholar]
Steinberg I. Z.; Oplatka A.; Katchalsky A. Mechanochemical Engines. Nature 1966, 210, 568–571 10.1038/210568a0. [DOI] [Google Scholar]
Sussman M. V.; Katchalsky A. Mechanochemical Turbine: A New Power Cycle. Science 1970, 167, 45–47 10.1126/science.167.3914.45. [DOI] [PubMed] [Google Scholar]
Yoshida R.; Kokufuta E.; Yamaguchi T. Beating polymer gels coupled with a nonlinear chemical reaction. Chaos 1999, 9, 260–266 10.1063/1.166402. [DOI] [PubMed] [Google Scholar]
Yoshida R.; Otoshi G.; Yamaguchi T.; Kokufuta E. Traveling Chemical Waves for Measuring Solute Diffusivity in Thermosensitive Poly(N-isopropylacrylamide) Gel. J. Phys. Chem. A 2001, 105, 3667–3672 10.1021/jp004187s. [DOI] [Google Scholar]
Yoshida R.; Takei K.; Yamaguchi T. Self-Beating Motion of Gels and Modulation of Oscillation Rhythm Synchronized with Organic Acid. Macromolecules 2003, 36, 1759–1761 10.1021/ma0259618. [DOI] [Google Scholar]
Crook C. J.; Smith A.; Jones R. A. L.; Ryan A. J. Chemically induced oscillations in a pH-responsive hydrogel. Phys. Chem. Chem. Phys. 2002, 4, 1367–1369 10.1039/b109977a. [DOI] [Google Scholar]
Howse J. R.; Topham P.; Crook C. J.; Gleeson A. J.; Bras W.; Jones R. A. L.; Ryan A. J. Reciprocating Power Generation in a Chemically Driven Synthetic Muscle. Nano Lett. 2006, 6, 73–77 10.1021/nl0520617. [DOI] [PubMed] [Google Scholar]
Jones C. D.; Lyon L. A. Synthesis and Characterization of Multiresponsive Core–Shell Microgels. Macromolecules 2000, 33, 8301–8306 10.1021/ma001398m. [DOI] [Google Scholar]
Berndt I.; Richtering W. Doubly Temperature Sensitive Core–Shell Microgels. Macromolecules 2003, 36, 8780–8785 10.1021/ma034771+. [DOI] [Google Scholar]
Beebe D. J.; Moore J. S.; Bauer J. M.; Yu Q.; Liu R. H.; Devadoss C.; Jo B.-H. Functional hydrogel structures for autonomous flow control inside microfluidic channels. Nature 2000, 404, 588–590 10.1038/35007047. [DOI] [PubMed] [Google Scholar]
Yu Q.; Bauer J. M.; Moore J. S.; Beebe D. J. Responsive biomimetic hydrogel valve for microfluidics. Appl. Phys. Lett. 2001, 78, 2589–2591 10.1063/1.1367010. [DOI] [Google Scholar]
Liu R. H.; Yu Q.; Beebe D. J. Fabrication and characterization of hydrogel-based microvalves. J. Microelectromech. Syst. 2002, 11, 45–53 10.1109/84.982862. [DOI] [Google Scholar]
Osada Y.; Okuzaki H.; Hori H. A polymer gel with electrically driven motility. Nature 1992, 355, 242–244 10.1038/355242a0. [DOI] [Google Scholar]
Galaev I. Y.; Mattiasson B. ‘Smart’ polymers and what they could do in biotechnology and medicine. Trends Biotechnol. 1999, 17, 335–340 10.1016/S0167-7799(99)01345-1. [DOI] [PubMed] [Google Scholar]
Peppas N. A.; Huang Y.; Torres-Lugo M.; Ward J. H.; Zhang J. Physicochemical Foundations and Structural Design of Hydrogels in Medicine and Biology. Annu. Rev. Biomed. Eng. 2000, 2, 9–29 10.1146/annurev.bioeng.2.1.9. [DOI] [PubMed] [Google Scholar]
Qiu Y.; Park K. Environment-sensitive hydrogels for drug delivery. Adv. Drug Delivery Rev. 2001, 53, 321–339 10.1016/S0169-409X(01)00203-4. [DOI] [PubMed] [Google Scholar]
Jeong B.; Gutowska A. Lessons from nature: stimuli-responsive polymers and their biomedical applications. Trends Biotechnol. 2002, 20, 305–311 10.1016/S0167-7799(02)01962-5. [DOI] [PubMed] [Google Scholar]
Kopecek J. Polymer chemistry: Swell gels. Nature 2002, 417, 388–391 10.1038/417388a. [DOI] [PubMed] [Google Scholar]
Langer R.; Tirrell D. A. Designing materials for biology and medicine. Nature 2004, 428, 487–492 10.1038/nature02388. [DOI] [PubMed] [Google Scholar]
Lin K.-J.; Fu S.-J.; Cheng C.-Y.; Chen W.-H.; Kao H.-M. Towards Electrochemical Artificial Muscles: A Supramolecular Machine Based on a One-Dimensional Copper-Containing Organophosphonate System. Angew. Chem., Int. Ed. 2004, 43, 4186–4189 10.1002/anie.200454159. [DOI] [PubMed] [Google Scholar]
Li C.; Madsen J.; Armes S. P.; Lewis A. L. A New Class of Biochemically Degradable, Stimulus-Responsive Triblock Copolymer Gelators. Angew. Chem., Int. Ed. 2006, 45, 3510–3513 10.1002/anie.200600324. [DOI] [PubMed] [Google Scholar]
Samoei G. K.; Wang W.; Escobedo J. O.; Xu X.; Schneider H.-J.; Cook R. L.; Strongin R. M. A Chemomechanical Polymer that Functions in Blood Plasma with High Glucose Selectivity. Angew. Chem., Int. Ed. 2006, 45, 5319–5322 10.1002/anie.200601398. [DOI] [PMC free article] [PubMed] [Google Scholar]
Dong L.; Agarwal A. K.; Beebe D. J.; Jiang H. Adaptive liquid microlenses activated by stimuli-responsive hydrogels. Nature 2006, 442, 551–554 10.1038/nature05024. [DOI] [PubMed] [Google Scholar]
Oya T.; Enoki T.; Grosberg A. Y.; Masamune S.; Sakiyama T.; Takeoka Y.; Tanaka K.; Wang G.; Yilmaz Y.; Feld M. S.; Dasari R.; Tanaka T. Reversible Molecular Adsorption Based on Multiple-Point Interaction by Shrinkable Gels. Science 1999, 286, 1543–1545 10.1126/science.286.5444.1543. [DOI] [PubMed] [Google Scholar]
Pennadam S. S.; Lavigne M. D.; Dutta C. F.; Firman K.; Mernagh D.; Górecki D. C.; Alexander C. Control of A Multisubunit DNA Motor by a Thermoresponsive Polymer Switch. J. Am. Chem. Soc. 2004, 126, 13208–13209 10.1021/ja045275j. [DOI] [PubMed] [Google Scholar]
Kokufata E.; Zhang Y.-Q.; Tanaka T. Saccharide-sensitive phase transition of a lectin-loaded gel. Nature 1991, 351, 302–304 10.1038/351302a0. [DOI] [Google Scholar]
Irie M.; Misumi Y.; Tanaka T. Stimuli-responsive polymers: chemical induced reversible phase separation of an aqueous solution of poly(N-isopropylacrylamide) with pendent crown ether groups. Polymer 1993, 34, 4531–4535 10.1016/0032-3861(93)90160-C. [DOI] [Google Scholar]
Lee K.; Asher S. A. Photonic Crystal Chemical Sensors: pH and Ionic Strength. J. Am. Chem. Soc. 2000, 122, 9534–9537 10.1021/ja002017n. [DOI] [Google Scholar]
Miyata T.; Asami N.; Uragami T. A reversibly antigen-responsive hydrogel. Nature 1999, 399, 766–769 10.1038/21619. [DOI] [PubMed] [Google Scholar]
Schneider H.-J.; Tianjun L.; Lomadze N. Molecular Recognition in a Supramolecular Polymer System Translated into Mechanical Motion. Angew. Chem., Int. Ed. 2003, 42, 3544–3546 10.1002/anie.200219965. [DOI] [PubMed] [Google Scholar]
Sharma A. C.; Jana T.; Kesavamoorthy R.; Shi L.; Virji M. A.; Finegold D. N.; Asher S. A. A General Photonic Crystal Sensing Motif: Creatinine in Bodily Fluids. J. Am. Chem. Soc. 2004, 126, 2971–2977 10.1021/ja038187s. [DOI] [PubMed] [Google Scholar]
Goponenko A. V.; Asher S. A. Modeling of Stimulated Hydrogel Volume Changes in Photonic Crystal Pb²⁺ Sensing Materials. J. Am. Chem. Soc. 2005, 127, 10753–10759 10.1021/ja051456p. [DOI] [PubMed] [Google Scholar]
Holtz J. H.; Asher S. A. Polymerized colloidal crystal hydrogel films as intelligent chemical sensing materials. Nature 1997, 389, 829–832 10.1038/39834. [DOI] [PubMed] [Google Scholar]
Holtz J. H.; Holtz J. S. W.; Munro C. H.; Asher S. A. Intelligent Polymerized Crystalline Colloidal Arrays: Novel Chemical Sensor Materials. Anal. Chem. 1998, 70, 780–791 10.1021/ac970853i. [DOI] [Google Scholar]
Asher S. A.; Alexeev V. L.; Goponenko A. V.; Sharma A. C.; Lednev I. K.; Wilcox C. S.; Finegold D. N. Photonic Crystal Carbohydrate Sensors: Low Ionic Strength Sugar Sensing. J. Am. Chem. Soc. 2003, 125, 3322–3329 10.1021/ja021037h. [DOI] [PubMed] [Google Scholar]
Alexeev V. L.; Sharma A. C.; Goponenko A. V.; Das S.; Lednev I. K.; Wilcox C. S.; Finegold D. N.; Asher S. A. High Ionic Strength Glucose-Sensing Photonic Crystal. Anal. Chem. 2003, 75, 2316–2323 10.1021/ac030021m. [DOI] [PubMed] [Google Scholar]
Asher S. A.; Sharma A. C.; Goponenko A. V.; Ward M. M. Photonic Crystal Aqueous Metal Cation Sensing Materials. Anal. Chem. 2003, 75, 1676–1683 10.1021/ac026328n. [DOI] [PubMed] [Google Scholar]
Schneider H.-J.; Liu T. Large macroscopic size changes in chemomechanical polymers with binding sites for metal ions. Chem. Commun. 2004, 100–101 10.1039/b310939a. [DOI] [PubMed] [Google Scholar]
Schneider H.-J.; Tianjun L.; Lomadze N. Sensitivity increase in molecular recognition by decrease of the sensing particle size and by increase of the receptor binding site - a case with chemomechanical polymers. Chem. Commun. 2004, 2436–2437 10.1039/b409331c. [DOI] [PubMed] [Google Scholar]
Schneider H. J.; Tianjun L.; Lomadze N.; Palm B. Cooperativity in a Chemomechanical Polymer: A Chemically Induced Macroscopic Logic Gate. Adv. Mater. 2004, 16, 613–615 10.1002/adma.200306249. [DOI] [Google Scholar]
Wei Z. G.; Sandstroröm R.; Miyazaki S. Shape-memory materials and hybrid composites for smart systems: Part I Shape-memory materials. J. Mater. Sci. 1998, 33, 3743–3762 10.1023/A:1004692329247. [DOI] [Google Scholar]
Lendlein A.; Kelch S. Shape-Memory Polymers. Angew. Chem., Int. Ed. 2002, 41, 2034–2057. [DOI] [PubMed] [Google Scholar]
Scott T. F.; Schneider A. D.; Cook W. D.; Bowman C. N. Photoinduced Plasticity in Cross-Linked Polymers. Science 2005, 308, 1615–1617 10.1126/science.1110505. [DOI] [PubMed] [Google Scholar]
Lendlein A.; Jiang H.; Junger O.; Langer R. Light-induced shape-memory polymers. Nature 2005, 434, 879–882 10.1038/nature03496. [DOI] [PubMed] [Google Scholar]
Baughman R. H.; Cui C.; Zakhidov A. A.; Iqbal Z.; Barisci J. N.; Spinks G. M.; Wallace G. G.; Mazzoldi A.; De Rossi D.; Rinzler A. G.; Jaschinski O.; Roth S.; Kertesz M. Carbon Nanotube Actuators. Science 1999, 284, 1340–1344 10.1126/science.284.5418.1340. [DOI] [PubMed] [Google Scholar]
Raguse B.; Müller K. H.; Wieczorek L. Nanoparticle Actuators. Adv. Mater. 2003, 15, 922–926 10.1002/adma.200304698. [DOI] [Google Scholar]
Herrmann L. O.; Valev V. K.; Tserkezis C.; Barnard J. S.; Kasera S.; Scherman O. A.; Aizpurua J.; Baumberg J. J. Threading plasmonic nanoparticle strings with light. Nat. Commun. 2014, 5, 4568. 10.1038/ncomms5568. [DOI] [PMC free article] [PubMed] [Google Scholar]
Jager E. W. H.; Smela E.; Inganäs O. Microfabricating Conjugated Polymer Actuators. Science 2000, 290, 1540–1545 10.1126/science.290.5496.1540. [DOI] [PubMed] [Google Scholar]
Smela E. Conjugated Polymer Actuators for Biomedical Applications. Adv. Mater. 2003, 15, 481–494 10.1002/adma.200390113. [DOI] [Google Scholar]
Baughman R. H. Conducting polymer artificial muscles. Synth. Met. 1996, 78, 339–353 10.1016/0379-6779(96)80158-5. [DOI] [Google Scholar]
Otero T. F.; Sansieña J. M. Soft and Wet Conducting Polymers for Artificial Muscles. Adv. Mater. 1998, 10, 491–494. [DOI] [PubMed] [Google Scholar]
Sansinena J.; Olazabal V.; Otero T.; Sansinena J.; Polo da Fonseca C.; De Paoli M.-A. A solid state artificial muscle based on polypyrrole and a solid polymeric electrolyte working in air. Chem. Commun. 1997, 2217–2218 10.1039/a705341j. [DOI] [Google Scholar]
Madden J. D.; Cush R. A.; Kanigan T. S.; Brenan C. J.; Hunter I. W. Encapsulated polypyrrole actuators. Synth. Met. 1999, 105, 61–64 10.1016/S0379-6779(99)00034-X. [DOI] [Google Scholar]
Lu W.; Fadeev A. G.; Qi B.; Smela E.; Mattes B. R.; Ding J.; Spinks G. M.; Mazurkiewicz J.; Zhou D.; Wallace G. G.; MacFarlane D. R.; Forsyth S. A.; Forsyth M. Use of Ionic Liquids for π-Conjugated Polymer Electrochemical Devices. Science 2002, 297, 983–987 10.1126/science.1072651. [DOI] [PubMed] [Google Scholar]
Yu H.-h.; Xu B.; Swager T. M. A Proton-Doped Calix[4]arene-Based Conducting Polymer. J. Am. Chem. Soc. 2003, 125, 1142–1143 10.1021/ja028545b. [DOI] [PubMed] [Google Scholar]
Scherlis D. A.; Marzari N. π-Stacking in Thiophene Oligomers as the Driving Force for Electroactive Materials and Devices. J. Am. Chem. Soc. 2005, 127, 3207–3212 10.1021/ja043557d. [DOI] [PubMed] [Google Scholar]
Hugel T.; Holland N. B.; Cattani A.; Moroder L.; Seitz M.; Gaub H. E. Single-Molecule Optomechanical Cycle. Science 2002, 296, 1103–1106 10.1126/science.1069856. [DOI] [PubMed] [Google Scholar]
Kumar G. S.; Neckers D. C. Photochemistry of azobenzene-containing polymers. Chem. Rev. 1989, 89, 1915–1925 10.1021/cr00098a012. [DOI] [Google Scholar]
Natansohn A.; Rochon P. Photoinduced Motions in Azo-Containing Polymers. Chem. Rev. 2002, 102, 4139–4176 10.1021/cr970155y. [DOI] [PubMed] [Google Scholar]
Maxein G.; Zentel R. Photochemical Inversion of the Helical Twist Sense in Chiral Polyisocyanates. Macromolecules 1995, 28, 8438–8440 10.1021/ma00128a068. [DOI] [Google Scholar]
Okamoto Y.; Nakano T. Asymmetric Polymerization. Chem. Rev. 1994, 94, 349–372 10.1021/cr00026a004. [DOI] [Google Scholar]
Nakano T.; Okamoto Y. Synthetic Helical Polymers: Conformation and Function. Chem. Rev. 2001, 101, 4013–4038 10.1021/cr0000978. [DOI] [PubMed] [Google Scholar]
Dumont M.; El Osman A. On spontaneous and photoinduced orientational mobility of dye molecules in polymers. Chem. Phys. 1999, 245, 437–462 10.1016/S0301-0104(99)00096-8. [DOI] [Google Scholar]
Delaire J. A.; Nakatani K. Linear and Nonlinear Optical Properties of Photochromic Molecules and Materials. Chem. Rev. 2000, 100, 1817–1846 10.1021/cr980078m. [DOI] [PubMed] [Google Scholar]
Kim D. Y.; Tripathy S. K.; Li L.; Kumar J. Laser-induced holographic surface relief gratings on nonlinear optical polymer films. Appl. Phys. Lett. 1995, 66, 1166–1168 10.1063/1.113845. [DOI] [Google Scholar]
Viswanathan N.; Yu Kim D.; Bian S.; Williams J.; Liu W.; Li L.; Samuelson L.; Kumar J.; K. Tripathy S. Surface relief structures on azo polymer films. J. Mater. Chem. 1999, 9, 1941–1955 10.1039/a902424g. [DOI] [Google Scholar]
Yager K. G.; Barrett C. J. All-optical patterning of azo polymer films. Curr. Opin. Solid State Mater. Sci. 2001, 5, 487–494 10.1016/S1359-0286(02)00020-7. [DOI] [Google Scholar]
Tanchak O. M.; Barrett C. J. Light-Induced Reversible Volume Changes in Thin Films of Azo Polymers: The Photomechanical Effect. Macromolecules 2005, 38, 10566–10570 10.1021/ma051564w. [DOI] [Google Scholar]
Labarthet F. L.; Bruneel J.-L.; Buffeteau T.; Sourisseau C.; Huber M. R.; Zilker S. J.; Bieringer T. Photoinduced orientations of azobenzene chromophores in two distinct holographic diffraction gratings as studied by polarized Raman confocal microspectrometry. Phys. Chem. Chem. Phys. 2000, 2, 5154–5167 10.1039/b005632o. [DOI] [Google Scholar]
Schulz B. M.; Huber M. R.; Bieringer T.; Krausch G.; Zilker S. J. Length-scale dependence of surface relief gratings in azobenzene side-chain polymers. Synth. Met. 2001, 124, 155–157 10.1016/S0379-6779(01)00457-X. [DOI] [Google Scholar]
Xie P.; Zhang R. Liquid crystal elastomers, networks and gels: advanced smart materials. J. Mater. Chem. 2005, 15, 2529–2550 10.1039/b413835j. [DOI] [Google Scholar]
Li M. H.; Keller P.; Li B.; Wang X.; Brunet M. Light-Driven Side-On Nematic Elastomer Actuators. Adv. Mater. 2003, 15, 569–572 10.1002/adma.200304552. [DOI] [Google Scholar]
Buguin A.; Li M.-H.; Silberzan P.; Ladoux B.; Keller P. Micro-Actuators: When Artificial Muscles Made of Nematic Liquid Crystal Elastomers Meet Soft Lithography. J. Am. Chem. Soc. 2006, 128, 1088–1089 10.1021/ja0575070. [DOI] [PubMed] [Google Scholar]
Finkelmann H.; Nishikawa E.; Pereira G. G.; Warner M. A New Opto-Mechanical Effect in Solids. Phys. Rev. Lett. 2001, 87, 015501. 10.1103/PhysRevLett.87.015501. [DOI] [PubMed] [Google Scholar]
Hogan P. M.; Tajbakhsh A. R.; Terentjev E. M. UV manipulation of order and macroscopic shape in nematic elastomers. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 2002, 65, 041720. 10.1103/PhysRevE.65.041720. [DOI] [PubMed] [Google Scholar]
Ikeda T.; Nakano M.; Yu Y.; Tsutsumi O.; Kanazawa A. Anisotropic Bending and Unbending Behavior of Azobenzene Liquid-Crystalline Gels by Light Exposure. Adv. Mater. 2003, 15, 201–205 10.1002/adma.200390045. [DOI] [Google Scholar]
Camacho-Lopez M.; Finkelmann H.; Palffy-Muhoray P.; Shelley M. Fast liquid-crystal elastomer swims into the dark. Nat. Mater. 2004, 3, 307–310 10.1038/nmat1118. [DOI] [PubMed] [Google Scholar]
Iamsaard S.; Aßhoff S. J.; Matt B.; Kudernac T.; Cornelissen Jeroen J. L. M.; Fletcher S. P.; Katsonis N. Conversion of light into macroscopic helical motion. Nat. Chem. 2014, 6, 229–235 10.1038/nchem.1859. [DOI] [PubMed] [Google Scholar]
Eelkema R.; Pollard M. M.; Vicario J.; Katsonis N.; Ramon B. S.; Bastiaansen C. W. M.; Broer D. J.; Feringa B. L. Molecular machines: Nanomotor rotates microscale objects. Nature 2006, 440, 163–163 10.1038/440163a. [DOI] [PubMed] [Google Scholar]
Chen J.; Kistemaker J. C.; Robertus J.; Feringa B. L. Molecular stirrers in action. J. Am. Chem. Soc. 2014, 136, 14924–14932 10.1021/ja507711h. [DOI] [PubMed] [Google Scholar]
Fritz J.; Baller M. K.; Lang H. P.; Rothuizen H.; Vettiger P.; Meyer E.-J.; Güntherodt H.; Gerber C.; Gimzewski J. K. Translating Biomolecular Recognition into Nanomechanics. Science 2000, 288, 316–318 10.1126/science.288.5464.316. [DOI] [PubMed] [Google Scholar]
Wu G.; Ji H.; Hansen K.; Thundat T.; Datar R.; Cote R.; Hagan M. F.; Chakraborty A. K.; Majumdar A. Origin of nanomechanical cantilever motion generated from biomolecular interactions. Proc. Natl. Acad. Sci. U. S. A. 2001, 98, 1560–1564 10.1073/pnas.98.4.1560. [DOI] [PMC free article] [PubMed] [Google Scholar]
Dhayal B.; Henne W. A.; Doorneweerd D. D.; Reifenberger R. G.; Low P. S. Detection of Bacillus subtilis Spores Using Peptide-Functionalized Cantilever Arrays. J. Am. Chem. Soc. 2006, 128, 3716–3721 10.1021/ja0570887. [DOI] [PubMed] [Google Scholar]
Wu G.; Datar R. H.; Hansen K. M.; Thundat T.; Cote R. J.; Majumdar A. Bioassay of prostate-specific antigen (PSA) using microcantilevers. Nat. Biotechnol. 2001, 19, 856–860 10.1038/nbt0901-856. [DOI] [PubMed] [Google Scholar]
McKendry R.; Zhang J.; Arntz Y.; Strunz T.; Hegner M.; Lang H. P.; Baller M. K.; Certa U.; Meyer E.; Güntherodt H.-J.; et al. Multiple label-free biodetection and quantitative DNA-binding assays on a nanomechanical cantilever array. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 9783–9788 10.1073/pnas.152330199. [DOI] [PMC free article] [PubMed] [Google Scholar]
Shu W.; Liu D.; Watari M.; Riener C. K.; Strunz T.; Welland M. E.; Balasubramanian S.; McKendry R. A. DNA Molecular Motor Driven Micromechanical Cantilever Arrays. J. Am. Chem. Soc. 2005, 127, 17054–17060 10.1021/ja0554514. [DOI] [PubMed] [Google Scholar]
Su M.; Dravid V. P. Surface Combustion Microengines Based on Photocatalytic Oxidations of Hydrocarbons at Room Temperature. Nano Lett. 2005, 5, 2023–2028 10.1021/nl0515605. [DOI] [PubMed] [Google Scholar]
Ji H.-F.; Feng Y.; Xu X.; Purushotham V.; Thundat T.; Brown G. M. Photon-driven nanomechanical cyclic motion. Chem. Commun. 2004, 2532–2533 10.1039/b408997a. [DOI] [PubMed] [Google Scholar]
Li Q.; Fuks G.; Moulin E.; Maaloum M.; Rawiso M.; Kulic I.; Foy J. T.; Giuseppone N. Macroscopic contraction of a gel induced by the integrated motion of light-driven molecular motors. Nat. Nanotechnol. 2015, 10, 161–165 10.1038/nnano.2014.315. [DOI] [PubMed] [Google Scholar]
Coleman A. C.; Beierle J. M.; Stuart M. C.; Macia B.; Caroli G.; Mika J. T.; van Dijken D. J.; Chen J.; Browne W. R.; Feringa B. L. Light-induced disassembly of self-assembled vesicle-capped nanotubes observed in real time. Nat. Nanotechnol. 2011, 6, 547–552 10.1038/nnano.2011.120. [DOI] [PubMed] [Google Scholar]
Milner S. T. Polymer Brushes. Science 1991, 251, 905–914 10.1126/science.251.4996.905. [DOI] [PubMed] [Google Scholar]
Tsukruk V. V. Assembly of supramolecular polymers in ultrathin films. Prog. Polym. Sci. 1997, 22, 247–311 10.1016/S0079-6700(96)00005-6. [DOI] [Google Scholar]
Nath N.; Chilkoti A. Creating “Smart” Surfaces Using Stimuli Responsive Polymers. Adv. Mater. 2002, 14, 1243–1247. [DOI] [Google Scholar]
Cole M. A.; Voelcker N. H.; Thissen H.; Griesser H. J. Stimuli-responsive interfaces and systems for the control of protein–surface and cell–surface interactions. Biomaterials 2009, 30, 1827–1850 10.1016/j.biomaterials.2008.12.026. [DOI] [PubMed] [Google Scholar]
Xia F.; Zhu Y.; Feng L.; Jiang L. Smart responsive surfaces switching reversibly between super-hydrophobicity and super-hydrophilicity. Soft Matter 2009, 5, 275–281 10.1039/B803951H. [DOI] [Google Scholar]
Luzinov I.; Minko S.; Tsukruk V. V. Adaptive and responsive surfaces through controlled reorganization of interfacial polymer layers. Prog. Polym. Sci. 2004, 29, 635–698 10.1016/j.progpolymsci.2004.03.001. [DOI] [Google Scholar]
Huber D. L.; Manginell R. P.; Samara M. A.; Kim B.-I.; Bunker B. C. Programmed Adsorption and Release of Proteins in a Microfluidic Device. Science 2003, 301, 352–354 10.1126/science.1080759. [DOI] [PubMed] [Google Scholar]
Rama Rao G. V.; López G. P. Encapsulation of Poly(N-Isopropyl Acrylamide) in Silica: A Stimuli-Responsive Porous Hybrid Material That Incorporates Molecular Nano-Valves. Adv. Mater. 2000, 12, 1692–1695. [DOI] [Google Scholar]
Rao G. V. R.; Balamurugan S.; Meyer D. E.; Chilkoti A.; López G. P. Hybrid Bioinorganic Smart Membranes That Incorporate Protein-Based Molecular Switches. Langmuir 2002, 18, 1819–1824 10.1021/la011188i. [DOI] [Google Scholar]
Rama Rao G. V.; Krug M. E.; Balamurugan S.; Xu H.; Xu Q.; López G. P. Synthesis and Characterization of Silica–Poly(N-isopropylacrylamide) Hybrid Membranes: Switchable Molecular Filters. Chem. Mater. 2002, 14, 5075–5080 10.1021/cm020627b. [DOI] [Google Scholar]
Liu; Dunphy D. R.; Atanassov P.; Bunge S. D.; Chen Z.; López G. P.; Boyle T. J.; Brinker C. J. Photoregulation of Mass Transport through a Photoresponsive Azobenzene-Modified Nanoporous Membrane. Nano Lett. 2004, 4, 551–554 10.1021/nl0350783. [DOI] [Google Scholar]
Casasús R.; Marcos M. D.; Martínez-Máñez R.; Ros-Lis J. V.; Soto J.; Villaescusa L. A.; Amorós P.; Beltrán D.; Guillem C.; Latorre J. Toward the Development of Ionically Controlled Nanoscopic Molecular Gates. J. Am. Chem. Soc. 2004, 126, 8612–8613 10.1021/ja048095i. [DOI] [PubMed] [Google Scholar]
Pardo-Yissar V.; Gabai R.; Shipway A. N.; Bourenko T.; Willner I. Gold Nanoparticle/Hydrogel Composites with Solvent-Switchable Electronic Properties. Adv. Mater. 2001, 13, 1320–1323. [DOI] [Google Scholar]
Huang F. H.; Scherman O. A. Supramolecular polymers. Chem. Soc. Rev. 2012, 41, 5879–5880 10.1039/c2cs90071h. [DOI] [PubMed] [Google Scholar]
Appel E. A.; del Barrio J.; Loh X. J.; Scherman O. A. Supramolecular polymeric hydrogels. Chem. Soc. Rev. 2012, 41, 6195–6214 10.1039/c2cs35264h. [DOI] [PubMed] [Google Scholar]
Nguyen T. D.; Tseng H.-R.; Celestre P. C.; Flood A. H.; Liu Y.; Stoddart J. F.; Zink J. I. A reversible molecular valve. Proc. Natl. Acad. Sci. U. S. A. 2005, 102, 10029–10034 10.1073/pnas.0504109102. [DOI] [PMC free article] [PubMed] [Google Scholar]
Klajn R.; Olson M. A.; Wesson P. J.; Fang L.; Coskun A.; Trabolsi A.; Soh S.; Stoddart J. F.; Grzybowski B. A. Dynamic hook-and-eye nanoparticle sponges. Nat. Chem. 2009, 1, 733–738 10.1038/nchem.432. [DOI] [PubMed] [Google Scholar]
Shipway A. N.; Willner I. Electronically Transduced Molecular Mechanical and Information Functions on Surfaces. Acc. Chem. Res. 2001, 34, 421–432 10.1021/ar000180h. [DOI] [PubMed] [Google Scholar]
Pardo-Yissar V.; Katz E.; Willner I.; Kotlyar A. B.; Sanders C.; Lill H. Biomaterial engineered electrodes for bioelectronics. Faraday Discuss. 2000, 116, 119–134 10.1039/b001508n. [DOI] [PubMed] [Google Scholar]
Willner I.; Willner B. Layered molecular optoelectronic assemblies. J. Mater. Chem. 1998, 8, 2543–2556 10.1039/a804135k. [DOI] [Google Scholar]
Willner I.; Pardo-Yissar V.; Katz E.; Ranjit K. T. A photoactivated ‘molecular train’ for optoelectronic applications: light-stimulated translocation of a β-cyclodextrin receptor within a stoppered azobenzene-alkyl chain supramolecular monolayer assembly on a Au-electrode. J. ElectroAnal. Chem. 2001, 497, 172–177 10.1016/S0022-0728(00)00455-1. [DOI] [Google Scholar]
Katz E.; Sheeney-Haj-Ichia L.; Willner I. Electrical Contacting of Glucose Oxidase in a Redox-Active Rotaxane Configuration. Angew. Chem., Int. Ed. 2004, 43, 3292–3300 10.1002/anie.200353455. [DOI] [PubMed] [Google Scholar]
Sheeney-Haj-Ichia L.; Willner I. Enhanced Photoelectrochemistry in Supramolecular CdS-Nanoparticle-Stoppered Pseudorotaxane Monolayers Assembled on Electrodes. J. Phys. Chem. B 2002, 106, 13094–13097 10.1021/jp022102c. [DOI] [Google Scholar]
Katz E.; Lioubashevsky O.; Willner I. Electromechanics of a Redox-Active Rotaxane in a Monolayer Assembly on an Electrode. J. Am. Chem. Soc. 2004, 126, 15520–15532 10.1021/ja045465u. [DOI] [PubMed] [Google Scholar]
Blossey R. Self-cleaning surfaces - virtual realities. Nat. Mater. 2003, 2, 301–306 10.1038/nmat856. [DOI] [PubMed] [Google Scholar]
Xin B.; Hao J. Reversibly switchable wettability. Chem. Soc. Rev. 2010, 39, 769–782 10.1039/B913622C. [DOI] [PubMed] [Google Scholar]
Hua Z.; Yang J.; Wang T.; Liu G.; Zhang G. Transparent Surface with Reversibly Switchable Wettability between Superhydrophobicity and Superhydrophilicity. Langmuir 2013, 29, 10307–10312 10.1021/la402584v. [DOI] [PubMed] [Google Scholar]
Brochard F. Motions of droplets on solid surfaces induced by chemical or thermal gradients. Langmuir 1989, 5, 432–438 10.1021/la00086a025. [DOI] [Google Scholar]
Chaudhury M. K.; Whitesides G. M. How to Make Water Run Uphill. Science 1992, 256, 1539–1541 10.1126/science.256.5063.1539. [DOI] [PubMed] [Google Scholar]
Daniel S.; Chaudhury M. K.; Chen J. C. Fast Drop Movements Resulting from the Phase Change on a Gradient Surface. Science 2001, 291, 633–636 10.1126/science.291.5504.633. [DOI] [PubMed] [Google Scholar]
Daniel S.; Sircar S.; Gliem J.; Chaudhury M. K. Ratcheting Motion of Liquid Drops on Gradient Surfaces†. Langmuir 2004, 20, 4085–4092 10.1021/la036221a. [DOI] [PubMed] [Google Scholar]
Liu Y.; Mu L.; Liu B.; Kong J. Controlled Switchable Surface. Chem. - Eur. J. 2005, 11, 2622–2631 10.1002/chem.200400931. [DOI] [PubMed] [Google Scholar]
Lahann J.; Mitragotri S.; Tran T.-N.; Kaido H.; Sundaram J.; Choi I. S.; Hoffer S.; Somorjai G. A.; Langer R. A Reversibly Switching Surface. Science 2003, 299, 371–374 10.1126/science.1078933. [DOI] [PubMed] [Google Scholar]
Wang X.; Kharitonov A. B.; Katz E.; Willner I. Potential-controlled molecular machinery of bipyridinium monolayer-functionalized surfaces: an electrochemical and contact angle analysis. Chem. Commun. 2003, 1542–1543 10.1039/b303845a. [DOI] [Google Scholar]
Wan P.; Jiang Y.; Wang Y.; Wang Z.; Zhang X. Tuning surface wettability through photocontrolled reversible molecular shuttle. Chem. Commun. 2008, 5710–5712 10.1039/b811729b. [DOI] [PubMed] [Google Scholar]
Zhang X.; Zhao H.; Tian D.; Deng H.; Li H. A Photoresponsive Wettability Switch Based on a Dimethylamino Calix[4]arene. Chem. - Eur. J. 2014, 20, 9367–9371 10.1002/chem.201402476. [DOI] [PubMed] [Google Scholar]
Chen K.-Y.; Ivashenko O.; Carroll G. T.; Robertus J.; Kistemaker J. C. M.; London G.; Browne W. R.; Rudolf P.; Feringa B. L. Control of Surface Wettability Using Tripodal Light-Activated Molecular Motors. J. Am. Chem. Soc. 2014, 136, 3219–3224 10.1021/ja412110t. [DOI] [PubMed] [Google Scholar]
Gau H.; Herminghaus S.; Lenz P.; Lipowsky R. Liquid Morphologies on Structured Surfaces: From Microchannels to Microchips. Science 1999, 283, 46–49 10.1126/science.283.5398.46. [DOI] [PubMed] [Google Scholar]
Gallardo B. S.; Gupta V. K.; Eagerton F. D.; Jong L. I.; Craig V. S.; Shah R. R.; Abbott N. L. Electrochemical Principles for Active Control of Liquids on Submillimeter Scales. Science 1999, 283, 57–60 10.1126/science.283.5398.57. [DOI] [PubMed] [Google Scholar]
Daniel S.; Chaudhury M. K. Rectified Motion of Liquid Drops on Gradient Surfaces Induced by Vibration. Langmuir 2002, 18, 3404–3407 10.1021/la025505c. [DOI] [Google Scholar]
Suda H.; Yamada S. Force Measurements for the Movement of a Water Drop on a Surface with a Surface Tension Gradient. Langmuir 2003, 19, 529–531 10.1021/la0264163. [DOI] [Google Scholar]
Choi S.-H.; Zhang Newby B.-m. Micrometer-Scaled Gradient Surfaces Generated Using Contact Printing of Octadecyltrichlorosilane. Langmuir 2003, 19, 7427–7435 10.1021/la035027l. [DOI] [Google Scholar]
Grunze M. Driven Liquids. Science 1999, 283, 41–42 10.1126/science.283.5398.41. [DOI] [Google Scholar]
Reyes D. R.; Iossifidis D.; Auroux P.-A.; Manz A. Micro Total Analysis Systems. 1. Introduction, Theory, and Technology. Anal. Chem. 2002, 74, 2623–2636 10.1021/ac0202435. [DOI] [PubMed] [Google Scholar]
Ichimura K.; Oh S.-K.; Nakagawa M. Light-Driven Motion of Liquids on a Photoresponsive Surface. Science 2000, 288, 1624–1626 10.1126/science.288.5471.1624. [DOI] [PubMed] [Google Scholar]
Minko S.; Müller M.; Motornov M.; Nitschke M.; Grundke K.; Stamm M. Two-Level Structured Self-Adaptive Surfaces with Reversibly Tunable Properties. J. Am. Chem. Soc. 2003, 125, 3896–3900 10.1021/ja0279693. [DOI] [PubMed] [Google Scholar]
Sun T.; Wang G.; Feng L.; Liu B.; Ma Y.; Jiang L.; Zhu D. Reversible Switching between Superhydrophilicity and Superhydrophobicity. Angew. Chem., Int. Ed. 2004, 43, 357–360 10.1002/anie.200352565. [DOI] [PubMed] [Google Scholar]
Fu Q.; Rama Rao G. V.; Basame S. B.; Keller D. J.; Artyushkova K.; Fulghum J. E.; López G. P. Reversible Control of Free Energy and Topography of Nanostructured Surfaces. J. Am. Chem. Soc. 2004, 126, 8904–8905 10.1021/ja047895q. [DOI] [PubMed] [Google Scholar]
Rosario R.; Gust D.; Garcia A. A.; Hayes M.; Taraci J. L.; Clement T.; Dailey J. W.; Picraux S. T. Lotus Effect Amplifies Light-Induced Contact Angle Switching. J. Phys. Chem. B 2004, 108, 12640–12642 10.1021/jp0473568. [DOI] [Google Scholar]
Ariga K.; Ji Q.; Mori T.; Naito M.; Yamauchi Y.; Abe H.; Hill J. P. Enzyme nanoarchitectonics: organization and device application. Chem. Soc. Rev. 2013, 42, 6322–6345 10.1039/c2cs35475f. [DOI] [PubMed] [Google Scholar]
Teller C.; Willner I. Functional nucleic acid nanostructures and DNA machines. Curr. Opin. Biotechnol. 2010, 21, 376–391 10.1016/j.copbio.2010.06.001. [DOI] [PubMed] [Google Scholar]
Hirokawa N.; Noda Y.; Tanaka Y.; Niwa S. Kinesin superfamily motor proteins and intracellular transport. Nat. Rev. Mol. Cell Biol. 2009, 10, 682–696 10.1038/nrm2774. [DOI] [PubMed] [Google Scholar]
Montemagno C.; Bachand G. Constructing nanomechanical devices powered by biomolecular motors. Nanotechnology 1999, 10, 225–231 10.1088/0957-4484/10/3/301. [DOI] [Google Scholar]
Hess H.; Vogel V. Molecular shuttles based on motor proteins: active transport in synthetic environments. Rev. Mol. Biotechnol. 2001, 82, 67–85 10.1016/S1389-0352(01)00029-0. [DOI] [PubMed] [Google Scholar]
Adachi K.; Yasuda R.; Noji H.; Itoh H.; Harada Y.; Yoshida M.; Kinosita K. Stepping rotation of F-1-ATPase visualized through angle-resolved single-fluorophore imaging. Proc. Natl. Acad. Sci. U. S. A. 2000, 97, 7243–7247 10.1073/pnas.120174297. [DOI] [PMC free article] [PubMed] [Google Scholar]
Yasuda R.; Noji H.; Yoshida M.; Kinosita K.; Itoh H. Resolution of distinct rotational substeps by submillisecond kinetic analysis of F-1-ATPase. Nature 2001, 410, 898–904 10.1038/35073513. [DOI] [PubMed] [Google Scholar]
Hirono-Hara Y.; Noji H.; Nishiura M.; Muneyuki E.; Hara K. Y.; Yasuda R.; Kinosita K. Jr.; Yoshida M. Pause and rotation of F(1)-ATPase during catalysis. Proc. Natl. Acad. Sci. U. S. A. 2001, 98, 13649–13654 10.1073/pnas.241365698. [DOI] [PMC free article] [PubMed] [Google Scholar]
Noji H.; Yasuda R.; Yoshida M.; Kinosita K. Jr. Direct observation of the rotation of F₁-ATPase. Nature 1997, 386, 299–302 10.1038/386299a0. [DOI] [PubMed] [Google Scholar]
Yasuda R.; Noji H.; Kinosita K.; Yoshida M. F₁-ATPase is a highly efficient molecular motor that rotates with discrete 120 degree steps. Cell 1998, 93, 1117–1124 10.1016/S0092-8674(00)81456-7. [DOI] [PubMed] [Google Scholar]
Diez M.; Zimmermann B.; Borsch M.; Konig M.; Schweinberger E.; Steigmiller S.; Reuter R.; Felekyan S.; Kudryavtsev V.; Seidel C. A. M.; Graber P. Proton-powered subunit rotation in single membrane-bound F₀F₁-ATP synthase. Nat. Struct. Mol. Biol. 2004, 11, 135–141 10.1038/nsmb718. [DOI] [PubMed] [Google Scholar]
Itoh H.; Takahashi A.; Adachi K.; Noji H.; Yasuda R.; Yoshida M.; Kinosita K. Mechanically driven ATP synthesis by F₁-ATPase. Nature 2004, 427, 465–468 10.1038/nature02212. [DOI] [PubMed] [Google Scholar]
Soong R. K.; Bachand G. D.; Neves H. P.; Olkhovets A. G.; Craighead H. G.; Montemagno C. D. Powering an inorganic nanodevice with a biomolecular motor. Science 2000, 290, 1555–1558 10.1126/science.290.5496.1555. [DOI] [PubMed] [Google Scholar]
Duan L.; He Q.; Wang K. W.; Yan X. H.; Cui Y.; Moewald H.; Li J. B. Adenosine triphosphate biosynthesis catalyzed by F0F1 ATP synthase assembled in polymer microcapsules. Angew. Chem., Int. Ed. 2007, 46, 6996–7000 10.1002/anie.200700331. [DOI] [PubMed] [Google Scholar]
Oiwa K.; Chaen S.; Kamitsubo E.; Shimmen T.; Sugi H. Steady-state force-velocity relation in the ATP-dependent sliding movement of myosin-coated beads on actin cables in vitro studied with a centrifuge microscope. Proc. Natl. Acad. Sci. U. S. A. 1990, 87, 7893–7897 10.1073/pnas.87.20.7893. [DOI] [PMC free article] [PubMed] [Google Scholar]
Reuther C.; Hajdo L.; Tucker R.; Kasprzak A. A.; Diez S. Biotemplated nanopatterning of planar surfaces with molecular motors. Nano Lett. 2006, 6, 2177–2183 10.1021/nl060922l. [DOI] [PubMed] [Google Scholar]
Ramachandran S.; Ernst K. H.; Bachand G. D.; Vogel V.; Hess H. Selective loading of kinesin-powered molecular shuttles with protein cargo and its application to biosensing. Small 2006, 2, 330–334 10.1002/smll.200500265. [DOI] [PubMed] [Google Scholar]
Diez S.; Reuther C.; Dinu C.; Seidel R.; Mertig M.; Pompe W.; Howard J. Stretching and transporting DNA molecules using motor proteins. Nano Lett. 2003, 3, 1251–1254 10.1021/nl034504h. [DOI] [Google Scholar]
Dumont E. L. P.; Do C.; Hess H. Molecular wear of microtubules propeled by surface-adhered kinesins. Nat. Nanotechnol. 2015, 10, 166–169 10.1038/nnano.2014.334. [DOI] [PubMed] [Google Scholar]
Yu T. Y.; Wang Q.; Johnson D. S.; Wang M. D.; Ober C. K. Functional hydrogel surfaces: Binding kinesin-based molecular motor proteins to selected patterned sites. Adv. Funct. Mater. 2005, 15, 1303–1309 10.1002/adfm.200400117. [DOI] [Google Scholar]
Yildiz A.; Selvin P. R. Kinesin: walking, crawling or sliding along?. Trends Cell Biol. 2005, 15, 112–120 10.1016/j.tcb.2004.12.007. [DOI] [PubMed] [Google Scholar]
Beeg J.; Klumpp S.; Dimova R.; Gracia R. S.; Unger E.; Lipowsky R. Transport of beads by several kinesin motors. Biophys. J. 2008, 94, 532–541 10.1529/biophysj.106.097881. [DOI] [PMC free article] [PubMed] [Google Scholar]
Yamasaki H.; Nakayama H. Fluctuation analysis of myosin-coated bead movement along actin bundles of Nitella. Biochem. Biophys. Res. Commun. 1996, 221, 831–836 10.1006/bbrc.1996.0682. [DOI] [PubMed] [Google Scholar]
Spudich J. A.; Kron S. J.; Sheetz M. P. Movement of Myosin-Coated Beads on Oriented Filaments Reconstituted from Purified Actin. Nature 1985, 315, 584–586 10.1038/315584a0. [DOI] [PubMed] [Google Scholar]
Sheetz M. P.; Spudich J. A. Movement of myosin-coated fluorescent beads on actin cables in vitro. Nature 1983, 303, 31–35 10.1038/303031a0. [DOI] [PubMed] [Google Scholar]
Yokokawa R.; Takeuchi S.; Kon T.; Nishiura M.; Sutoh K.; Fujita H. Unidirectional transport of kinesin-coated beads on microtubules oriented in a microfluidic device. Nano Lett. 2004, 4, 2265–2270 10.1021/nl048851i. [DOI] [Google Scholar]
Bormuth V.; Varga V.; Howard J.; Schaffer E. Protein Friction Limits Diffusive and Directed Movements of Kinesin Motors on Microtubules. Science 2009, 325, 870–873 10.1126/science.1174923. [DOI] [PubMed] [Google Scholar]
Agarwal A.; Katira P.; Hess H. Millisecond Curing Time of a Molecular Adhesive Causes Velocity-Dependent Cargo-Loading of Molecular Shuttles. Nano Lett. 2009, 9, 1170–1175 10.1021/nl803831y. [DOI] [PubMed] [Google Scholar]
Bohm K. J.; Stracke R.; Muhlig P.; Unger E. Motor protein-driven unidirectional transport of micrometer-sized cargoes across isopolar microtubule arrays. Nanotechnology 2001, 12, 238–244 10.1088/0957-4484/12/3/307. [DOI] [Google Scholar]
Bottier C.; Fattaccioli J.; Tarhan M. C.; Yokokawa R.; Morin F. O.; Kim B.; Collard D.; Fujita H. Active transport of oil droplets along oriented microtubules by kinesin molecular motors. Lab Chip 2009, 9, 1694–1700 10.1039/b822519b. [DOI] [PubMed] [Google Scholar]
Nitta T.; Tanahashi A.; Obara Y.; Hirano M.; Razumova M.; Regnier M.; Hess H. Comparing guiding track requirements for myosin- and kinesin-powered molecular shuttles. Nano Lett. 2008, 8, 2305–2309 10.1021/nl8010885. [DOI] [PubMed] [Google Scholar]
Vikhorev P. G.; Vikhoreva N. N.; Mansson A. Bending flexibility of actin filaments during motor-induced sliding. Biophys. J. 2008, 95, 5809–5819 10.1529/biophysj.108.140335. [DOI] [PMC free article] [PubMed] [Google Scholar]
Vikhorev P. G.; Vikhoreva N. N.; Sundberg M.; Balaz M.; Albet-Torres N.; Bunk R.; Kvennefors A.; Liljesson K.; Nicholls I. A.; Nilsson L.; Omling P.; Tagerud S.; Montelius L.; Mansson A. Diffusion dynamics of motor-driven transport: gradient production and self-organization of surfaces. Langmuir 2008, 24, 13509–13517 10.1021/la8016112. [DOI] [PubMed] [Google Scholar]
Campbell J.; Paul D.; Kurabayashi K.; Meyhofer E. A Kinesin Driven Enzyme Linked Immunosorbant Assay (ELISA) for Ultra Low Protein Detection Applications. Biophys. J. 2014, 106, 622a–622a 10.1016/j.bpj.2013.11.3441. [DOI] [Google Scholar]
Kakugo A.; Sugimoto S.; Gong J. P.; Osada Y. Gel machines constructed from chemically cross-linked actins and myosins. Adv. Mater. 2002, 14, 1124–1126. [DOI] [Google Scholar]
Sanchez T.; Chen D. T. N.; DeCamp S. J.; Heymann M.; Dogic Z. Spontaneous motion in hierarchically assembled active matter. Nature 2012, 491, 431–434 10.1038/nature11591. [DOI] [PMC free article] [PubMed] [Google Scholar]
Marchetti M. C. Active Matter Spontaneous flows and self-propeled drops. Nature 2012, 491, 340–341 10.1038/nature11750. [DOI] [PubMed] [Google Scholar]
Kinosita K.; Yasuda R.; Noji H.; Adachi K. A rotary molecular motor that can work at near 100% efficiency. Philos. Trans. R. Soc., B 2000, 355, 473–489 10.1098/rstb.2000.0589. [DOI] [PMC free article] [PubMed] [Google Scholar]
Boyer P. D. The ATP synthase - A splendid molecular machine. Annu. Rev. Biochem. 1997, 66, 717–749 10.1146/annurev.biochem.66.1.717. [DOI] [PubMed] [Google Scholar]
Yoshida M.; Muneyuki E.; Hisabori T. ATP synthase - A marvellous rotary engine of the cell. Nat. Rev. Mol. Cell Biol. 2001, 2, 669–677 10.1038/35089509. [DOI] [PubMed] [Google Scholar]
Howard J. The movement of kinesin along microtubules. Annu. Rev. Physiol. 1996, 58, 703–729 10.1146/annurev.ph.58.030196.003415. [DOI] [PubMed] [Google Scholar]
Oesterhelt D.; Brauchle C.; Hampp N. Bacteriorhodopsin - a Biological-Material for Information-Processing. Q. Rev. Biophys. 1991, 24, 425–478 10.1017/S0033583500003863. [DOI] [PubMed] [Google Scholar]
Schick G. A.; Lawrence A. F.; Birge R. R. Biotechnology and Molecular Computing. Trends Biotechnol. 1988, 6, 159–163 10.1016/0167-7799(88)90086-8. [DOI] [Google Scholar]
Birge R. R. Photophysics and Molecular Electronic Applications of the Rhodopsins. Annu. Rev. Phys. Chem. 1990, 41, 683–733 10.1146/annurev.pc.41.100190.003343. [DOI] [PubMed] [Google Scholar]
Chen Z. P.; Birge R. R. Protein-Based Artificial Retinas. Trends Biotechnol. 1993, 11, 292–300 10.1016/0167-7799(93)90017-4. [DOI] [PubMed] [Google Scholar]
Hampp N.; Silber A. Functional dyes from nature: Potentials for technical applications. Pure Appl. Chem. 1996, 68, 1361–1366 10.1351/pac199668071361. [DOI] [Google Scholar]
Birge R. R.; Gillespie N. B.; Izaguirre E. W.; Kusnetzow A.; Lawrence A. F.; Singh D.; Song Q. W.; Schmidt E.; Stuart J. A.; Seetharaman S.; Wise K. J. Biomolecular electronics: Protein-based associative processors and volumetric memories. J. Phys. Chem. B 1999, 103, 10746–10766 10.1021/jp991883n. [DOI] [Google Scholar]
Hampp N. Bacteriorhodopsin as a photochromic retinal protein for optical memories. Chem. Rev. 2000, 100, 1755–1776 10.1021/cr980072x. [DOI] [PubMed] [Google Scholar]
Masthay M. B.; Sammeth D. M.; Helvenston M. C.; Buckman C. B.; Li W. Y.; Cde-Baca M. J.; Kofron J. T. The laser-induced blue state of bacteriorhodopsin: Mechanistic and color regulatory roles of protein-protein interactions, protein-lipid interactions, and metal ions. J. Am. Chem. Soc. 2002, 124, 3418–3430 10.1021/ja010116a. [DOI] [PubMed] [Google Scholar]
Einati H.; Mishra D.; Friedman N.; Sheves M.; Naaman R. Light-Controlled Spin Filtering in Bacteriorhodopsin. Nano Lett. 2015, 15, 1052–1056 10.1021/nl503961p. [DOI] [PMC free article] [PubMed] [Google Scholar]
Rakovich A.; Nabiev I.; Sukhanova A.; Lesnyak V.; Gaponik N.; Rakovich Y. P.; Donegan J. F. Large Enhancement of Nonlinear Optical Response in a Hybrid Nanobiomaterial Consisting of Bacteriorhodopsin and Cadmium Telluride Quantum Dots. ACS Nano 2013, 7, 2154–2160 10.1021/nn3049939. [DOI] [PubMed] [Google Scholar]
Jin Y. D.; Friedman N.; Sheves M.; Cahen D. Bacteriorhodopsin-monolayer-based planar metal-insulator-metal junctions via biomimetic vesicle fusion: Preparation, characterization, and bio-optoelectronic characteristics. Adv. Funct. Mater. 2007, 17, 1417–1428 10.1002/adfm.200600545. [DOI] [Google Scholar]
Szacilowski K. Digital information processing in molecular systems. Chem. Rev. 2008, 108, 3481–3548 10.1021/cr068403q. [DOI] [PubMed] [Google Scholar]
Matile S.; Som A.; Sorde N. Recent synthetic ion channels and pores. Tetrahedron 2004, 60, 6405–6435 10.1016/j.tet.2004.05.052. [DOI] [Google Scholar]
Gokel G. W.; Negin S. Synthetic Ion Channels: From Pores to Biological Applications. Acc. Chem. Res. 2013, 46, 2824–2833 10.1021/ar400026x. [DOI] [PubMed] [Google Scholar]
Sakai N.; Matile S. Synthetic Ion Channels. Langmuir 2013, 29, 9031–9040 10.1021/la400716c. [DOI] [PubMed] [Google Scholar]
Fyles T. M. Synthetic ion channels in bilayer membranes. Chem. Soc. Rev. 2007, 36, 335–347 10.1039/B603256G. [DOI] [PubMed] [Google Scholar]
Carr R.; Weinstock I. A.; Sivaprasadarao A.; Muller A.; Aksimentiev A. Synthetic Ion Channels via Self-Assembly: A Route for Embedding Porous Polyoxometalate Nanocapsules in Lipid Bilayer Membranes. Nano Lett. 2008, 8, 3916–3921 10.1021/nl802366k. [DOI] [PMC free article] [PubMed] [Google Scholar]
Branton D.; Deamer D. W.; Marziali A.; Bayley H.; Benner S. A.; Butler T.; Di Ventra M.; Garaj S.; Hibbs A.; Huang X.; Jovanovich S. B.; Krstic P. S.; Lindsay S.; Ling X. S.; Mastrangelo C. H.; Meller A.; Oliver J. S.; Pershin Y. V.; Ramsey J. M.; Riehn R.; Soni G. V.; Tabard-Cossa V.; Wanunu M.; Wiggin M.; Schloss J. A. The potential and challenges of nanopore sequencing. Nat. Biotechnol. 2008, 26, 1146–1153 10.1038/nbt.1495. [DOI] [PMC free article] [PubMed] [Google Scholar]
Kang X.-f.; Gu L.-Q.; Cheley S.; Bayley H. Single Protein Pores Containing Molecular Adapters at High Temperatures. Angew. Chem., Int. Ed. 2005, 44, 1495–1499 10.1002/anie.200461885. [DOI] [PubMed] [Google Scholar]
Meller A.; Nivon L.; Branton D. Voltage-Driven DNA Translocations through a Nanopore. Phys. Rev. Lett. 2001, 86, 3435–3438 10.1103/PhysRevLett.86.3435. [DOI] [PubMed] [Google Scholar]
Gershow M.; Golovchenko J. A. Recapturing and trapping single molecules with a solid-state nanopore. Nat. Nanotechnol. 2007, 2, 775–779 10.1038/nnano.2007.381. [DOI] [PMC free article] [PubMed] [Google Scholar]
Lubensky D. K.; Nelson D. R. Driven Polymer Translocation Through a Narrow Pore. Biophys. J. 1999, 77, 1824–1838 10.1016/S0006-3495(99)77027-X. [DOI] [PMC free article] [PubMed] [Google Scholar]
Holden M. A.; Bayley H. Direct Introduction of Single Protein Channels and Pores into Lipid Bilayers. J. Am. Chem. Soc. 2005, 127, 6502–6503 10.1021/ja042470p. [DOI] [PubMed] [Google Scholar]
González J. E.; Oades K.; Leychkis Y.; Harootunian A.; Negulescu P. A. Cell-based assays and instrumentation for screening ion-channel targets. Drug Discovery Today 1999, 4, 431–439 10.1016/S1359-6446(99)01383-5. [DOI] [PubMed] [Google Scholar]
Jentsch T. J.; Hubner C. A.; Fuhrmann J. C. Ion channels: Function unravelled by dysfunction. Nat. Cell Biol. 2004, 6, 1039–1047 10.1038/ncb1104-1039. [DOI] [PubMed] [Google Scholar]
Majd S.; Yusko E. C.; Billeh Y. N.; Macrae M. X.; Yang J.; Mayer M. Applications of biological pores in nanomedicine, sensing, and nanoelectronics. Curr. Opin. Biotechnol. 2010, 21, 439–476 10.1016/j.copbio.2010.05.002. [DOI] [PMC free article] [PubMed] [Google Scholar]
Koçer A.; Walko M.; Bulten E.; Halza E.; Feringa B. L.; Meijberg W. Rationally Designed Chemical Modulators Convert a Bacterial Channel Protein into a pH-Sensory Valve. Angew. Chem., Int. Ed. 2006, 45, 3126–3130 10.1002/anie.200503403. [DOI] [PubMed] [Google Scholar]
Kiwada T.; Sonomura K.; Sugiura Y.; Asami K.; Futaki S. Transmission of Extramembrane Conformational Change into Current: Construction of Metal-Gated Ion Channel. J. Am. Chem. Soc. 2006, 128, 6010–6011 10.1021/ja060515b. [DOI] [PubMed] [Google Scholar]
Sukharev S.; Anishkin A. Mechanosensitive channels: what can we learn from ‘simple’ model systems?. Trends Neurosci. 2004, 27, 345–351 10.1016/j.tins.2004.04.006. [DOI] [PubMed] [Google Scholar]
Louhivuori M.; Risselada H. J.; van der Giessen E.; Marrink S. J. Release of content through mechano-sensitive gates in pressurized liposomes. Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 19856–19860 10.1073/pnas.1001316107. [DOI] [PMC free article] [PubMed] [Google Scholar]
Steinberg-Yfrach G.; Rigaud J.-L.; Durantini E. N.; Moore A. L.; Gust D.; Moore T. A. Light-driven production of ATP catalysed by F0F1-ATP synthase in an artificial photosynthetic membrane. Nature 1998, 392, 479–482 10.1038/33116. [DOI] [PubMed] [Google Scholar]
Banghart M.; Borges K.; Isacoff E.; Trauner D.; Kramer R. H. Light-activated ion channels for remote control of neuronal firing. Nat. Neurosci. 2004, 7, 1381–1386 10.1038/nn1356. [DOI] [PMC free article] [PubMed] [Google Scholar]
Volgraf M.; Gorostiza P.; Numano R.; Kramer R. H.; Isacoff E. Y.; Trauner D. Allosteric control of an ionotropic glutamate receptor with an optical switch. Nat. Chem. Biol. 2006, 2, 47–52 10.1038/nchembio756. [DOI] [PMC free article] [PubMed] [Google Scholar]
Stein M.; Breit A.; Fehrentz T.; Gudermann T.; Trauner D. Optical Control of TRPV1 Channels. Angew. Chem., Int. Ed. 2013, 52, 9845–9848 10.1002/anie.201302530. [DOI] [PubMed] [Google Scholar]
Schoenberger M.; Damijonaitis A.; Zhang Z. N.; Nagel D.; Trauner D. Development of a New Photochromic Ion Channel Blocker via Azologization of Fomocaine. ACS Chem. Neurosci. 2014, 5, 514–518 10.1021/cn500070w. [DOI] [PMC free article] [PubMed] [Google Scholar]
Schonberger M.; Althaus M.; Fronius M.; Clauss W.; Trauner D. Controlling epithelial sodium channels with light using photoswitchable amilorides. Nat. Chem. 2014, 6, 712–719 10.1038/nchem.2004. [DOI] [PubMed] [Google Scholar]
Kramer R. H.; Chambers J. J.; Trauner D. Photochemical tools for remote control of ion channels in excitable cells. Nat. Chem. Biol. 2005, 1, 360–365 10.1038/nchembio750. [DOI] [PubMed] [Google Scholar]
Banghart M. R.; Mourot A.; Fortin D. L.; Yao J. Z.; Kramer R. H.; Trauner D. Photochromic Blockers of Voltage-Gated Potassium Channels. Angew. Chem., Int. Ed. 2009, 48, 9097–9101 10.1002/anie.200904504. [DOI] [PMC free article] [PubMed] [Google Scholar]
Mourot A.; Fehrentz T.; Le Feuvre Y.; Smith C. M.; Herold C.; Dalkara D.; Nagy F.; Trauner D.; Kramer R. H. Rapid optical control of nociception with an ion-channel photoswitch. Nat. Methods 2012, 9, 396–402 10.1038/nmeth.1897. [DOI] [PMC free article] [PubMed] [Google Scholar]
Lougheed T.; Borisenko V.; Hennig T.; Ruck-Braun K.; Woolley G. A. Photomodulation of ionic current through hemithioindigo-modified gramicidin channels. Org. Biomol. Chem. 2004, 2, 2798–2801 10.1039/b408485c. [DOI] [PubMed] [Google Scholar]
Banghart M. R.; Volgraf M.; Trauner D. Engineering light-gated ion channels. Biochemistry 2006, 45, 15129–15141 10.1021/bi0618058. [DOI] [PubMed] [Google Scholar]
Brieke C.; Rohrbach F.; Gottschalk A.; Mayer G.; Heckel A. Light-Controlled Tools. Angew. Chem., Int. Ed. 2012, 51, 8446–8476 10.1002/anie.201202134. [DOI] [PubMed] [Google Scholar]
Shinbo T.; Kurihara K.; Kobatake Y.; Kamo N. Active transport of picrate anion through organic liquid membrane. Nature 1977, 270, 277–278 10.1038/270277a0. [DOI] [PubMed] [Google Scholar]
Grimaldi J. J.; Boileau S.; Lehn J.-M. Light-driven, carrier-mediated electron transfer across artificial membranes. Nature 1977, 265, 229–230 10.1038/265229a0. [DOI] [PubMed] [Google Scholar]
Grimaldi J. J.; Lehn J.-M. Transport processes in organic chemistry. 5. Multicarrier transport: coupled transport of electrons and metal cations mediated by an electron carrier and a selective cation carrier. J. Am. Chem. Soc. 1979, 101, 1333–1334 10.1021/ja00499a074. [DOI] [Google Scholar]
Anderson S. S.; Lyle I. G.; Paterson R. Electron transfer across membranes using vitamin K1 and coenzyme Q10 as carrier molecules. Nature 1976, 259, 147–148 10.1038/259147a0. [DOI] [PubMed] [Google Scholar]
Steinberg-Yfrach G.; Liddell P. A.; Hung S.-C.; Moore A. L.; Gust D.; Moore T. A. Conversion of light energy to proton potential in liposomes by artificial photosynthetic reaction centers. Nature 1997, 385, 239–241 10.1038/385239a0. [DOI] [Google Scholar]
Bennett I. M.; Farfano H. M. V.; Bogani F.; Primak A.; Liddell P. A.; Otero L.; Sereno L.; Silber J. J.; Moore A. L.; Moore T. A.; Gust D. Active transport of Ca²⁺ by an artificial photosynthetic membrane. Nature 2002, 420, 398–401 10.1038/nature01209. [DOI] [PubMed] [Google Scholar]
Meyer T. J. Chemical approaches to artificial photosynthesis. Acc. Chem. Res. 1989, 22, 163–170 10.1021/ar00161a001. [DOI] [Google Scholar]
Wasielewski M. R. Photoinduced electron transfer in supramolecular systems for artificial photosynthesis. Chem. Rev. 1992, 92, 435–461 10.1021/cr00011a005. [DOI] [Google Scholar]
Gust D.; Moore T. A.; Moore A. L. Molecular mimicry of photosynthetic energy and electron transfer. Acc. Chem. Res. 1993, 26, 198–205 10.1021/ar00028a010. [DOI] [Google Scholar]
Kurreck H.; Huber M. Model Reactions for Photosynthesis—Photoinduced Charge and Energy Transfer between Covalently Linked Porphyrin and Quinone Units. Angew. Chem., Int. Ed. Engl. 1995, 34, 849–866 10.1002/anie.199508491. [DOI] [Google Scholar]
Balzani V.; Credi A.; Venturi M. Photoprocesses. Curr. Opin. Chem. Biol. 1997, 1, 506–513 10.1016/S1367-5931(97)80045-2. [DOI] [PubMed] [Google Scholar]
Gust D.; Moore T. A.; Moore A. L. Mimicking Photosynthetic Solar Energy Transduction. Acc. Chem. Res. 2001, 34, 40–48 10.1021/ar9801301. [DOI] [PubMed] [Google Scholar]
Dürr H.; Bossmann S. Ruthenium Polypyridine Complexes. On the Route to Biomimetic Assemblies as Models for the Photosynthetic Reaction Center. Acc. Chem. Res. 2001, 34, 905–917 10.1021/ar9901220. [DOI] [PubMed] [Google Scholar]
Sun L.; Hammarstrom L.; Akermark B.; Styring S. Towards artificial photosynthesis: ruthenium-manganese chemistry for energy production. Chem. Soc. Rev. 2001, 30, 36–49 10.1039/a801490f. [DOI] [Google Scholar]
Holten D.; Bocian D. F.; Lindsey J. S. Probing Electronic Communication in Covalently Linked Multiporphyrin Arrays. A Guide to the Rational Design of Molecular Photonic Devices. Acc. Chem. Res. 2002, 35, 57–69 10.1021/ar970264z. [DOI] [PubMed] [Google Scholar]
Imahori H.; Mori Y.; Matano Y. Nanostructured artificial photosynthesis. J. Photochem. Photobiol., C 2003, 4, 51–83 10.1016/S1389-5567(03)00004-2. [DOI] [Google Scholar]
Guldi D. M. Fullerene-porphyrin architectures; photosynthetic antenna and reaction center models. Chem. Soc. Rev. 2002, 31, 22–36 10.1039/b106962b. [DOI] [PubMed] [Google Scholar]
Imahori H. Porphyrin-fullerene linked systems as artificial photosynthetic mimics. Org. Biomol. Chem. 2004, 2, 1425–1433 10.1039/b403024a. [DOI] [PubMed] [Google Scholar]
Alstrum-Acevedo J. H.; Brennaman M. K.; Meyer T. J. Chemical Approaches to Artificial Photosynthesis. 2. Inorg. Chem. 2005, 44, 6802–6827 10.1021/ic050904r. [DOI] [PubMed] [Google Scholar]
Paddon-Row M. N. Investigating long-range electron-transfer processes with rigid, covalently linked donor-(norbornylogous bridge)-acceptor systems. Acc. Chem. Res. 1994, 27, 18–25 10.1021/ar00037a003. [DOI] [Google Scholar]
Nicoletta F. P.; Cupelli D.; Formoso P.; De Filpo G.; Colella V.; Gugliuzza A. Light Responsive Polymer Membranes: A Review. Membranes 2012, 2, 134–197 10.3390/membranes2010134. [DOI] [PMC free article] [PubMed] [Google Scholar]
Limburg B.; Laisné G.; Bouwman E.; Bonnet S. Enhanced Photoinduced Electron Transfer at the Surface of Charged Lipid Bilayers. Chem. - Eur. J. 2014, 20, 8965–8972 10.1002/chem.201402712. [DOI] [PubMed] [Google Scholar]
Banerji N.; Fürstenberg A.; Bhosale S.; Sisson A. L.; Sakai N.; Matile S.; Vauthey E. Ultrafast Photoinduced Charge Separation in Naphthalene Diimide Based Multichromophoric Systems in Liquid Solutions and in a Lipid Membrane. J. Phys. Chem. B 2008, 112, 8912–8922 10.1021/jp801276p. [DOI] [PubMed] [Google Scholar]
Numata T.; Murakami T.; Kawashima F.; Morone N.; Heuser J. E.; Takano Y.; Ohkubo K.; Fukuzumi S.; Mori Y.; Imahori H. Utilization of Photoinduced Charge-Separated State of Donor–Acceptor-Linked Molecules for Regulation of Cell Membrane Potential and Ion Transport. J. Am. Chem. Soc. 2012, 134, 6092–6095 10.1021/ja3007275. [DOI] [PubMed] [Google Scholar]
Garg V.; Kodis G.; Chachisvilis M.; Hambourger M.; Moore A. L.; Moore T. A.; Gust D. Conformationally Constrained Macrocyclic Diporphyrin–Fullerene Artificial Photosynthetic Reaction Center. J. Am. Chem. Soc. 2011, 133, 2944–2954 10.1021/ja1083078. [DOI] [PMC free article] [PubMed] [Google Scholar]
Rutherford A. W.; Moore T. A. Mimicking photosynthesis, but just the best bits. Nature 2008, 453, 449–449 10.1038/453449b. [DOI] [PubMed] [Google Scholar]
Bhosale S.; Sisson A. L.; Talukdar P.; Fürstenberg A.; Banerji N.; Vauthey E.; Bollot G.; Mareda J.; Röger C.; Würthner F.; Sakai N.; Matile S. Photoproduction of Proton Gradients with π-Stacked Fluorophore Scaffolds in Lipid Bilayers. Science 2006, 313, 84–86 10.1126/science.1126524. [DOI] [PubMed] [Google Scholar]
Tan S. C.; Crouch L. I.; Jones M. R.; Welland M. Generation of Alternating Current in Response to Discontinuous Illumination by Photoelectrochemical Cells Based on Photosynthetic Proteins. Angew. Chem., Int. Ed. 2012, 51, 6667–6671 10.1002/anie.201200466. [DOI] [PubMed] [Google Scholar]
Xie X.; Crespo G. A.; Mistlberger G.; Bakker E. Photocurrent generation based on a light-driven proton pump in an artificial liquid membrane. Nat. Chem. 2014, 6, 202–207 10.1038/nchem.1858. [DOI] [PubMed] [Google Scholar]
Simmel F. C.; Yurke B. Using DNA to construct and power a nanoactuator. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 2001, 63, 041913. 10.1103/PhysRevE.63.041913. [DOI] [PubMed] [Google Scholar]
Li J. W. J.; Tan W. H. A single DNA molecule nanomotor. Nano Lett. 2002, 2, 315–318 10.1021/nl015713+. [DOI] [PMC free article] [PubMed] [Google Scholar]
Niemeyer C. M.; Adler M. Nanomechanical devices based on DNA. Angew. Chem., Int. Ed. 2002, 41, 3779–3783. [DOI] [PubMed] [Google Scholar]
Simmel F. C.; Yurke B. A DNA-based molecular device switchable between three distinct mechanical states. Appl. Phys. Lett. 2002, 80, 883–885 10.1063/1.1447008. [DOI] [Google Scholar]
Yan H.; Zhang X. P.; Shen Z. Y.; Seeman N. C. A robust DNA mechanical device controlled by hybridization topology. Nature 2002, 415, 62–65 10.1038/415062a. [DOI] [PubMed] [Google Scholar]
Seeman N. C. Biochemistry and structural DNA nanotechnology: An evolving symbiotic relationship. Biochemistry 2003, 42, 7259–7269 10.1021/bi030079v. [DOI] [PubMed] [Google Scholar]
Feng L. P.; Park S. H.; Reif J. H.; Yan H. A two-state DNA lattice switched by DNA nanoactuator. Angew. Chem., Int. Ed. 2003, 42, 4342–4346 10.1002/anie.200351818. [DOI] [PubMed] [Google Scholar]
Liu D. S.; Balasubramanian S. A proton-fueled DNA nanomachine. Angew. Chem., Int. Ed. 2003, 42, 5734–5736 10.1002/anie.200352402. [DOI] [PubMed] [Google Scholar]
Chen Y.; Lee S. H.; Mao C. A DNA nanomachine based on a duplex-triplex transition. Angew. Chem., Int. Ed. 2004, 43, 5335–5338 10.1002/anie.200460789. [DOI] [PubMed] [Google Scholar]
Chen Y.; Wang M. S.; Mao C. D. An autonomous DNA nanomotor powered by a DNA enzyme. Angew. Chem., Int. Ed. 2004, 43, 3554–3557 10.1002/anie.200453779. [DOI] [PubMed] [Google Scholar]
Chen Y.; Mao C. D. Putting a brake on an autonomous DNA nanomotor. J. Am. Chem. Soc. 2004, 126, 8626–8627 10.1021/ja047991r. [DOI] [PubMed] [Google Scholar]
Seeman N. C. From genes to machines: DNA nanomechanical devices. Trends Biochem. Sci. 2005, 30, 119–125 10.1016/j.tibs.2005.01.007. [DOI] [PMC free article] [PubMed] [Google Scholar]
Simmel F. C.; Dittmer W. U. DNA nanodevices. Small 2005, 1, 284–299 10.1002/smll.200400111. [DOI] [PubMed] [Google Scholar]
Beissenhirtz M. K.; Willner I. DNA-based machines. Org. Biomol. Chem. 2006, 4, 3392–3401 10.1039/b607033g. [DOI] [PubMed] [Google Scholar]
Bath J.; Turberfield A. J. DNA nanomachines. Nat. Nanotechnol. 2007, 2, 275–284 10.1038/nnano.2007.104. [DOI] [PubMed] [Google Scholar]
Krishnan Y.; Simmel F. C. Nucleic Acid Based Molecular Devices. Angew. Chem., Int. Ed. 2011, 50, 3124–3156 10.1002/anie.200907223. [DOI] [PubMed] [Google Scholar]
Liu X. Q.; Lu C. H.; Willner I. Switchable Reconfiguration of Nucleic Acid Nanostructures by Stimuli-Responsive DNA Machines. Acc. Chem. Res. 2014, 47, 1673–1680 10.1021/ar400316h. [DOI] [PubMed] [Google Scholar]
Wang F.; Willner B.; Willner I. DNA-based machines. Top. Curr. Chem. 2014, 354, 279–338 10.1007/128_2013_515. [DOI] [PubMed] [Google Scholar]
Tang Y.; Ge B.; Sen D.; Yu H. Z. Functional DNA switches: rational design and electrochemical signaling. Chem. Soc. Rev. 2014, 43, 518–529 10.1039/C3CS60264H. [DOI] [PubMed] [Google Scholar]
Venkataraman S.; Dirks R. M.; Rothemund P. W.; Winfree E.; Pierce N. A. An autonomous polymerization motor powered by DNA hybridization. Nat. Nanotechnol. 2007, 2, 490–494 10.1038/nnano.2007.225. [DOI] [PubMed] [Google Scholar]
Tomov T. E.; Tsukanov R.; Liber M.; Masoud R.; Plavner N.; Nir E. Rational design of DNA motors: fuel optimization through single-molecule fluorescence. J. Am. Chem. Soc. 2013, 135, 11935–11941 10.1021/ja4048416. [DOI] [PubMed] [Google Scholar]
Dittmer W. U.; Simmel F. C. Transcriptional control of DNA-based nanomachines. Nano Lett. 2004, 4, 689–691 10.1021/nl049784v. [DOI] [Google Scholar]
Dittmer W. U.; Kempter S.; Radler J. O.; Simmel F. C. Using gene regulation to program DNA-based molecular devices. Small 2005, 1, 709–712 10.1002/smll.200500074. [DOI] [PubMed] [Google Scholar]
Shin J. S.; Pierce N. A. A synthetic DNA walker for molecular transport. J. Am. Chem. Soc. 2004, 126, 10834–10835 10.1021/ja047543j. [DOI] [PubMed] [Google Scholar]
Sherman W. B.; Seeman N. C. A precisely controlled DNA biped walking device. (vol 4, pg 1801, 2004). Nano Lett. 2004, 4, 1801–1801 10.1021/nl048887a. [DOI] [Google Scholar]
Kelly T. R. Molecular motors: synthetic DNA-based walkers inspired by kinesin. Angew. Chem., Int. Ed. 2005, 44, 4124–4127 10.1002/anie.200500568. [DOI] [PubMed] [Google Scholar]
Omabegho T.; Sha R.; Seeman N. C. A bipedal DNA Brownian motor with coordinated legs. Science 2009, 324, 67–71 10.1126/science.1170336. [DOI] [PMC free article] [PubMed] [Google Scholar]
Reif J. H. The design of autonomous DNA nanomechanical devices: Walking and rolling DNA. DNA Comp. 2003, 2568, 22–37 10.1007/3-540-36440-4_3. [DOI] [Google Scholar]
Yin P.; Turberfield A. J.; Reif J. H. Designs of autonomous unidirectional walking DNA devices. DNA Comp. 2005, 3384, 410–425 10.1007/11493785_36. [DOI] [Google Scholar]
Yurke B.; Turberfield A. J.; Mills A. P.; Simmel F. C.; Neumann J. L. A DNA-fueled molecular machine made of DNA. Nature 2000, 406, 605–608 10.1038/35020524. [DOI] [PubMed] [Google Scholar]
Tian Y.; Mao C. D. Molecular gears: A pair of DNA circles continuously rolls against each other. J. Am. Chem. Soc. 2004, 126, 11410–11411 10.1021/ja046507h. [DOI] [PubMed] [Google Scholar]
Wang C.; Huang Z.; Lin Y.; Ren J.; Qu X. Artificial DNA nano-spring powered by protons. Adv. Mater. 2010, 22, 2792–2798 10.1002/adma.201000445. [DOI] [PubMed] [Google Scholar]
Lund K.; Manzo A. J.; Dabby N.; Michelotti N.; Johnson-Buck A.; Nangreave J.; Taylor S.; Pei R.; Stojanovic M. N.; Walter N. G.; Winfree E.; Yan H. Molecular robots guided by prescriptive landscapes. Nature 2010, 465, 206–210 10.1038/nature09012. [DOI] [PMC free article] [PubMed] [Google Scholar]
Muscat R. A.; Bath J.; Turberfield A. J. A programmable molecular robot. Nano Lett. 2011, 11, 982–987 10.1021/nl1037165. [DOI] [PubMed] [Google Scholar]
Shelley F. J.; Wickham M. E.; Katsuda Y.; Hidaka K.; Bath J.; Sugiyama H.; Turberfield A. J. Nat. Nanotechnol. 2011, 6, 166–169 10.1038/nnano.2010.284. [DOI] [PubMed] [Google Scholar]
Ackermann D.; Jester S.-S.; Famulok M. Design Strategy for DNA Rotaxanes with a Mechanically Reinforced PX100 Axle. Angew. Chem., Int. Ed. 2012, 51, 6771–6775 10.1002/anie.201202816. [DOI] [PubMed] [Google Scholar]
Ackermann Damian; S T. L.; Hannam Jeffrey S.; Purohit Chandra S.; Heckel Alexander; Famulok Michael A Double-Stranded DNA Rotaxane. Nat. Nanotechnol. 2010, 5, 436–442 10.1038/nnano.2010.65. [DOI] [PubMed] [Google Scholar]
Schmidt T. L.; Heckel A. Construction of a structurally defined double-stranded DNA catenane. Nano Lett. 2011, 11, 1739–1742 10.1021/nl200303m. [DOI] [PubMed] [Google Scholar]
Lohmann F.; Ackermann D.; Famulok M. Reversible light switch for macrocycle mobility in a DNA rotaxane. J. Am. Chem. Soc. 2012, 134, 11884–11887 10.1021/ja3042096. [DOI] [PMC free article] [PubMed] [Google Scholar]
Elbaz J.; Wang Z. G.; Wang F.; Willner I. Programmed dynamic topologies in DNA catenanes. Angew. Chem., Int. Ed. 2012, 51, 2349–2353 10.1002/anie.201107591. [DOI] [PubMed] [Google Scholar]
Onizuka K.; Nagatsugi F.; Ito Y.; Abe H. Automatic pseudorotaxane formation targeting on nucleic acids using a pair of reactive oligodeoxynucleotides. J. Am. Chem. Soc. 2014, 136, 7201–7204 10.1021/ja5018283. [DOI] [PubMed] [Google Scholar]
Niemeyer C. M. DNA as a material for Nanotechnology. Angew. Chem., Int. Ed. Engl. 1997, 36, 585–587 10.1002/anie.199705851. [DOI] [Google Scholar]
Seeman N. C. Nucleic Acid Nanostructures and Topology. Angew. Chem., Int. Ed. 1998, 37, 3220–3238. [DOI] [PubMed] [Google Scholar]
Seeman N. C. DNA nanotechnology: novel DNA constructions. Annu. Rev. Biophys. Biomol. Struct. 1998, 27, 225–248 10.1146/annurev.biophys.27.1.225. [DOI] [PubMed] [Google Scholar]
Seeman N. C.; Wang H.; Yang X.; Liu F.; Mao C.; Sun W.; Wenzler L.; Shen Z.; Sha R.; Yan H.; et al. New Motifs in DNA Nanotechnology. Nanotechnology 1998, 9, 257–273 10.1088/0957-4484/9/3/018. [DOI] [Google Scholar]
Yang X.; Vologodskii A. V.; Liu B.; Kemper B.; Seeman N. C. Torsional control of double-stranded DNA branch migration. Biopolymers 1998, 45, 69–83. [DOI] [PubMed] [Google Scholar]
Mao C.; Sun W.; Shen Z.; Seeman N. C. A nanomechanical device based on the B–Z transition of DNA. Nature 1999, 397, 144–146 10.1038/16437. [DOI] [PubMed] [Google Scholar]
Niemeyer C. M. Progress in “engineering up” nanotechnology devices utilizing DNA asa construction material. Appl. Phys. A: Mater. Sci. Process. 1999, 68, 119–124 10.1007/s003390050865. [DOI] [Google Scholar]
Seeman N. C. DNA engineering and its application to nanotechnology. Trends Biotechnol. 1999, 17, 437–443 10.1016/S0167-7799(99)01360-8. [DOI] [PubMed] [Google Scholar]
Niemeyer C. M. Self-assembled nanostructures based on DNA: towards the development of nanobiotechnology. Curr. Opin. Chem. Biol. 2000, 4, 609–618 10.1016/S1367-5931(00)00140-X. [DOI] [PubMed] [Google Scholar]
Seeman N. C.; Belcher A. M. Emulating biology: building nanostructures from the bottom up. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 6451–6455 10.1073/pnas.221458298. [DOI] [PMC free article] [PubMed] [Google Scholar]
Seeman N. C. At the Crossroads of Chemistry, Biology, and Materials. Chem. Biol. 2003, 10, 1151–1159 10.1016/j.chembiol.2003.12.002. [DOI] [PubMed] [Google Scholar]
Seeman N. C. DNA in a Material World. Nature 2003, 421, 427–431 10.1038/nature01406. [DOI] [PubMed] [Google Scholar]
Seeman N. C. Molecular Engineering: Nanotechnology and the Double Helix. Sci. Am. 2004, 290, 34–43. [DOI] [PubMed] [Google Scholar]
Yan H. Materials science. Nucleic acid nanotechnology. Science 2004, 306, 2048–2049 10.1126/science.1106754. [DOI] [PubMed] [Google Scholar]
Brucale M.; Zuccheri G.; Samori B. The dynamic properties of an intramolecular transition from DNA duplex to cytosine-thymine motif triplex. Org. Biomol. Chem. 2005, 3, 575–577 10.1039/b418353n. [DOI] [PubMed] [Google Scholar]
Aldaye F. A.; Palmer A. L.; Sleiman H. F. Assembling materials with DNA as the guide. Science 2008, 321, 1795–1799 10.1126/science.1154533. [DOI] [PubMed] [Google Scholar]
Gothelf K. V. Materials science. LEGO-like DNA structures. Science 2012, 338, 1159–1160 10.1126/science.1229960. [DOI] [PubMed] [Google Scholar]
Marras A. E.; Zhou L. F.; Su H. J.; Castro C. E. Programmable motion of DNA origami mechanisms. Proc. Natl. Acad. Sci. U. S. A. 2015, 112, 713–718 10.1073/pnas.1408869112. [DOI] [PMC free article] [PubMed] [Google Scholar]
Zhang D. Y.; Seelig G. Dynamic DNA nanotechnology using strand-displacement reactions. Nat. Chem. 2011, 3, 103–113 10.1038/nchem.957. [DOI] [PubMed] [Google Scholar]
Hamada S.; Murata S. Substrate-Assisted Assembly of Interconnected Single-Duplex DNA Nanostructures. Angew. Chem., Int. Ed. 2009, 48, 6820–6823 10.1002/anie.200902662. [DOI] [PubMed] [Google Scholar]
Kalle Gehring J.-L. L. a. M. G. A tetrameric DNA structure with protonated cytosine. Nature 1993, 363, 561–565 10.1038/363561a0. [DOI] [PubMed] [Google Scholar]
Chen L.; C L.; Zhang X.; Rich A. Crystal structure of a four-stranded intercalated DNA: d(C4). Biochemistry 1994, 33, 13540–13546 10.1021/bi00250a005. [DOI] [PubMed] [Google Scholar]
Alberti P.; Mergny J. L. DNA duplex-quadruplex exchange as the basis for a nanomolecular machine. Proc. Natl. Acad. Sci. U. S. A. 2003, 100, 1569–1573 10.1073/pnas.0335459100. [DOI] [PMC free article] [PubMed] [Google Scholar]
Dittmer W. U.; Reuter A.; Simmel F. C. A DNA-based machine that can cyclically bind and release thrombin. Angew. Chem., Int. Ed. 2004, 43, 3550–3553 10.1002/anie.200353537. [DOI] [PubMed] [Google Scholar]
Davis J. T.; Spada G. P. Supramolecular architectures generated by self-assembly of guanosine derivatives. Chem. Soc. Rev. 2007, 36, 296–313 10.1039/B600282J. [DOI] [PubMed] [Google Scholar]
Collie G. W.; Parkinson G. N. The application of DNA and RNA G-quadruplexes to therapeutic medicines. Chem. Soc. Rev. 2011, 40, 5867–5892 10.1039/c1cs15067g. [DOI] [PubMed] [Google Scholar]
Miyake Y.; Togashi H.; Tashiro M.; Yamaguchi M.; Oda S.; Kudo M.; Tanaka Y.; Kondo Y.; Sawa R.; Fujimoto T.; et al. Mercury^II-Mediated Formation of Thymine–Hg^II–Thymine Base Pairs in DNA Duplexes. J. Am. Chem. Soc. 2006, 128, 2172–2173 10.1021/ja056354d. [DOI] [PubMed] [Google Scholar]
Tanaka Y.; Oda S.; Yamaguchi H.; Kondo Y.; Kojima C.; Ono A. 15N–15N J-Coupling Across Hg^II: Direct Observation of Hg^II-Mediated T–T Base Pairs in a DNA Duplex. J. Am. Chem. Soc. 2007, 129, 244–245 10.1021/ja065552h. [DOI] [PubMed] [Google Scholar]
Yurke B.; Tuberfield A. J.; Mills A. P. Jr.; Simmel F. C.; Neumann J. L. A DNA-fuelled molecular machine made of DNA. Nature 2000, 406, 605–608 10.1038/35020524. [DOI] [PubMed] [Google Scholar]
Turberfield A.; Mitchell J.; Yurke B.; Mills A.; Blakey M.; Simmel F. DNA Fuel for Free-Running Nanomachines. Phys. Rev. Lett. 2003, 90, 118102. 10.1103/PhysRevLett.90.118102. [DOI] [PubMed] [Google Scholar]
Liu D.; Bruckbauer A.; Abell C.; Balasubramanian S.; Kang D.-J.; Klenerman D.; Zhou D. A Reversible pH-Driven DNA Nanoswitch Array. J. Am. Chem. Soc. 2006, 128, 2067–2071 10.1021/ja0568300. [DOI] [PubMed] [Google Scholar]
Liang X.; Nishioka H.; Takenaka N.; Asanuma H. A DNA nanomachine powered by light irradiation. ChemBioChem 2008, 9, 702–705 10.1002/cbic.200700649. [DOI] [PubMed] [Google Scholar]
Li D.; Wieckowska A.; Willner I. Optical Analysis of Hg²⁺ Ions by Oligonucleotide–Gold-Nanoparticle Hybrids and DNA-Based Machines. Angew. Chem. 2008, 120, 3991–3995 10.1002/ange.200705991. [DOI] [PubMed] [Google Scholar]
Song G.; Chen M.; Chen C.; Wang C.; Hu D.; Ren J.; Qu X. Design of proton-fueled tweezers for controlled, multi-function DNA-based molecular device. Biochimie 2010, 92, 121–127 10.1016/j.biochi.2009.10.007. [DOI] [PubMed] [Google Scholar]
Saghatelian A.; Volcker N. H.; Guckian K. M.; Lin V. S. Y.; Ghadin M. R. DNA-Based Photonic Logic Gates: AND, NAND, and INHIBIT. J. Am. Chem. Soc. 2003, 125, 346–347 10.1021/ja029009m. [DOI] [PubMed] [Google Scholar]
Okamoto A.; Tanaka K.; Saito I. DNA Logic Gates. J. Am. Chem. Soc. 2004, 126, 9458–9463 10.1021/ja047628k. [DOI] [PubMed] [Google Scholar]
Lee J. F.; Stovall G. M.; Ellington A. D. Aptamer therapeutics advance. Curr. Opin. Chem. Biol. 2006, 10, 282–289 10.1016/j.cbpa.2006.03.015. [DOI] [PubMed] [Google Scholar]
Shlyahovsky B.; Li Y.; Lioubashevski O.; Elbaz J.; Willner I. Logic Gates and Antisense DNA Devices Operating on a Translator Nucleic Acid Scaffold. ACS Nano 2009, 3, 1831–1843 10.1021/nn900085x. [DOI] [PubMed] [Google Scholar]
Wilner O. I.; Shimron S.; Weizmann Y.; Wang Z.-G.; Willner I. Self-Assembly of Enzymes on DNA Scaffolds: En Route to Biocatalytic Cascades and the Synthesis of Metallic Nanowires. Nano Lett. 2009, 9, 2040–2043 10.1021/nl900302z. [DOI] [PubMed] [Google Scholar]
Wilner O. I.; Weizmann Y.; Gill R.; Lioubashevski O.; Freeman R.; Willner I. Enzyme cascades activated on topologically programmed DNA scaffolds. Nat. Nanotechnol. 2009, 4, 249–254 10.1038/nnano.2009.50. [DOI] [PubMed] [Google Scholar]
Teller C.; Willner I. Organizing protein-DNA hybrids as nanostructures with programmed functionalities. Trends Biotechnol. 2010, 28, 619–628 10.1016/j.tibtech.2010.09.005. [DOI] [PubMed] [Google Scholar]
Qian L.; Winfree E.; Bruck J. Neural network computation with DNA strand displacement cascades. Nature 2011, 475, 368–372 10.1038/nature10262. [DOI] [PubMed] [Google Scholar]
Winfree L. Q. a. E. Scaling Up Digital Circuit Computation with DNA Strand Displacement Cascades. Science 2011, 332, 1196–1201 10.1126/science.1200520. [DOI] [PubMed] [Google Scholar]
Pei H.; Liang L.; Yao G.; Li J.; Huang Q.; Fan C. Reconfigurable Three-Dimensional DNA Nanostructures for the Construction of Intracellular Logic Sensors. Angew. Chem., Int. Ed. 2012, 51, 9020–9024 10.1002/anie.201202356. [DOI] [PubMed] [Google Scholar]
Fu Y.; Zeng D.; Chao J.; Jin Y.; Zhang Z.; Liu H.; Li D.; Ma H.; Huang Q.; Gothelf K. V.; Fan C. Single-step rapid assembly of DNA origami nanostructures for addressable nanoscale bioreactors. J. Am. Chem. Soc. 2013, 135, 696–702 10.1021/ja3076692. [DOI] [PubMed] [Google Scholar]
Miyamoto T.; Razavi S.; DeRose R.; Inoue T. Synthesizing biomolecule-based Boolean logic gates. ACS Synth. Biol. 2013, 2, 72–82 10.1021/sb3001112. [DOI] [PMC free article] [PubMed] [Google Scholar]
Gibbons A.; Amos M.; Hodgson D. DNA computing. Curr. Opin. Biotechnol. 1997, 8, 103–106 10.1016/S0958-1669(97)80164-4. [DOI] [PubMed] [Google Scholar]
Cox J. C.; Cohen D. S.; Ellington A. D. The complexities of DNA computation. Trends Biotechnol. 1999, 17, 151–154 10.1016/S0167-7799(99)01312-8. [DOI] [PubMed] [Google Scholar]
Ruben A. J.; Landweber L. F. The past, present and future of molecular computing. Nat. Rev. Mol. Cell Biol. 2000, 1, 69–72 10.1038/35036086. [DOI] [PubMed] [Google Scholar]
Gillmor S. D.; Rugheimer P. P.; Lagally M. G. Computation with DNA on surfaces. Surf. Sci. 2002, 500, 699–721 10.1016/S0039-6028(01)01524-2. [DOI] [Google Scholar]
Reif J. H. Computing: Successes and challenges. Science 2002, 296, 478–479 10.1126/science.1070978. [DOI] [PubMed] [Google Scholar]
Livstone M. S.; van Noort D.; Landweber L. F. Molecular computing revisited: a Moore’s law?. Trends Biotechnol. 2003, 21, 98–101 10.1016/S0167-7799(03)00007-6. [DOI] [PubMed] [Google Scholar]
Condon A. Automata make antisense. Nature 2004, 429, 351–352 10.1038/429351a. [DOI] [PubMed] [Google Scholar]
Hasty J.; McMillen D.; Collins J. J. Engineered gene circuits. Nature 2002, 420, 224–230 10.1038/nature01257. [DOI] [PubMed] [Google Scholar]
Kim J.; Lee J.; Hamada S.; Murata S.; Ha Park S. Self-replication of DNA rings. Nat. Nanotechnol. 2015, 10, 528–533 10.1038/nnano.2015.87. [DOI] [PubMed] [Google Scholar]
Park S. Y.; Lytton-Jean A. K.; Lee B.; Weigand S.; Schatz G. C.; Mirkin C. A. DNA-programmable nanoparticle crystallization. Nature 2008, 451, 553–556 10.1038/nature06508. [DOI] [PubMed] [Google Scholar]
Nykypanchuk D.; Maye M. M.; van der Lelie D.; Gang O. DNA-guided crystallization of colloidal nanoparticles. Nature 2008, 451, 549–552 10.1038/nature06560. [DOI] [PubMed] [Google Scholar]
Wang T.; Sha R. J.; Dreyfus R.; Leunissen M. E.; Maass C.; Pine D. J.; Chaikin P. M.; Seeman N. C. Self-replication of information-bearing nanoscale patterns. Nature 2011, 478, 225–228 10.1038/nature10500. [DOI] [PMC free article] [PubMed] [Google Scholar]
Stojanovic M. N.; Stefanovic D. A deoxyribozyme-based molecular automaton. Nat. Biotechnol. 2003, 21, 1069–1074 10.1038/nbt862. [DOI] [PubMed] [Google Scholar]
Tabor J. J.; Ellington A. D. Playing to win at DNA computation. Nat. Biotechnol. 2003, 21, 1013–1015 10.1038/nbt0903-1013. [DOI] [PubMed] [Google Scholar]
Macdonald J.; Li Y.; Sutovic M.; Lederman H.; Pendri K.; Lu W. H.; Andrews B. L.; Stefanovic D.; Stojanovic M. N. Medium scale integration of molecular logic gates in an automaton. Nano Lett. 2006, 6, 2598–2603 10.1021/nl0620684. [DOI] [PubMed] [Google Scholar]
Liu M.; Fu J.; Hejesen C.; Yang Y.; Woodbury N. W.; Gothelf K.; Liu Y.; Yan H. A DNA tweezer-actuated enzyme nanoreactor. Nat. Commun. 2013, 4, 2127. 10.1038/ncomms3127. [DOI] [PubMed] [Google Scholar]
Elbaz J.; Wang Z.-G.; Orbach R.; Willner I. pH-stimulated concurrent mechanical activation of two DNA ″tweezers″. A ″SET-RESET″ logic gate system. Nano Lett. 2009, 9, 4510–4514 10.1021/nl902859m. [DOI] [PubMed] [Google Scholar]
Wang Z.-G.; Elbaz J.; Remacle F.; Levine R. D.; Willner I. All-DNA finite-state automata with finite memory. Proc. Natl. Acad. Sci. U. S. A. 2010, 107, 21996–22001 10.1073/pnas.1015858107. [DOI] [PMC free article] [PubMed] [Google Scholar]
Xin L.; Zhou C.; Yang Z.; Liu D. Regulation of an enzyme cascade reaction by a DNA machine. Small 2013, 9, 3088–3091 10.1002/smll.201300019. [DOI] [PubMed] [Google Scholar]
Elbaz J.; Cecconello A.; Fan Z.; Govorov A. O.; Willner I. Powering the programmed nanostructure and function of gold nanoparticles with catenated DNA machines. Nat. Commun. 2013, 4, 2000. 10.1038/ncomms3000. [DOI] [PMC free article] [PubMed] [Google Scholar]
Lange H.; Juarez B. H.; Carl A.; Richter M.; Bastus N. G.; Weller H.; Thomsen C.; von Klitzing R.; Knorr A. Tunable plasmon coupling in distance-controlled gold nanoparticles. Langmuir 2012, 28, 8862–8866 10.1021/la3001575. [DOI] [PubMed] [Google Scholar]
Kuzyk A.; Schreiber R.; Fan Z.; Pardatscher G.; Roller E. M.; Hogele A.; Simmel F. C.; Govorov A. O.; Liedl T. DNA-based self-assembly of chiral plasmonic nanostructures with tailored optical response. Nature 2012, 483, 311–314 10.1038/nature10889. [DOI] [PubMed] [Google Scholar]
Liu Y.; Kuzuya A.; Sha R.; Guillaume J.; Wang R.; Canary J. W.; Seeman N. C. Coupling Across a DNA Helical Turn Yields a Hybrid DNA/Organic Catenane Doubly Tailed with Functional Termini. J. Am. Chem. Soc. 2008, 130, 10882–10883 10.1021/ja8041096. [DOI] [PMC free article] [PubMed] [Google Scholar]
Han D.; Pal S.; Liu Y.; Yan H. Folding and cutting DNA into reconfigurable topological nanostructures. Nat. Nanotechnol. 2010, 5, 712–717 10.1038/nnano.2010.193. [DOI] [PMC free article] [PubMed] [Google Scholar]
Lu C. H.; Cecconello A.; Elbaz J.; Credi A.; Willner I. A three-station DNA catenane rotary motor with controlled directionality. Nano Lett. 2013, 13, 2303–2308 10.1021/nl401010e. [DOI] [PubMed] [Google Scholar]
Samori B.; Zuccheri G. DNA codes for nanoscience. Angew. Chem., Int. Ed. 2005, 44, 1166–1181 10.1002/anie.200400652. [DOI] [PubMed] [Google Scholar]
Chen Y.; Mao C. Reprogramming DNA-directed reactions on the basis of a DNA conformational change. J. Am. Chem. Soc. 2004, 126, 13240–13241 10.1021/ja045718j. [DOI] [PubMed] [Google Scholar]
Storhoff J. J.; Mirkin C. A. Programmed materials synthesis with DNA. Chem. Rev. 1999, 99, 1849–1862 10.1021/cr970071p. [DOI] [PubMed] [Google Scholar]
Braun E.; Keren K. From DNA to transistors. Adv. Phys. 2004, 53, 441–496 10.1080/00018730412331294688. [DOI] [Google Scholar]
Wengel J. Nucleic acid nanotechnology - towards Angstrom-scale engineering. Org. Biomol. Chem. 2004, 2, 277–280 10.1039/b313986g. [DOI] [PubMed] [Google Scholar]
Feldkamp U.; Niemeyer C. M. Rational design of DNA nanoarchitectures. Angew. Chem., Int. Ed. 2006, 45, 1856–1876 10.1002/anie.200502358. [DOI] [PubMed] [Google Scholar]
Broude N. E. Stem-loop oligonucleotides: a robust tool for molecular biology and biotechnology. Trends Biotechnol. 2002, 20, 249–256 10.1016/S0167-7799(02)01942-X. [DOI] [PubMed] [Google Scholar]
Tan W. H.; Wang K. M.; Drake T. J. Molecular beacons. Curr. Opin. Chem. Biol. 2004, 8, 547–553 10.1016/j.cbpa.2004.08.010. [DOI] [PubMed] [Google Scholar]
Shen W. Q.; Bruist M. F.; Goodman S. D.; Seeman N. C. A protein-driven DNA device that measures the excess binding energy of proteins that distort DNA. Angew. Chem., Int. Ed. 2004, 43, 4750–4752 10.1002/anie.200460302. [DOI] [PubMed] [Google Scholar]
Nutiu R.; Li Y. F. A DNA-protein nanoengine for ″On-Demand″ release and precise delivery of molecules. Angew. Chem., Int. Ed. 2005, 44, 5464–5467 10.1002/anie.200501214. [DOI] [PubMed] [Google Scholar]
Loh I. Y.; Cheng J.; Tee S. R.; Efremov A.; Wang Z. S. From Bistate Molecular Switches to Self-Directed Track-Walking Nanomotors. ACS Nano 2014, 8, 10293–10304 10.1021/nn5034983. [DOI] [PubMed] [Google Scholar]
Leigh D. A.; Lewandowska U.; Lewandowski B.; Wilson M. R. Synthetic Molecular Walkers. Top. Curr. Chem. 2014, 354, 111–138 10.1007/128_2014_546. [DOI] [PubMed] [Google Scholar]
Wang C. Y.; Ren J. S.; Qu X. G. A stimuli responsive DNA walking device. Chem. Commun. 2011, 47, 1428–1430 10.1039/C0CC04234J. [DOI] [PubMed] [Google Scholar]
Liedl T.; Olapinski M.; Simmel F. C. A Surface-Bound DNA Switch Driven by a Chemical Oscillator. Angew. Chem., Int. Ed. 2006, 45, 5007–5010 10.1002/anie.200600353. [DOI] [PubMed] [Google Scholar]
Bromley E. H.; Kuwada N. J.; Zuckermann M. J.; Donadini R.; Samii L.; Blab G. A.; Gemmen G. J.; Lopez B. J.; Curmi P. M.; Forde N. R.; Woolfson D. N.; Linke H. The Tumbleweed: towards a synthetic proteinmotor. HFSP J. 2009, 3, 204–212 10.2976/1.3111282. [DOI] [PMC free article] [PubMed] [Google Scholar]
Rothemund P. W. Folding DNA to create nanoscale shapes and patterns. Nature 2006, 440, 297–302 10.1038/nature04586. [DOI] [PubMed] [Google Scholar]
Smith L. M. Nanotechnology: Molecular robots on the move. Nature 2010, 465, 167–168 10.1038/465167a. [DOI] [PubMed] [Google Scholar]
Wickham S. F.; Endo M.; Katsuda Y.; Hidaka K.; Bath J.; Sugiyama H.; Turberfield A. J. Direct observation of stepwise movement of a synthetic molecular transporter. Nat. Nanotechnol. 2011, 6, 166–169 10.1038/nnano.2010.284. [DOI] [PubMed] [Google Scholar]
Bath J.; Green S. J.; Turberfield A. J. A free-running DNA motor powered by a nicking enzyme. Angew. Chem., Int. Ed. 2005, 44, 4358–4361 10.1002/anie.200501262. [DOI] [PubMed] [Google Scholar]
Mai J.; Sokolov I. M.; Blumen A. Directed particle diffusion under ″burnt bridges″ conditions. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 2001, 64, 011102. 10.1103/PhysRevE.64.011102. [DOI] [PubMed] [Google Scholar]
Antal T.; Krapivsky P. L.. “Burnt-bridge” mechanism of molecular motor motion. Phys. Rev. E 2005, 72, 10.1103/PhysRevE.72.046104. [DOI] [PubMed] [Google Scholar]
Yin P.; Choi H. M.; Calvert C. R.; Pierce N. A. Programming biomolecular self-assembly pathways. Nature 2008, 451, 318–322 10.1038/nature06451. [DOI] [PubMed] [Google Scholar]
Green S. J.; Bath J.; Turberfield A. J. Coordinated chemomechanical cycles: a mechanism for autonomous molecular motion. Phys. Rev. Lett. 2008, 101, 238101. 10.1103/PhysRevLett.101.238101. [DOI] [PubMed] [Google Scholar]
Bath J.; Green S. J.; Allen K. E.; Turberfield A. J. Mechanism for a directional, processive, and reversible DNA motor. Small 2009, 5, 1513–1516 10.1002/smll.200900078. [DOI] [PubMed] [Google Scholar]
Pei R.; Taylor S. K.; Stefanovic D.; Rudchenko S.; Mitchell T. E.; Stojanovic M. N. Behavior of polycatalytic assemblies in a substrate-displaying matrix. J. Am. Chem. Soc. 2006, 128, 12693–12699 10.1021/ja058394n. [DOI] [PubMed] [Google Scholar]
You M.; Chen Y.; Zhang X.; Liu H.; Wang R.; Wang K.; Williams K. R.; Tan W. An autonomous and controllable light-driven DNA walking device. Angew. Chem., Int. Ed. 2012, 51, 2457–2460 10.1002/anie.201107733. [DOI] [PMC free article] [PubMed] [Google Scholar]
Kay E. R.; Leigh D. A. Rise of the Molecular Machines. Angew. Chem., Int. Ed. 2015, 54, 10080–10088 10.1002/anie.201503375. [DOI] [PMC free article] [PubMed] [Google Scholar]
Turing A. M. Proc. London Math. Soc. 1937, 42, 230–265 10.1112/plms/s2-42.1.230. [DOI] [Google Scholar]

[ref1] Brown R. A Brief Account of Microscopical Observations Made on the Particles Contained in the Pollen of Plants. Philos. Mag. 1828, 4, 171–173 10.1080/14786442808674769. [DOI] [Google Scholar]

[ref2] Brown R. On the Particles Contained in the Pollen of Plants; and on the General Existence of Active Molecules in Organic and Inorganic Bodies. Edinb. New Philos. J. 1828, 5, 358–371. [Google Scholar]

[ref3] Perrin J. In Atoms (English Translation), 2nd ed.; Hammick D. L., Ed.; Constable and Co.: London, 1923. [Google Scholar]

[ref4] Einstein A. Über die von der Molekularkinetischen Theorie der Wärme Geforderte Bewegung von in Ruhenden Flüssigkeiten Suspendierten Teilchen. Ann. Phys. 1905, 17, 549–560 10.1002/andp.19053220806. [DOI] [Google Scholar]

[ref5] Feynman R. P.; Leighton R. B.; Sands M.. The Feynman Lectures on Physics; Addison-Wesley: Reading, MA, 1963; Vol. 1, Chapter 46. [Google Scholar]

[ref6] Smalley R. E.; Drexler K. E. Nanotechnology. Chem. Eng. News 2003, 81, 37–42. [Google Scholar]

[ref7] Balzani V.; Credi A.; Raymo F. M.; Stoddart J. F. Artificial Molecular Machines. Angew. Chem., Int. Ed. 2000, 39, 3348–3391. [DOI] [PubMed] [Google Scholar]

[ref8] Credi A. Artificial Molecular Motors Powered by Light. Aust. J. Chem. 2006, 59, 157–169 10.1071/CH06025. [DOI] [Google Scholar]

[ref9] Paxton W. F.; Sundararajan S.; Mallouk T. E.; Sen A. Chemical Locomotion. Angew. Chem., Int. Ed. 2006, 45, 5420–5429 10.1002/anie.200600060. [DOI] [PubMed] [Google Scholar]

[ref10] Tian H.; Wang Q.-C. Recent Progress on Switchable Rotaxanes. Chem. Soc. Rev. 2006, 35, 361–374 10.1039/b512178g. [DOI] [PubMed] [Google Scholar]

[ref11] Leigh D.; Pérez E.. Dynamic Chirality: Molecular Shuttles and Motors. In Supramolecular Chirality; Crego-Calama M., Reinhoudt D., Eds.; Springer: Berlin, Heidelberg, 2006; Vol. 265, pp 185–208. [Google Scholar]

[ref12] Hess H. Self-assembly Driven by Molecular Motors. Soft Matter 2006, 2, 669–677 10.1039/b518281f. [DOI] [PubMed] [Google Scholar]

[ref13] Browne W. R.; Feringa B. L. Making Molecular Machines Work. Nat. Nanotechnol. 2006, 1, 25–35 10.1038/nnano.2006.45. [DOI] [PubMed] [Google Scholar]

[ref14] Kay E. R.; Leigh D. A.; Zerbetto F. Synthetic Molecular Motors and Mechanical Machines. Angew. Chem., Int. Ed. 2007, 46, 72–191 10.1002/anie.200504313. [DOI] [PubMed] [Google Scholar]

[ref15] Balzani V.; Credi A.; Venturi M. Molecular Machines Working on Surfaces and at Interfaces. ChemPhysChem 2008, 9, 202–220 10.1002/cphc.200700528. [DOI] [PubMed] [Google Scholar]

[ref16] Ma X.; Tian H. Bright Functional Rotaxanes. Chem. Soc. Rev. 2010, 39, 70–80 10.1039/B901710K. [DOI] [PubMed] [Google Scholar]

[ref17] Wang J.; Manesh K. M. Motion Control at the Nanoscale. Small 2010, 6, 338–345 10.1002/smll.200901746. [DOI] [PubMed] [Google Scholar]

[ref18] Coskun A.; Banaszak M.; Astumian R. D.; Stoddart J. F.; Grzybowski B. A. Great Expectations: Can Artificial Molecular Machines Deliver on Their Promise?. Chem. Soc. Rev. 2012, 41, 19–30 10.1039/C1CS15262A. [DOI] [PubMed] [Google Scholar]

[ref19] Yang W.; Li Y.; Liu H.; Chi L.; Li Y. Design and Assembly of Rotaxane-Based Molecular Switches and Machines. Small 2012, 8, 504–516 10.1002/smll.201101738. [DOI] [PubMed] [Google Scholar]

[ref20] Neal E. A.; Goldup S. M. Chemical Consequences of Mechanical Bonding in Catenanes and Rotaxanes: Isomerism, Modification, Catalysis and Molecular Machines for Synthesis. Chem. Commun. 2014, 50, 5128–5142 10.1039/c3cc47842d. [DOI] [PubMed] [Google Scholar]

[ref21] van Dongen S. F. M.; Cantekin S.; Elemans J. A. A. W.; Rowan A. E.; Nolte R. J. M. Functional Interlocked Systems. Chem. Soc. Rev. 2014, 43, 99–122 10.1039/C3CS60178A. [DOI] [PubMed] [Google Scholar]

[ref22] Zhang M. M.; Yan X. Z.; Huang F. H.; Niu Z. B.; Gibson H. W. Stimuli-Responsive Host-Guest Systems Based on the Recognition of Cryptands by Organic Guests. Acc. Chem. Res. 2014, 47, 1995–2005 10.1021/ar500046r. [DOI] [PubMed] [Google Scholar]

[ref23] Xue M.; Yang Y.; Chi X. D.; Zhang Z. B.; Huang F. H. New Class of Macrocycles for Supramolecular Chemistry. Acc. Chem. Res. 2012, 45, 1294–1308 10.1021/ar2003418. [DOI] [PubMed] [Google Scholar]

[ref24] Gil-Ramirez G.; Leigh D. A.; Stephens A. J. Catenanes Fifty Years of Molecular Links. Angew. Chem., Int. Ed. 2015, 54, 6110–6150 10.1002/anie.201411619. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref25] Colinvaux P. Life at Low Reynolds-Number. Nature 1979, 277, 353–354 10.1038/277353a0. [DOI] [Google Scholar]

[ref26] Purcell E. M. Life at Low Reynolds-Number. Am. J. Phys. 1977, 45, 3–11 10.1119/1.10903. [DOI] [Google Scholar]

[ref27] Shenker O. R. Maxwell’s Demon 2: Entropy, Classical and Quantum Information, Computing. Stud. Hist. Philos. M. P. 2004, 35B, 537–540 10.1016/j.shpsb.2004.04.001. [DOI] [Google Scholar]

[ref28] Maxwell J. C.Theory of Heat; Longmans, Green and Co.: London, 1871; Chapter 22. [Google Scholar]

[ref29] Smoluchowski M. S. On Opalescence of Gases in the Critical State. Philos. Mag. 1912, 23, 165–173 10.1080/14786440108637209. [DOI] [Google Scholar]

[ref30] Feynman R. P.; Vernon F. L. The Theory of a General Quantum System Interacting with a Linear Dissipative System. Ann. Phys. 1963, 24, 118–173 10.1016/0003-4916(63)90068-X. [DOI] [Google Scholar]

[ref31] Ehrenberg W. Maxwell’s Demon. Sci. Am. 1967, 217, 103–110 10.1038/scientificamerican1167-103. [DOI] [Google Scholar]

[ref32] For the first private written discussion of the “temperature demon”, see:; Maxwell J. C.Letter to P. G. Tait, 11 December 1867; quoted in C. G. Knott, Life and Scientific Work of Peter Guthrie Tait; Cambridge University Press: London, 1911; p 213; [Google Scholar]; and reproduced in: The Scientific Letters and Papers of James Clerk Maxwell 1862; Harman P. M., Ed.; Cambridge University Press: Cambridge, 1995; Vol. II, p 331. [Google Scholar]

[ref33] Szilard L. On the Minimization of Entropy in a Thermodynamic System with Interferences of Intelligent Beings. Eur. Phys. J. A 1929, 53, 840–856 10.1007/BF01341281. [DOI] [Google Scholar]

[ref34] Bennett C. The Thermodynamics of Computation—A Review. Int. J. Theor. Phys. 1982, 21, 905–940 10.1007/BF02084158. [DOI] [Google Scholar]

[ref35] Landauer R. Irreversibility and Heat Generation in the Computing Process. IBM J. Res. Dev. 1961, 5, 183–191 10.1147/rd.53.0183. [DOI] [Google Scholar]

[ref36] Berut A.; Arakelyan A.; Petrosyan A.; Ciliberto S.; Dillenschneider R.; Lutz E. Experimental Verification of Landauer’s Principle Linking Information and Thermodynamics. Nature 2012, 483, 187–189 10.1038/nature10872. [DOI] [PubMed] [Google Scholar]

[ref37] The idea of a “pressure demon” was introduced by Maxwell in a later letter to Tait (believed to date from early 1875); quoted in: Knott C. G.Life and Scientific Work of Peter Guthrie Tait; Cambridge University Press: London, Cambridge, 1911; p 214; and reproduced in: The Scientific Letters and Papers of James Clerk Maxwell 1874; Harman P. M., Ed.; Cambridge University Press: London, Cambridge, 2002; Vol. III, p 185. [Google Scholar]

[ref38] Zheng J. Z.; Zheng X.; Zhao Y.; Xie Y.; Yam C. Y.; Chen G. H.; Jiang Q.; Chwang A. T. Maxwell’s Demon and Smoluchowski’s Trap Door (vol 75, art no 041109, 2007). Phys. Rev. E 2007, 75, 041109. 10.1103/PhysRevE.75.041109. [DOI] [PubMed] [Google Scholar]

[ref39] Skordos P. A.; Zurek W. H. Maxwell’s Demon, Rectifiers, and the Second Law: Computer Simulation of Smoluchowski’s Trapdoor. Am. J. Phys. 1992, 60, 876–882 10.1119/1.17007. [DOI] [Google Scholar]

[ref40] Parrondo J. M. R.; Espanol P. Criticism of Feynman’s Analysis of the Ratchet as an Engine. Am. J. Phys. 1996, 64, 1125–1130 10.1119/1.18393. [DOI] [Google Scholar]

[ref41] Sakaguchi H. A Langevin Simulation for the Feynman Ratchet Model. J. Phys. Soc. Jpn. 1998, 67, 709–712 10.1143/JPSJ.67.709. [DOI] [Google Scholar]

[ref42] Hondou T.; Takagi F. Irreversible Operation in a Stalled State of Feynman’s Ratchet. J. Phys. Soc. Jpn. 1998, 67, 2974–2976 10.1143/JPSJ.67.2974. [DOI] [Google Scholar]

[ref43] Magnasco M. O.; Stolovitzky G. Feynman’s Ratchet and Pawl. J. Stat. Phys. 1998, 93, 615–632 10.1023/B:JOSS.0000033245.43421.14. [DOI] [Google Scholar]

[ref44] Jarzynski C.; Mazonka O. Feynman’s Ratchet and Pawl: An Exactly Solvable Model. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1999, 59, 6448–6459 10.1103/PhysRevE.59.6448. [DOI] [PubMed] [Google Scholar]

[ref45] Jahn R.; Fasshauer D. Molecular Machines Governing Exocytosis of Synaptic Vesicles. Nature 2012, 490, 201–207 10.1038/nature11320. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref46] Piccolino M. Biological Machines: From Mills to Molecules. Nat. Rev. Mol. Cell Biol. 2000, 1, 149–153 10.1038/35040097. [DOI] [PubMed] [Google Scholar]

[ref47] Kinbara K.; Aida T. Toward Intelligent Molecular Machines: Directed Motions of Biological and Artificial Molecules and Assemblies. Chem. Rev. 2005, 105, 1377–1400 10.1021/cr030071r. [DOI] [PubMed] [Google Scholar]

[ref48] Pomorski T.; Hrafnsdóttir S.; Devaux P. F.; Meer G. V. Lipid Distribution and Transport Across Cellular Membranes. Semin. Cell Dev. Biol. 2001, 12, 139–148 10.1006/scdb.2000.0231. [DOI] [PubMed] [Google Scholar]

[ref49] Haydon D. A.; Hladky S. B. Ion Transport Across Thin Lipid Membranes: A Critical Discussion of Mechanisms in Selected Systems. Q. Rev. Biophys. 1972, 5, 187–282 10.1017/S0033583500000883. [DOI] [PubMed] [Google Scholar]

[ref50] Whittam R.; Wheeler K. P. Transport Across Cell Membranes. Annu. Rev. Physiol. 1970, 32, 21–60 10.1146/annurev.ph.32.030170.000321. [DOI] [PubMed] [Google Scholar]

[ref51] Gouaux E.; MacKinnon R. Principles of Selective Ion Transport in Channels and Pumps. Science 2005, 310, 1461–1465 10.1126/science.1113666. [DOI] [PubMed] [Google Scholar]

[ref52] Jorgensen P. L.; Hakansson K. O.; Karlish S. J. D. Structure and Mechanism of Na,K-ATPase: Functional Sites and Their Interactions. Annu. Rev. Physiol. 2003, 65, 817–849 10.1146/annurev.physiol.65.092101.142558. [DOI] [PubMed] [Google Scholar]

[ref53] Hayashi S.; Ueno H.; Shaikh A. R.; Umemura M.; Kamiya M.; Ito Y.; Ikeguchi M.; Komoriya Y.; Iino R.; Noji H. Molecular Mechanism of ATP Hydrolysis in F₁-ATPase Revealed by Molecular Simulations and Single-Molecule Observations. J. Am. Chem. Soc. 2012, 134, 8447–8454 10.1021/ja211027m. [DOI] [PubMed] [Google Scholar]

[ref54] Nakanishi-Matsui M.; Sekiya M.; Nakamoto R. K.; Futai M. The Mechanism of Rotating Proton Pumping ATPases. Biochim. Biophys. Acta, Bioenerg. 2010, 1797, 1343–1352 10.1016/j.bbabio.2010.02.014. [DOI] [PubMed] [Google Scholar]

[ref55] von Ballmoos C.; Wiedenmann A.; Dimroth P. Essentials for ATP Synthesis by F₁F₀ ATP Synthases. Annu. Rev. Biochem. 2009, 78, 649–672 10.1146/annurev.biochem.78.081307.104803. [DOI] [PubMed] [Google Scholar]

[ref56] Nyblom M.; Poulsen H.; Gourdon P.; Reinhard L.; Andersson M.; Lindahl E.; Fedosova N.; Nissen P. Crystal Structure of Na⁺, K⁺-ATPase in the Na⁺-Bound State. Science 2013, 342, 123–127 10.1126/science.1243352. [DOI] [PubMed] [Google Scholar]

[ref57] Nakamoto R. K.; Scanlon J. A. B.; Al-Shawi M. K. The Rotary Mechanism of the ATP Synthase. Arch. Biochem. Biophys. 2008, 476, 43–50 10.1016/j.abb.2008.05.004. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref58] Toyoshima C.; Inesi G. Structural Basis of Ion Pumping by Ca²⁺-ATPase of the Sarcoplasmic Reticulum. Annu. Rev. Biochem. 2004, 73, 269–292 10.1146/annurev.biochem.73.011303.073700. [DOI] [PubMed] [Google Scholar]

[ref59] Kastritis P. L.; Bonvin A. M. J. J. On the Binding of Macromolecular Interactions: Daring to Ask Why Proteins Interact. J. R. Soc., Interface 2012, 10, 20120835. 10.1098/rsif.2012.0835. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref60] Maloney P. C.; Kashket E. R.; Wilson T. H. A Protonmotive Force Drives ATP Synthesis in Bacteria. Proc. Natl. Acad. Sci. U. S. A. 1974, 71, 3896–3900 10.1073/pnas.71.10.3896. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref61] Møller J. V.; Nissen P.; Sørensen T. L. M.; Maire M. l. Transport Mechanism of the Sarcoplasmic Reticulum Ca²⁺-ATPase Pump. Curr. Opin. Struct. Biol. 2005, 15, 387–393 10.1016/j.sbi.2005.06.005. [DOI] [PubMed] [Google Scholar]

[ref62] Birge R. R. Nature of the Primary Photochemical Events in Rhodopsin and Bacteriorhodopsin. Biochim. Biophys. Acta, Bioenerg. 1990, 1016, 293–327 10.1016/0005-2728(90)90163-X. [DOI] [PubMed] [Google Scholar]

[ref63] Neutze R.; Pebay-Peyroula E.; Edman K.; Royant A.; Navarro J.; Landau E. M. Bacteriorhodopsin: A High-resolution Structural View of Vectorial Proton Transport. Biochim. Biophys. Acta, Biomembr. 2002, 1565, 144–167 10.1016/S0005-2736(02)00566-7. [DOI] [PubMed] [Google Scholar]

[ref64] Lanyi J. K.; Luecke H. Bacteriorhodopsin. Curr. Opin. Struct. Biol. 2001, 11, 415–419 10.1016/S0959-440X(00)00226-8. [DOI] [PubMed] [Google Scholar]

[ref65] Shibata M.; Yamashita H.; Uchihashi T.; Kandori H.; Ando T. High-speed Atomic Force Microscopy Shows Dynamic Molecular Processes in Photoactivated Bacteriorhodopsin. Nat. Nanotechnol. 2010, 5, 208–212 10.1038/nnano.2010.7. [DOI] [PubMed] [Google Scholar]

[ref66] Hirai T.; Subramaniam S. Protein Conformational Changes in the Bacteriorhodopsin Photocycle: Comparison of Findings from Electron and X-Ray Crystallographic Analyses. PLoS One 2009, 4, e5769. 10.1371/journal.pone.0005769. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref67] Haupts U.; Tittor J.; Oesterhelt D. Closing in on Bactereorhodopsin: Progress in Understanding the Molecule. Annu. Rev. Biophys. Biomol. Struct. 1999, 28, 367–399 10.1146/annurev.biophys.28.1.367. [DOI] [PubMed] [Google Scholar]

[ref68] Yonath A. Hibernating Bears, Antibiotics, and the Evolving Ribosome (Nobel Lecture). Angew. Chem., Int. Ed. 2010, 49, 4340–4354 10.1002/anie.201001297. [DOI] [PubMed] [Google Scholar]

[ref69] Ramakrishnan V. Unraveling the Structure of the Ribosome (Nobel Lecture). Angew. Chem., Int. Ed. 2010, 49, 4355–4380 10.1002/anie.201001436. [DOI] [PubMed] [Google Scholar]

[ref70] Steitz T. A. From the Structure and Function of the Ribosome to New Antibiotics (Nobel Lecture). Angew. Chem., Int. Ed. 2010, 49, 4381–4398 10.1002/anie.201000708. [DOI] [PubMed] [Google Scholar]

[ref71] Bruck I.; O’Donnell M. The Ring-type Polymerase Sliding Clamp Family. Genome Biol. 2001, 2, reviews3001.1–reviews3001.3 10.1186/gb-2001-2-1-reviews3001. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref72] Astumian R. D. Comment: Detailed Balance Revisited. Phys. Chem. Chem. Phys. 2009, 11, 9592–9594 10.1039/b911608g. [DOI] [PubMed] [Google Scholar]

[ref73] Astumian R. D. Adiabatic Operation of a Molecular Machine. Proc. Natl. Acad. Sci. U. S. A. 2007, 104, 19715–19718 10.1073/pnas.0708040104. [DOI] [Google Scholar]

[ref74] Mattia E.; Otto S. Supramolecular Systems Chemistry. Nat. Nanotechnol. 2015, 10, 111–119 10.1038/nnano.2014.337. [DOI] [PubMed] [Google Scholar]

[ref75] Chatterjee M. N.; Kay E. R.; Leigh D. A. Beyond Switches: Ratcheting a Particle Energetically Uphill with a Compartmentalized Molecular Machine. J. Am. Chem. Soc. 2006, 128, 4058–4073 10.1021/ja057664z. [DOI] [PubMed] [Google Scholar]

[ref76] Astumian R. D. Stochastic Conformational Pumping: A Mechanism for Free-energy Transduction by Molecules. Annu. Rev. Biophys. 2011, 40, 289–313 10.1146/annurev-biophys-042910-155355. [DOI] [PubMed] [Google Scholar]

[ref77] Astumian R. D. Microscopic Reversibility as the Organizing Principle of Molecular Machines. Nat. Nanotechnol. 2012, 7, 684–688 10.1038/nnano.2012.188. [DOI] [PubMed] [Google Scholar]

[ref78] Simon M. S.; Peskin C. S.; Oster G. F. What Drives the Translocation of Proteins?. Proc. Natl. Acad. Sci. U. S. A. 1992, 89, 3770–3774 10.1073/pnas.89.9.3770. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref79] Astumian R. D. Thermodynamics and Kinetics of a Brownian Motor. Science 1997, 276, 917–922 10.1126/science.276.5314.917. [DOI] [PubMed] [Google Scholar]

[ref80] Bier M. Brownian Ratchets in Physics and Biology. Contemp. Phys. 1997, 38, 371–379 10.1080/001075197182180. [DOI] [Google Scholar]

[ref81] Juelicher F.; Ajdari A.; Prost J. Modeling Molecular Motors. Rev. Mod. Phys. 1997, 69, 1269–1281 10.1103/RevModPhys.69.1269. [DOI] [Google Scholar]

[ref82] Astumian R. D. Making Molecules into Motors. Sci. Am. 2001, 285, 56–64 10.1038/scientificamerican0701-56. [DOI] [PubMed] [Google Scholar]

[ref83] Lipowsky R.; Jaster N. Molecular Motor Cycles: From Ratchets to Networks. J. Stat. Phys. 2003, 110, 1141–1167 10.1023/A:1022101011650. [DOI] [Google Scholar]

[ref84] Parrondo J. M. R.; Dinís L. Brownian Motion and Gambling: From Ratchets to Paradoxical Games. Contemp. Phys. 2004, 45, 147–157 10.1080/00107510310001644836. [DOI] [Google Scholar]

[ref85] Astumian R. D. Design Principles for Brownian Molecular Machines: How to Swim in Molasses and Walk in a Hurricane. Phys. Chem. Chem. Phys. 2007, 9, 5067–5083 10.1039/b708995c. [DOI] [PubMed] [Google Scholar]

[ref86] Parrondo J. M. R.; de Cisneros B. J. Energetics of Brownian Motors: A Review. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 179–191 10.1007/s003390201332. [DOI] [Google Scholar]

[ref87] Reimann P.; Hänggi P. Introduction to the Physics of Brownian Motors. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 169–178 10.1007/s003390201331. [DOI] [Google Scholar]

[ref88] Landauer R. Inadequacy of Entropy and Entropy Derivatives in Characterizing the Steady State. Phys. Rev. A: At., Mol., Opt. Phys. 1975, 12, 636–638 10.1103/PhysRevA.12.636. [DOI] [Google Scholar]

[ref89] Büttiker M. Transport as a Consequence of State-dependent Diffusion. Z. Phys. B: Condens. Matter 1987, 68, 161–167 10.1007/BF01304221. [DOI] [Google Scholar]

[ref90] Landauer R. Motion out of Noisy States. J. Stat. Phys. 1988, 53, 233–248 10.1007/BF01011555. [DOI] [Google Scholar]

[ref91] Van Kampen N. G. Relative Stability in Nonuniform Temperature. IBM J. Res. Dev. 1988, 32, 107–111 10.1147/rd.321.0107. [DOI] [Google Scholar]

[ref92] Sinha K.; Moss F. Analog Simulation of a Simple System with State-dependent Diffusion. J. Stat. Phys. 1989, 54, 1411–1423 10.1007/BF01044724. [DOI] [Google Scholar]

[ref93] Rousselet J.; Salome L.; Ajdari A.; Prostt J. Directional Motion of Brownian Particles Induced by a Periodic Asymmetric Potential. Nature 1994, 370, 446–447 10.1038/370446a0. [DOI] [PubMed] [Google Scholar]

[ref94] Faucheux L. P.; Bourdieu L. S.; Kaplan P. D.; Libchaber A. J. Optical Thermal Ratchet. Phys. Rev. Lett. 1995, 74, 1504–1507 10.1103/PhysRevLett.74.1504. [DOI] [PubMed] [Google Scholar]

[ref95] Faucheux L. P.; Libchaber A. Selection of Brownian Particles. J. Chem. Soc., Faraday Trans. 1995, 91, 3163–3166 10.1039/ft9959103163. [DOI] [Google Scholar]

[ref96] Faucheux L. P.; Stolovitzky G.; Libchaber A. Periodic Forcing of a Brownian Particle. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1995, 51, 5239–5250 10.1103/PhysRevE.51.5239. [DOI] [PubMed] [Google Scholar]

[ref97] Astumian R. D.; Bier M. Mechanochemical Coupling of the Motion of Molecular Motors to ATP Hydrolysis. Biophys. J. 1996, 70, 637–653 10.1016/S0006-3495(96)79605-4. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref98] Gorre L.; Ioannidis E.; Silberzan P. Rectified Motion of a Mercury Drop in an Asymmetric Structure. Europhys. Lett. 1996, 33, 267–272 10.1209/epl/i1996-00331-2. [DOI] [Google Scholar]

[ref99] Zhou H.-X.; Chen Y.-D. Chemically Driven Motility of Brownian Particles. Phys. Rev. Lett. 1996, 77, 194–197 10.1103/PhysRevLett.77.194. [DOI] [PubMed] [Google Scholar]

[ref100] Gorre-Talini L.; Jeanjean S.; Silberzan P. Sorting of Brownian Particles by the Pulsed Application of an Asymmetric Potential. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1997, 56, 2025–2034 10.1103/PhysRevE.56.2025. [DOI] [Google Scholar]

[ref101] Gorre-Talini L.; Silberzan P. Force-Free Motion of a Mercury Drop Alternatively Submitted to Shifted Asymmetric Potentials. J. Phys. I (France) 1997, 7, 1475–1485. [Google Scholar]

[ref102] Astumian R. D.; Derényi I. Fluctuation Driven Transport and Models of Molecular Motors and Pumps. Eur. Biophys. J. 1998, 27, 474–489 10.1007/s002490050158. [DOI] [PubMed] [Google Scholar]

[ref103] Gorre-Talini L.; Spatz J. P.; Silberzan P. Dielectrophoretic Ratchets. Chaos 1998, 8, 650–656 10.1063/1.166347. [DOI] [PubMed] [Google Scholar]

[ref104] Linke H.; Sheng W.; Löfgren A.; Hongqi X.; Omling P.; Lindelof P. E. A Quantum Dot Ratchet: Experiment and Theory. Europhys. Lett. 1998, 44, 341–347 10.1209/epl/i1998-00562-1. [DOI] [Google Scholar]

[ref105] Lorke A.; Wimmer S.; Jager B.; Kotthaus J. P.; Wegscheider W.; Bichler M. Far-infrared and Transport Properties of Antidot Arrays with Broken Symmetry. Phys. B 1998, 249–251, 312–316 10.1016/S0921-4526(98)00121-5. [DOI] [Google Scholar]

[ref106] Bekele M.; Rajesh S.; Ananthakrishna G.; Kumar N. Effect of Landauer’s Blow Torch on the Equilibration Rate in a Bistable Potential. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1999, 59, 143–149 10.1103/PhysRevE.59.143. [DOI] [Google Scholar]

[ref107] Derényi I.; Bier M.; Astumian R. D. Generalized Efficiency and its Application to Microscopic Engines. Phys. Rev. Lett. 1999, 83, 903–906 10.1103/PhysRevLett.83.903. [DOI] [Google Scholar]

[ref108] Linke H.; Humphrey T. E.; Löfgren A.; Sushkov A. O.; Newbury R.; Taylor R. P.; Omling P. Experimental Tunneling Ratchets. Science 1999, 286, 2314–2317 10.1126/science.286.5448.2314. [DOI] [PubMed] [Google Scholar]

[ref109] Mennerat-Robilliard C.; Lucas D.; Guibal S.; Tabosa J.; Jurczak C.; Courtois J. Y.; Grynberg G. Ratchet for Cold Rubidium Atoms: The Asymmetric Optical Lattice. Phys. Rev. Lett. 1999, 82, 851–854 10.1103/PhysRevLett.82.851. [DOI] [Google Scholar]

[ref110] Parmeggiani A.; Jülicher F.; Ajdari A.; Prost J. Energy Transduction of Isothermal Ratchets: Generic Aspects and Specific Examples Close to and Far from Equilibrium. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 1999, 60, 2127–2140 10.1103/PhysRevE.60.2127. [DOI] [PubMed] [Google Scholar]

[ref111] Switkes M.; Marcus C. M.; Campman K.; Gossard A. C. An Adiabatic Quantum Electron Pump. Science 1999, 283, 1905–1908 10.1126/science.283.5409.1905. [DOI] [PubMed] [Google Scholar]

[ref112] van Oudenaarden A.; Boxer S. G. Brownian Ratchets: Molecular Separations in Lipid Bilayers Supported on Patterned Arrays. Science 1999, 285, 1046–1048 10.1126/science.285.5430.1046. [DOI] [PubMed] [Google Scholar]

[ref113] Linke H.; Sheng W. D.; Svensson A.; Löfgren A.; Christensson L.; Xu H. Q.; Omling P.; Lindelof P. E. Asymmetric Nonlinear Conductance of Quantum Dots with Broken Inversion Symmetry. Phys. Rev. B: Condens. Matter Mater. Phys. 2000, 61, 15914–15926 10.1103/PhysRevB.61.15914. [DOI] [Google Scholar]

[ref114] Lipowsky R.Molecular Motors and Stochastic Models. In Stochastic Processes in Physics, Chemistry, and Biology; Freund J., Pöschel T., Eds.; Springer: Berlin Heidelberg, 2000; Vol. 557, pp 21–31. [Google Scholar]

[ref115] Mahadevan L.; Matsudaira P. Motility Powered by Supramolecular Springs and Ratchets. Science 2000, 288, 95–99 10.1126/science.288.5463.95. [DOI] [PubMed] [Google Scholar]

[ref116] Bustamante C.; Keller D.; Oster G. The Physics of Molecular Motors. Acc. Chem. Res. 2001, 34, 412–420 10.1021/ar0001719. [DOI] [PubMed] [Google Scholar]

[ref117] Höhberger E. M.; Lorke A.; Wegscheider W.; Bichler M. Adiabatic Pumping of Two-dimensional Electrons in a Ratchet-type Lateral Superlattice. Appl. Phys. Lett. 2001, 78, 2905–2907 10.1063/1.1355672. [DOI] [Google Scholar]

[ref118] Astumian R. D. Protein Conformational Fluctuations and Free-energy Transduction. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 193–206 10.1007/s003390201406. [DOI] [Google Scholar]

[ref119] Linke H.; Humphrey T. E.; Lindelof P. E.; Löfgren A.; Newbury R.; Omling P.; Sushkov A. O.; Taylor R. P.; Xu H. Quantum Ratchets and Quantum Heat Pumps. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 237–246 10.1007/s003390201335. [DOI] [Google Scholar]

[ref120] Marquet C.; Buguin A.; Talini L.; Silberzan P. Rectified Motion of Colloids in Asymmetrically Structured Channels. Phys. Rev. Lett. 2002, 88, 168301. 10.1103/PhysRevLett.88.168301. [DOI] [PubMed] [Google Scholar]

[ref121] Huang L. R.; Cox E. C.; Austin R. H.; Sturm J. C. Tilted Brownian Ratchet for DNA Analysis. Anal. Chem. 2003, 75, 6963–6967 10.1021/ac0348524. [DOI] [PubMed] [Google Scholar]

[ref122] Matthias S.; Muller F. Asymmetric Pores in a Silicon Membrane Acting as Massively Parallel Brownian Ratchets. Nature 2003, 424, 53–57 10.1038/nature01736. [DOI] [PubMed] [Google Scholar]

[ref123] Mogilner A.; Oster G. Polymer Motors: Pushing out the Front and Pulling up the Back. Curr. Biol. 2003, 13, R721–R733 10.1016/j.cub.2003.08.050. [DOI] [PubMed] [Google Scholar]

[ref124] Oster G.; Wang H. Rotary Protein Motors. Trends Cell Biol. 2003, 13, 114–121 10.1016/S0962-8924(03)00004-7. [DOI] [PubMed] [Google Scholar]

[ref125] Kurzyński M.; Chełminiak P. Stochastic Action of Actomyosin Motor. Phys. A 2004, 336, 123–132 10.1016/j.physa.2004.01.017. [DOI] [Google Scholar]

[ref126] de Souza Silva C. C.; Van de Vondel J.; Morelle M.; Moshchalkov V. V. Controlled Multiple Reversals of a Ratchet Effect. Nature 2006, 440, 651–654 10.1038/nature04595. [DOI] [PubMed] [Google Scholar]

[ref127] Linke H.; Downton M. T.; Zuckermann M. J. Performance Characteristics of Brownian Motors. Chaos 2005, 15, 26111. 10.1063/1.1871432. [DOI] [PubMed] [Google Scholar]

[ref128] Reimann P. Brownian Motors: Noisy Transport Far from Equilibrium. Phys. Rep. 2002, 361, 57–265 10.1016/S0370-1573(01)00081-3. [DOI] [Google Scholar]

[ref129] Gabryś B. J.; Pesz K.; Bartkiewicz S. J. Brownian Motion, Molecular Motors and Ratchets. Phys. A 2004, 336, 112–122 10.1016/j.physa.2004.01.016. [DOI] [Google Scholar]

[ref130] Mislow K. Stereochemical Consequences of Correlated Rotation in Molecular Propellers. Acc. Chem. Res. 1976, 9, 26–33 10.1021/ar50097a005. [DOI] [Google Scholar]

[ref131] Rappoport Z.; Biali S. E. Sterically Crowded Stable Simple Enols. Acc. Chem. Res. 1988, 21, 442–449 10.1021/ar00156a002. [DOI] [Google Scholar]

[ref132] Rappoport Z.; Biali S. E. Threshold Rotational Mechanisms and Enantiomerization Barriers of Polyarylvinyl Propellers. Acc. Chem. Res. 1997, 30, 307–314 10.1021/ar960216z. [DOI] [Google Scholar]

[ref133] Wolf C.Dynamic Stereochemistry of Chiral Compounds; RSC Publishing: UK, 2008; Chapter 8, pp 399–443. [Google Scholar]

[ref134] Gust D.; Mislow K. Analysis of Isomerization in Compounds Displaying Restricted Rotation of Aryl Groups. J. Am. Chem. Soc. 1973, 95, 1535–1547 10.1021/ja00786a031. [DOI] [Google Scholar]

[ref135] Mislow K.; Gust D.; Finocchiaro P.; Boettcher R.. Stereochemical Correspondence Among Molecular Propellers. Stereochemistry I; Springer: Berlin, Heidelberg, 1974; Vol. 47, pp 1–28. [Google Scholar]

[ref136] Katoono R.; Kawai H.; Fujiwara K.; Suzuki T. Dynamic Molecular Propeller: Supramolecular Chirality Sensing by Enhanced Chiroptical Response through the Transmission of Point Chirality to Mobile Helicity. J. Am. Chem. Soc. 2009, 131, 16896–16904 10.1021/ja906810b. [DOI] [PubMed] [Google Scholar]

[ref137] Driesschaert B.; Robiette R.; Le Duff C. S.; Collard L.; Robeyns K.; Gallez B.; Marchand-Brynaert J. Configurationally Stable Tris(tetrathioaryl)methyl Molecular Propellers. Eur. J. Org. Chem. 2012, 6517–6525 10.1002/ejoc.201200801. [DOI] [Google Scholar]

[ref138] Katoono R.; Kawai H.; Ohkita M.; Fujiwara K.; Suzuki T. A C(3)-symmetric Chiroptical Molecular Propeller Based on Hexakis(phenylethynyl)benzene with a Threefold Terephthalamide: Stereospecific Propeller Generation Through the Cooperative Transmission of Point Chiralities on the Host and Guest upon Complexation. Chem. Commun. 2013, 49, 10352–10354 10.1039/c3cc43571g. [DOI] [PubMed] [Google Scholar]

[ref139] Finocchiaro P.; Gust D.; Mislow K. Structure and Dynamic Stereochemistry of Trimesitylmethane. I. Synthesis and Nuclear Magnetic Resonance Studies. J. Am. Chem. Soc. 1974, 96, 2165–2167 10.1021/ja00814a028. [DOI] [Google Scholar]

[ref140] O̅ki M. Unusually High Barriers to Rotation Involving the Tetrahedral Carbon Atom. Angew. Chem., Int. Ed. Engl. 1976, 15, 87–93 10.1002/anie.197600871. [DOI] [Google Scholar]

[ref141] Yamamoto G.; O̅ki M. Dual Mechanisms of the Aryl Group Rotation in 9-(3,5-dimethylbenzyl) Triptycene Derivatives. Chem. Lett. 1979, 1251–1254 10.1246/cl.1979.1251. [DOI] [Google Scholar]

[ref142] Yamamoto G.; O̅ki M. Two Consecutive Gear Motions in Conformational Interconversion in 9-(2-methylbenzyl)triptycene Derivatives. Chem. Lett. 1979, 1255–1258 10.1246/cl.1979.1255. [DOI] [Google Scholar]

[ref143] Yamaoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. XXXV. Stereodynamics of 9-(3,5-Dimethylbenzyl)triptycene Derivatives. Bull. Chem. Soc. Jpn. 1981, 54, 473–480 10.1246/bcsj.54.473. [DOI] [Google Scholar]

[ref144] Yamamoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. XXXVI. Stereodynamics of 9-(2-MethylbenzyI)triptycene Derivatives. Bull. Chem. Soc. Jpn. 1981, 54, 481–487 10.1246/bcsj.54.481. [DOI] [Google Scholar]

[ref145] Yamamoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. Part 46. Correlated Rotation in 9-(2,4,6-trimethylbenzyl)triptycenes. Direct and Roundabout Enantiomerization-diastereomerization Processes. J. Org. Chem. 1983, 48, 1233–1236 10.1021/jo00156a017. [DOI] [Google Scholar]

[ref146] Yamamoto G. Molecular Gears with Two-toothed and Three-toothed Wheels. J. Mol. Struct. 1985, 126, 413–420 10.1016/0022-2860(85)80130-7. [DOI] [Google Scholar]

[ref147] Yamamoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. LVII. Stereodynamics of 9-(2-Alkylphenoxy)-1,4-dimethyltriptycenes. Bull. Chem. Soc. Jpn. 1985, 58, 1953–1961 10.1246/bcsj.58.1953. [DOI] [Google Scholar]

[ref148] Yamamoto G.; O̅ki M. Restricted Rotation Involving the Tetrahedral Carbon. LIX. Stereodynamics of Singly peri-Substituted 9-(3,5-Dimethylphenoxy)triptycene Derivatives. Bull. Chem. Soc. Jpn. 1986, 59, 3597–3603 10.1246/bcsj.59.3597. [DOI] [Google Scholar]

[ref149] Yamamoto G. Detailed Dynamic NMR Study of a Molecular Gear, 1-Methoxy-9-(3,5-dimethylbenzyl)triptycene. Bull. Chem. Soc. Jpn. 1989, 62, 4058–4060 10.1246/bcsj.62.4058. [DOI] [Google Scholar]

[ref150] Hiizu Iwamura K. M. Stereochemical Consequences of Dynamic Gearing. Acc. Chem. Res. 1988, 21, 175–182 10.1021/ar00148a007. [DOI] [Google Scholar]

[ref151] Kawada Y.; Iwamura H. Unconventional Synthesis and Conformational Flexibility of Bis(1-triptycyl) ether. J. Org. Chem. 1980, 45, 2548–2550 10.1021/jo01300a069. [DOI] [Google Scholar]

[ref152] Kawada Y.; Iwamura H. Bis(4-chloro-1-triptycyl) ether. Separation of a Pair of Phase Isomers of Labeled Bevel Gears. J. Am. Chem. Soc. 1981, 103, 958–960 10.1021/ja00394a049. [DOI] [Google Scholar]

[ref153] Kawada Y.; Iwamura H. Bis(4-chloro-1-triptycyl) ether. Separation of a Pair of Phase Isomers of Labeled Bevel Gears. Tetrahedron Lett. 1981, 22, 1533–1536 10.1016/S0040-4039(01)90370-3. [DOI] [Google Scholar]

[ref154] Kawada Y.; Iwamura H. Correlated Rotation in Bis(9-triptycyl)methanes and Bis(9-triptycyl) Ethers. Separation and Interconversion of the Phase Isomers of Labeled Bevel Gears. J. Am. Chem. Soc. 1983, 105, 1449–1459 10.1021/ja00344a006. [DOI] [Google Scholar]

[ref155] Kawada Y.; Okamoto Y.; Iwamura H. Correlated Internal Rotation in Bis(2,6-dichloro-9-triptycyl)methane. To what Extent can Phase Isomers be Separated and Identified?. Tetrahedron Lett. 1983, 24, 5359–5362 10.1016/S0040-4039(00)87868-5. [DOI] [Google Scholar]

[ref156] Iwamura H.; Ito T.; Ito H.; Toriumi K.; Kawada Y.; Osawa E.; Fujiyoshi T.; Jaime C. Crystal and Molecular Structure of Bis(9-triptycyl) Ether. J. Am. Chem. Soc. 1984, 106, 4712–4717 10.1021/ja00329a013. [DOI] [Google Scholar]

[ref157] Iwamura H. Molecular Design of Correlated Internal Rotation. J. Mol. Struct. 1985, 126, 401–412 10.1016/0022-2860(85)80129-0. [DOI] [Google Scholar]

[ref158] Koga N.; Iwamura H. Barrier to Coupled Internal Rotation in Bis(9-triptycyl) Ether. Kinetics of Intramolecular Exciplex Formation in Racemic 2,3-Benzo-9-triptycyl 2-(N,N-dimethylaminomethyl)-9-triptycyl ether. J. Am. Chem. Soc. 1985, 107, 1426–1427 10.1021/ja00291a061. [DOI] [Google Scholar]

[ref159] Koga N.; Iwamura H. A Kinetic Study of Coupled Internal Rotation in Racemic 2,3-Benzo-9-triptycyl 2-(dimethylaminomethyl)-9-triptycyl ether by Means of Exciplex Fluorescence Dynamics. Chem. Lett. 1986, 247–250 10.1246/cl.1986.247. [DOI] [Google Scholar]

[ref160] Kawada Y.; Yamazaki H.; Koga G.; Murata S.; Iwamura H. Bis(9-triptycyl)amines, A Missing Link Between the Corresponding Methanes and Ethers. An Unconventional Synthesis and Influence of Nitrogen Configurational Inversion on the Coupled Disrotatory Trajectory. J. Org. Chem. 1986, 51, 1472–1477 10.1021/jo00359a016. [DOI] [Google Scholar]

[ref161] Kawada Y.; Ishikawa J.; Yamazaki H.; Koga G.; Murata S.; Iwamura H. Bis(9-triptycyl)amines, A Missing Link Between the Corresponding Methanes and Ethers. An Unconventional Synthesis and Influence of Nitrogen Configurational Inversion on the Coupled Disrotatory Trajectory. Tetrahedron Lett. 1987, 28, 445–448 10.1016/S0040-4039(00)95752-6. [DOI] [Google Scholar]

[ref162] Hounshell W. D.; Johnson C. A.; Guenzi A.; Cozzi F.; Mislow K. Sterochemical Consequences of Dynamic Gearing in Substituted bis (9-triptycyl) Methanes and Related Molecules. Proc. Natl. Acad. Sci. U. S. A. 1980, 77, 6961–6964 10.1073/pnas.77.12.6961. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref163] Cozzi F.; Guenzi A.; Johnson C. A.; Mislow K. Stereoisomerism and Correlated Rotation in Molecular Gear Systems. Residual Diastereomers of Bis(2,3-dimethyl-9-triptycyl)methane. J. Am. Chem. Soc. 1981, 103, 957–958 10.1021/ja00394a048. [DOI] [Google Scholar]

[ref164] Johnson C. A.; Guenzi A.; Mislow K. Restricted Gearing and Residual Stereoisomerism in Bis(1,4-dimethyl-9-triptycyl)methane. J. Am. Chem. Soc. 1981, 103, 6240–6242 10.1021/ja00410a054. [DOI] [Google Scholar]

[ref165] Johnson C. A.; Guenzi A.; Nachbar R. B. Jr.; Blount J. F.; Wennerstroem O.; Mislow K. Crystal and Molecular Structure of Bis(9-triptycyl) ketone and Bis(9-triptycyl)methane. J. Am. Chem. Soc. 1982, 104, 5163–5168 10.1021/ja00383a028. [DOI] [Google Scholar]

[ref166] Buergi H. B.; Hounshell W. D.; Nachbar J. R. B.; Mislow K. Conformational Dynamics of Propane, di-tert-Butylmethane, and Bis(9-triptycyl)methane. An Analysis of the Symmetry of Two Threefold Rotors on a Rigid Frame in Terms of Nonrigid Molecular Structure and Energy Hypersurfaces. J. Am. Chem. Soc. 1983, 105, 1427–1438 10.1021/ja00344a004. [DOI] [Google Scholar]

[ref167] Guenzi A.; Johnson C. A.; Cozzi F.; Mislow K. Dynamic Gearing and Residual Stereoisomerism in Labeled Bis(9-triptycyl)methane and Related Molecules. Synthesis and Stereochemistry of Bis(2,3-dimethyl-9-triptycyl)methane, Bis(2,3-dimethyl-9-triptycyl)carbinol, and Bis(1,4-dimethyl-9-triptycyl) Methane. J. Am. Chem. Soc. 1983, 105, 1438–1448 10.1021/ja00344a005. [DOI] [Google Scholar]

[ref168] Koga N.; Kawada Y.; Iwamura H. Recognition of the Phase Relationship between Remote Substituents in 9,10-Bis(3-chloro-9-triptycycloxy)triptycene Molecules Undergoing Rapid Internal Rotation Cooperatively. J. Am. Chem. Soc. 1983, 105, 5498–5499 10.1021/ja00354a063. [DOI] [Google Scholar]

[ref169] Yamamoto G. Molecular Gears with Two-toothed and Three-thoothed Wheels. J. Mol. Struct. 1985, 126, 413–420 10.1016/0022-2860(85)80130-7. [DOI] [Google Scholar]

[ref170] Yamamoto G. Dynamic Stereochemistry of Molecular Geras, 9-Benzyltriptycene and 9-Phenoxytriptycene, Studied by ¹³C Dynamic NMR Spectroscopy and Molecular Mechanics Calculations. Tetrahedron 1990, 46, 2761–2772 10.1016/S0040-4020(01)88370-8. [DOI] [Google Scholar]

[ref171] Chance J. M.; Geiger J. H.; Okamoto Y.; Aburatani R.; Mislow K. Stereochemical Consequences of a Parity Restriction on Dynamic Gearing in Tris(9-triptycyl)germanium Chloride and Tris(9-triptycyl)cyclopropenium Perchlorate. J. Am. Chem. Soc. 1990, 112, 3540–3547 10.1021/ja00165a044. [DOI] [Google Scholar]

[ref172] Kawada Y.; Sakai H.; Oguri M.; Koga G. Preparation of an Dynamic Gearing in cis-1,2-Bis(9-triptycyl)ethylene. Tetrahedron Lett. 1994, 35, 139–142 10.1016/0040-4039(94)88184-7. [DOI] [Google Scholar]

[ref173] Nikitin K.; Müller-Bunz H.; Ortin Y.; Risse W.; McGlinchey M. J. Twin Triptycyl Spinning Tops: A Simple Case of Molecular Gearing with Dynamic C₂ Symmetry. Eur. J. Org. Chem. 2008, 2008, 3079–3084 10.1002/ejoc.200800202. [DOI] [Google Scholar]

[ref174] Frantz D. K.; Linden A.; Baldridge K. K.; Siegel J. S. Molecular Spur Gears Comprising Triptycene Rotators and Bibenzimidazole-based Stators. J. Am. Chem. Soc. 2012, 134, 1528–1535 10.1021/ja2063346. [DOI] [PubMed] [Google Scholar]

[ref175] Stevens A. M.; Richards C. J. A Metallocene Molecular Gear. Tetrahedron Lett. 1997, 38, 7805–7808 10.1016/S0040-4039(97)10042-9. [DOI] [Google Scholar]

[ref176] Brydges S.; Harrington L. E.; McGlinchey M. J. Sterically Hindered Organometallics: Multi-n-rotor (n = 5, 6 and 7) Molecular Propellers and the Search for Correlated Rotations. Coord. Chem. Rev. 2002, 233, 75–105 10.1016/S0010-8545(02)00098-X. [DOI] [Google Scholar]

[ref177] Kuttenberger M.; Frieser M.; Hofweber M.; Mannschreck A. Axially Chiral Thioamides of Acrylic Acid: Correlated and Uncorrelated Internal Rotations. Tetrahedron: Asymmetry 1998, 9, 3629–3645 10.1016/S0957-4166(98)00373-5. [DOI] [Google Scholar]

[ref178] Clayden J.; Pink J. H. Concerted Rotation in a Tertiary Aromatic Amide: Towards a Simple Molecular Gear. Angew. Chem., Int. Ed. 1998, 37, 1937–1939. [DOI] [Google Scholar]

[ref179] Johnston E. R.; Fortt R.; Barborak J. C. Correlated Rotation in a Conformationally Restricted Amide. Magn. Reson. Chem. 2000, 38, 932–936. [DOI] [Google Scholar]

[ref180] Bragg R. A.; Clayden J. Using Symmetry to Monitor Geared Bond Rotation in Aromatic Amides by Dynamic NMR. Org. Lett. 2000, 2, 3351–3354 10.1021/ol0064462. [DOI] [PubMed] [Google Scholar]

[ref181] Bragg R. A.; Clayden J.; Morris G. A.; Pink J. H. Stereodynamics of Bond Rotation in Tertiary Aromatic Amides. Chem. - Eur. J. 2002, 8, 1279–1289. [DOI] [PubMed] [Google Scholar]

[ref182] Hellwinkel D.; Melan M.; Degel C. R. Die Stereochemie ortho-Substituierter Triphenylamin-derivate. Tetrahedron 1973, 29, 1895–1907 10.1016/S0040-4020(01)83217-8. [DOI] [Google Scholar]

[ref183] Hummel J. P.; Gust D.; Mislow K. Mechanism of Stereoisomerization in Triarylboranes. J. Am. Chem. Soc. 1974, 96, 3679–3681 10.1021/ja00818a068. [DOI] [Google Scholar]

[ref184] Wille E. E.; Stephenson D. S.; Capriel P.; Binsch G. Iterative Analysis of Exchange-Broadened NMR Band Shapes. The Mechanism of Correlated Rotations in Triaryl Derivatives of Phosphorus and Arsenic. J. Am. Chem. Soc. 1982, 104, 405–415 10.1021/ja00366a006. [DOI] [Google Scholar]

[ref185] Clegg W.; Lockhart J. C.; McDonnell M. B. Comparison of the Steric Barriers in Three- and Two-bladed Propeller Crowns. J. Chem. Soc., Perkin Trans. 1 1985, 1019–1023 10.1039/p19850001019. [DOI] [Google Scholar]

[ref186] Berg U.; Liljefors T.; Roussel C.; Sandstroem J. Steric Interplay Between Alkyl Groups Bonded to Planar Frameworks. Acc. Chem. Res. 1985, 18, 80–86 10.1021/ar00111a003. [DOI] [Google Scholar]

[ref187] Biali S. E.; Rappoport Z. Stable Simple Enols. 8.′ Synthesis and Keto Enol Equilibria of the Elusive 2,2-Dimesitylethanal and 1,2,2-Trimesitylethanone. Conformations of 1,2,2-Trimesitylethanone and 1,2,2-Trimesitylethanol. J. Am. Chem. Soc. 1985, 107, 1007–1015 10.1021/ja00290a043. [DOI] [Google Scholar]

[ref188] Hansen P. E.; Spanget-Lansen J.; Laali K. K. Conformational Studies of Phenyl and (1-Pyrenyl) Triarylmethylcarbenium Ions: Semiempirical Calculations and NMR Investigations under Stable Ion Conditions. J. Org. Chem. 1998, 63, 1827–1835 10.1021/jo9715480. [DOI] [Google Scholar]

[ref189] Yamaguchi S.; Akiyama S.; Tamao K. Synthesis, Structures, Photophysical Properties, and Dynamic Stereochemistry of Tri(9-anthryl)silane Derivatives. Organometallics 1998, 17, 4347–4352 10.1021/om9804778. [DOI] [Google Scholar]

[ref190] Sedo J.; Ventosa N.; Molins M. A.; Pons M.; Rovira C.; Veciana J. Stereoisomerism of Molecular Multipropellers. 2. Dynamic Stereochemistry of Bis- and Tris-Triaryl Systems. J. Org. Chem. 2001, 66, 1579–1589 10.1021/jo000474g. [DOI] [PubMed] [Google Scholar]

[ref191] Grilli S.; Lunazzi L.; Mazzanti A. Conformational Studies by Dynamic NMR. 83.1 Correlated Enantiomerization Pathways for the Stereolabile Propeller Antipodes of Dimesityl Substituted Ethanol and Ethers. J. Org. Chem. 2001, 66, 5853–5858 10.1021/jo010420m. [DOI] [PubMed] [Google Scholar]

[ref192] Benincori T.; Celentano G.; Pilati T.; Ponti A.; Rizzo S.; Sannicolò F. Configurationally Stable Molecular Propellers: First Resolution of Residual Enantiomers. Angew. Chem., Int. Ed. 2006, 45, 6193–6196 10.1002/anie.200601869. [DOI] [PubMed] [Google Scholar]

[ref193] Bulo R. E.; Allaart F.; Ehlers A. W.; de Kanter F. J. J.; Schakel M.; Lutz M.; Spek A. L.; Lammertsma K. Circumambulatory Rearrangement with Characteristics of a 2:1 Covalent Molecular Bevel Gear. J. Am. Chem. Soc. 2006, 128, 12169–12173 10.1021/ja0627895. [DOI] [PubMed] [Google Scholar]

[ref194] Romeo R.; Carnabuci S.; Fenech L.; Plutino M. R.; Albinati A. Overcrowded Organometallic Platinum(II) Complexes That Behave as Molecular Gears. Angew. Chem., Int. Ed. 2006, 45, 4494–4498 10.1002/anie.200600827. [DOI] [PubMed] [Google Scholar]

[ref195] Peck T.-G.; Lai Y.-H. Conformational Isomerism in 1,2-Di-o-tolylnaphthalenes: Selective Rotation of the 2-Aryl Ring. Tetrahedron 2009, 65, 3664–3667 10.1016/j.tet.2009.02.068. [DOI] [Google Scholar]

[ref196] Mati I. K.; Cockroft S. L. Molecular Balances for Quantifying Non-covalent Interactions. Chem. Soc. Rev. 2010, 39, 4195–4205 10.1039/b822665m. [DOI] [PubMed] [Google Scholar]

[ref197] Hiraoka S.; Harano K.; Tanaka T.; Shiro M.; Shionoya M. Quantitative Formation of Sandwich-shaped Trinuclear Silver(I) Complexes and Dynamic Nature of Their P ≤ > M Flip Motion in Solution. Angew. Chem., Int. Ed. 2003, 42, 5182–5185 10.1002/anie.200351068. [DOI] [PubMed] [Google Scholar]

[ref198] Hiraoka S.; Shiro M.; Shionoya M. Heterotopic Assemblage of Two Different Disk-Shaped Ligands through Trinuclear Silver (I) Complexation: Ligand Exchange-Driven Molecular Motion. J. Am. Chem. Soc. 2004, 126, 1214–1218 10.1021/ja036388q. [DOI] [PubMed] [Google Scholar]

[ref199] Hiraoka S.; Okuno E.; Tanaka T.; Shiro M.; Shionoya M. Ranging Correlated Motion (1.5 nm) of Two Coaxially Arranged Rotors Mediated by Helix Inversion of a Supramolecular Transmitter. J. Am. Chem. Soc. 2008, 130, 9089–9098 10.1021/ja8014583. [DOI] [PubMed] [Google Scholar]

[ref200] Hiraoka S.; Hirata K.; Shionoya M. A Molecular Ball Bearing Mediated by Multiligand Exchange in Concert. Angew. Chem., Int. Ed. 2004, 43, 3814–3818 10.1002/anie.200453753. [DOI] [PubMed] [Google Scholar]

[ref201] Okuno E.; Hiraoka S.; Shionoya M. A Synthetic Approach to a Molecular Crank Mechanism: Toward Intramolecular Motion Transformation Between Rotation and Translation. Dalton Trans. 2010, 39, 4107–4116 10.1039/b926154k. [DOI] [PubMed] [Google Scholar]

[ref202] Liu S.; Kondratuk D. V.; Rousseaux S. A.; Gil-Ramirez G.; O’Sullivan M. C.; Cremers J.; Claridge T. D.; Anderson H. L. Caterpillar Track Complexes in Template-directed Synthesis and Correlated Molecular Motion. Angew. Chem., Int. Ed. 2015, 54, 5355–5359 10.1002/anie.201412293. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref203] Kelly T. R.; Bowyer M. C.; Bhaskar K. V.; Bebbington D.; Garcia A.; Lang F.; Kim M. H.; Jette M. P. A Molecular Brake. J. Am. Chem. Soc. 1994, 116, 3657–3658 10.1021/ja00087a085. [DOI] [Google Scholar]

[ref204] Kelly T. R. Progress Toward a Rationally Designed Molecular Motor. Acc. Chem. Res. 2001, 34, 514–522 10.1021/ar000167x. [DOI] [PubMed] [Google Scholar]

[ref205] Sestelo J. P.; Kelly T. R. A Prototype of a Rationally Designed Chemically Powered Brownian Motor. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 337–343 10.1007/s003390201328. [DOI] [Google Scholar]

[ref206] Jog P. V.; Brown R. E.; Bates D. K. A Redox-Mediated Molecular Brake: Dynamic NMR Study of 2-[2-(Methylthio)phenyl]isoindolin-1-one and S-Oxidized Counterparts. J. Org. Chem. 2003, 68, 8240–8243 10.1021/jo034613g. [DOI] [PubMed] [Google Scholar]

[ref207] Dial B. E.; Pellechia P. J.; Smith M. D.; Shimizu K. D. Proton Grease: An Acid Accelerated Molecular Rotor. J. Am. Chem. Soc. 2012, 134, 3675–3678 10.1021/ja2120184. [DOI] [PubMed] [Google Scholar]

[ref208] Dial B. E.; Rasberry R. D.; Bullock B. N.; Smith M. D.; Pellechia P. J.; Profeta S.; Shimizu K. D. Guest-Accelerated Molecular Rotor. Org. Lett. 2011, 13, 244–247 10.1021/ol102659n. [DOI] [PubMed] [Google Scholar]

[ref209] Kanazawa H.; Higuchi M.; Yamamoto K. An Electric Cyclophane: Cavity Control Based on the Rotation of a Paraphenylene by Redox Switching. J. Am. Chem. Soc. 2005, 127, 16404–16405 10.1021/ja055681i. [DOI] [PubMed] [Google Scholar]

[ref210] Tomohiro Y.; Satake A.; Kobuke Y. Synthesis of Bipyridylene-Bridged Bisporphyrin by Nickel-Mediated Coupling Reaction: ON–OFF Control of Cofacial Porphyrin Unit by Reversible Complexation. J. Org. Chem. 2001, 66, 8442–8446 10.1021/jo015852b. [DOI] [PubMed] [Google Scholar]

[ref211] Zehm D.; Fudickar W.; Linker T. Molecular Switches Flipped by Oxygen. Angew. Chem., Int. Ed. 2007, 46, 7689–7692 10.1002/anie.200700443. [DOI] [PubMed] [Google Scholar]

[ref212] Kelly T. R.; Tellitu I.; Sestelo J. P. In Search of Molecular Ratchets. Angew. Chem., Int. Ed. Engl. 1997, 36, 1866–1868 10.1002/anie.199718661. [DOI] [Google Scholar]

[ref213] Kelly T. R.; Sestelo J. P.; Tellitu I. New Molecular Devices: In Search of a Molecular Ratchet. J. Org. Chem. 1998, 63, 3655–3665 10.1021/jo9723218. [DOI] [Google Scholar]

[ref214] Sebastian K. L. Molecular Ratchets: Verification of the Principle of Detailed Balance and the Second Law of Dynamics. Phys. Rev. E: Stat. Phys., Plasmas, Fluids, Relat. Interdiscip. Top. 2000, 61, 937–939 10.1103/PhysRevE.61.937. [DOI] [PubMed] [Google Scholar]

[ref215] Davis A. P. Tilting at Windmills? The Second Law Survives. Angew. Chem., Int. Ed. 1998, 37, 909–910. [DOI] [PubMed] [Google Scholar]

[ref216] Kelly T. R.; De Silva H.; Silva R. A. Unidirectional Rotary Motion in a Molecular System. Nature 1999, 401, 150–152 10.1038/43639. [DOI] [PubMed] [Google Scholar]

[ref217] Kelly T. R.; Silva R. A.; Silva H. D.; Jasmin S.; Zhao Y. A Rationally Designed Prototype of a Molecular Motor. J. Am. Chem. Soc. 2000, 122, 6935–6949 10.1021/ja001048f. [DOI] [PubMed] [Google Scholar]

[ref218] Kelly T. R.; Cai X.; Damkaci F.; Panicker S. B.; Tu B.; Bushell S. M.; Cornella I.; Piggott M. J.; Salives R.; Cavero M. Progress Toward a Rationally Designed, Chemically Powered Rotary Molecular Motor. J. Am. Chem. Soc. 2007, 129, 376–386 10.1021/ja066044a. [DOI] [PubMed] [Google Scholar]

[ref219] Mock W. L.; Ochwat K. J. Theory and Example of a Small-molecule Motor. J. Phys. Org. Chem. 2003, 16, 175–182 10.1002/poc.591. [DOI] [Google Scholar]

[ref220] Dahl B. J.; Branchaud B. P. Synthesis and Characterization of a Functionalized Chiral Biaryl Capable of Exhibiting Unidirectional Bond Rotation. Tetrahedron Lett. 2004, 45, 9599–9602 10.1016/j.tetlet.2004.10.147. [DOI] [Google Scholar]

[ref221] Lin Y.; Dahl B. J.; Branchaud B. P. Net Directed 180° Aryl–aryl Bond Rotation in a Prototypical Achiral Biaryl Lactone Synthetic Molecular Motor. Tetrahedron Lett. 2005, 46, 8359–8362 10.1016/j.tetlet.2005.09.151. [DOI] [Google Scholar]

[ref222] Fletcher S. P.; Dumur F.; Pollard M. M.; Feringa B. L. A Reversible, Unidirectional Molecular Rotary Motor Driven by Chemical Energy. Science 2005, 310, 80–82 10.1126/science.1117090. [DOI] [PubMed] [Google Scholar]

[ref223] Siegel J. Chemistry. Inventing the Nanomolecular Wheel. Science 2005, 310, 63–64 10.1126/science.1118765. [DOI] [PubMed] [Google Scholar]

[ref224] Tashiro K.; Konishi K.; Aida T. Enantiomeric Resolution of Chiral Metallobis(porphyrin)s: Studies on Rotatbility of Electronically Coupled Porphyrin Ligands. Angew. Chem., Int. Ed. Engl. 1997, 36, 856–858 10.1002/anie.199708561. [DOI] [Google Scholar]

[ref225] Tashiro K.; Fujiwara T.; Konishi K.; Aida T. Chem. Commun. 1998, 1121–1122 10.1039/a801350k. [DOI] [Google Scholar]

[ref226] Ikeda M.; Takeuchi M.; Shinkai S.; Tani F.; Naruta Y. Synthesis of New Diaryl-Substituted Triple-Decker and Tetraaryl-substituted Double-Decker Lanthanum(III) Porphyrins and Their Porphyrin Ring Rotational Speed as Compared with that of Double-Decker Cerium(IV) Porphyrins. Bull. Chem. Soc. Jpn. 2001, 74, 739–746 10.1246/bcsj.74.739. [DOI] [Google Scholar]

[ref227] Tashiro K.; Konishi K.; Aida T. Metal Bisporphyrin Double-decker Complexes as Redox-Responsive Rotating Modules. Studies on Ligand Rotation Activities of the Reduced and Oxidized Forms Using Chirality as a Probe. J. Am. Chem. Soc. 2000, 122, 7921–7926 10.1021/ja000356a. [DOI] [Google Scholar]

[ref228] Buchler J. W.; Decian A.; Fischer J.; Hammerschmitt P.; Loffler J.; Scharbert B.; Weiss R. Metal-Complexes with Tetrapyrrole Ligands 0.54. Synthesis, Spectra, Structure, and Redox Properties of Cerium(Iv) Bisporphyrinates with Identical and Different Porphyrin Rings in the Sandwich System. Chem. Ber. 1989, 122, 2219–2228 10.1002/cber.19891221203. [DOI] [Google Scholar]

[ref229] Takeuchi M.; Imada I.; Shinkai S. A Strong Positive Allosteric Effect in the Molecular Recognition of Dicarboxylic Acids by a Cerium(IV)Bis[tetrakis(4-pyridyl)-porphyrinte] Double Decker. Angew. Chem., Int. Ed. 1998, 37, 2096–2099. [DOI] [PubMed] [Google Scholar]

[ref230] Sugasaki A.; Ikeda M.; Takeuchi M.; Robertson A.; Shinkai S. Efficient Chirality Transcription Utilizing a Cerium(IV) Double Decker Porphyrin: A Prototype for Development of a Molecular Memory Systems. J. Chem. Soc., Perkin Trans. 1 1999, 3259–3264 10.1039/a904890a. [DOI] [Google Scholar]

[ref231] Yamamoto M.; Sugasaki A.; Ikeda M.; Takeuchi M.; Frimat K.; James T. D.; Shinkai S. Efficient Anion Binding to Cerium(IV)Bis(porphyrinate) Double Decker Utilizing Positive Homotropic Allosterim. Chem. Lett. 2001, 520–521 10.1246/cl.2001.520. [DOI] [Google Scholar]

[ref232] Robertson A.; Ikeda M.; Takeuchi M.; Shinkai S. Allosteric Binding of K⁺ to Crown Ether Macrocycles Appended to a Lanthanum Double Decker System. Bull. Chem. Soc. Jpn. 2001, 74, 883–888 10.1246/bcsj.74.883. [DOI] [Google Scholar]

[ref233] Sugasaki A.; Ikeda M.; Takeuchi M.; Shinkai S. Novel Oligosaccharide Binding to the Cerium(IV) Bis(porphyrinoate) Double Decker: Effective Amplification of a Binding Signal through Positive Homotropic Allosterism. Angew. Chem., Int. Ed. 2000, 39, 3839–3842. [DOI] [PubMed] [Google Scholar]

[ref234] Ikeda M.; Shinkai S.; Osuka A. Meso–meso-linked Porphyrin Dimer as a Novel Scaffold for the Selective Binding of Oligosaccharides. Chem. Commun. 2000, 1047–1048 10.1039/b003365k. [DOI] [Google Scholar]

[ref235] Sugasaki A.; Ikeda M.; Takeuchi M.; Koumoto K.; Shinkai S. The First Example of Positive Allosterism in an Aqueous Saccharide-Binding System Designed on a Ce(IV) Bis(porphyrinate) Double Decker Scaffold. Tetrahedron 2000, 56, 4717–4723 10.1016/S0040-4020(00)00395-1. [DOI] [Google Scholar]

[ref236] Ikeda M.; Tanida T.; Takeuchi M.; Shinkai S. Allosteric Silver (I) Ion Binding with Peripheral π Clefts of a Ce (IV) Double Decker Porphyrin. Org. Lett. 2000, 2, 1803–1805 10.1021/ol005807a. [DOI] [PubMed] [Google Scholar]

[ref237] Ikeda M.; Takeuchi M.; Shinkai S.; Tani F.; Naruta Y.; Sakamoto S.; Yamaguchi K. Allosteric Binding of a Ag⁺ Ion to Cerium (IV) Bis-porphyrinates Enhances the Rotational Activity of Porphyrin Ligands. Chem. - Eur. J. 2002, 8, 5541–5550. [DOI] [PubMed] [Google Scholar]

[ref238] Kubo Y.; Ikeda M.; Sugasaki A.; Takeuchi M.; Shinkai S. A Porphyrin Tetramer for a Positive Homotropic Allosteric Recognition System: Efficient Binding Information Transduction Through Butadiynyl Axis Rotation. Tetrahedron Lett. 2001, 42, 7435–7438 10.1016/S0040-4039(01)01546-5. [DOI] [Google Scholar]

[ref239] Shinkai S.; Ikeda M.; Sugasaki A.; Takeuchi M. Positive Allosteric Systems Designed on Dynamic Supramolecular Scaffolds: Toward Switching and Amplification of Guest Affinity and Selectivity. Acc. Chem. Res. 2001, 34, 494–503 10.1021/ar000177y. [DOI] [PubMed] [Google Scholar]

[ref240] Takeuchi M.; Ikeda M.; Sugasaki A.; Shinkai S. Molecular Design of Artificial Molecular and Ion Recognition Systems with Allosteric Guest Responses. Acc. Chem. Res. 2001, 34, 865–873 10.1021/ar0000410. [DOI] [PubMed] [Google Scholar]

[ref241] Ayabe M.; Ikeda A.; Kubo Y.; Takeuchi M.; Shinkai S. A Dendritic Porphyrin Receptor for C₆₀ Which Features a Profound Positive Allosteric Effect. Angew. Chem., Int. Ed. 2002, 41, 2790–2792. [DOI] [PubMed] [Google Scholar]

[ref242] Kubo Y.; Sugasaki A.; Ikeda M.; Sugiyasu K.; Sonoda K.; Ikeda A.; Takeuchi M.; Shinkai S. Cooperative C-60 Binding to a Porphyrin Tetramer Arranged Around a p-Terphenyl Axis in 1:2 Host-guest Stoichiometry. Org. Lett. 2002, 4, 925–928 10.1021/ol017299q. [DOI] [PubMed] [Google Scholar]

[ref243] Ercolani G. The Origin of Cooperativity in Double-Wheel Receptors. Freezing of Internal Rotation or Ligand-Induced Torsional Strain?. Org. Lett. 2005, 7, 803–805 10.1021/ol047620f. [DOI] [PubMed] [Google Scholar]

[ref244] Shinkai S.; Takeuchi M. Molecular Design of Synthetic Receptors with Dynamic, Imprinting, and Allosteric Functions. Bull. Chem. Soc. Jpn. 2005, 78, 40–51 10.1246/bcsj.78.40. [DOI] [PubMed] [Google Scholar]

[ref245] Ikeda T.; Tsukahara T.; Iino R.; Takeuchi M.; Noji H. Motion Capture and Manipulation of a Single Synthetic Molecular Rotor by Optical Microscopy. Angew. Chem., Int. Ed. 2014, 53, 10082–10085 10.1002/anie.201403091. [DOI] [PubMed] [Google Scholar]

[ref246] Tanaka H.; Ikeda T.; Takeuchi M.; Sada K.; Shinkai S.; Kawai T. Molecular Rotation in Self-Assembled Multidecker Porphyrin Complexes. ACS Nano 2011, 5, 9575–9582 10.1021/nn203773p. [DOI] [PubMed] [Google Scholar]

[ref247] Ogi S.; Ikeda T.; Wakabayashi R.; Shinkai S.; Takeuchi M. A Bevel-gear-shaped Rotor Bearing a Double-decker Porphyrin Complex. Chem. - Eur. J. 2010, 16, 8285–8290 10.1002/chem.201000276. [DOI] [PubMed] [Google Scholar]

[ref248] Ogi S.; Ikeda T.; Wakabayashi R.; Shinkai S.; Takeuchi M. Mechanically Interlocked Porphyrin Gears Propagating Two Different Rotational Frequencies. Eur. J. Org. Chem. 2011, 2011, 1831–1836 10.1002/ejoc.201001656. [DOI] [Google Scholar]

[ref249] Ogi S.; Ikeda T.; Takeuchi M. Synthetic Molecular Gear Based on Double-Decker Porphyrin Complexes. J. Inorg. Organomet. Polym. Mater. 2013, 23, 193–199 10.1007/s10904-012-9749-x. [DOI] [Google Scholar]

[ref250] Shibata M.; Tanaka S.; Ikeda T.; Shinkai S.; Kaneko K.; Ogi S.; Takeuchi M. Stimuli-Responsive Folding and Unfolding of a Polymer Bearing Multiple Cerium(IV) Bis(porphyrinate) Joints: Mechano-imitation of the Action of a Folding Ruler. Angew. Chem., Int. Ed. 2013, 52, 397–400 10.1002/anie.201205584. [DOI] [PubMed] [Google Scholar]

[ref251] Hiraoka S.; Hisanaga Y.; Shiro M.; Shionoya M. A Molecular Double Ball Bearing: An Ag^I–Pt^II Dodecanuclear Quadruple-Decker Complex with Three Rotors. Angew. Chem., Int. Ed. 2010, 49, 1669–1673 10.1002/anie.200905947. [DOI] [PubMed] [Google Scholar]

[ref252] Bohn R. K.; Haaland A. On the Molecular Structure of Ferrocene, Fe(C₅H₅)₂. J. Organomet. Chem. 1966, 5, 470–476 10.1016/S0022-328X(00)82382-7. [DOI] [Google Scholar]

[ref253] Wang X. B.; Dai B.; Woo H. K.; Wang L. S. Intramolecular Rotation Through Proton Transfer: [Fe(η⁵-C₅H₄CO₂-)₂] versus [(η⁵-C₅H₄CO₂-)Fe(η⁵-C₅H₄CO₂H)]. Angew. Chem., Int. Ed. 2005, 44, 6022–6024 10.1002/anie.200501564. [DOI] [PubMed] [Google Scholar]

[ref254] Crowley J. D.; Steele I. M.; Bosnich B. Protonmotive Force: Development of Electrostatic Drivers for Synthetic Molecular Motors. Chem. - Eur. J. 2006, 12, 8935–8951 10.1002/chem.200500519. [DOI] [PubMed] [Google Scholar]

[ref255] Iordache A.; Oltean M.; Milet A.; Thomas F.; Baptiste B.; Saint-Aman E.; Bucher C. Redox Control of Rotary Motions in Ferrocene-based Elemental Ball Bearings. J. Am. Chem. Soc. 2012, 134, 2653–2671 10.1021/ja209766e. [DOI] [PubMed] [Google Scholar]

[ref256] Fukino T.; Joo H.; Hisada Y.; Obana M.; Yamagishi H.; Hikima T.; Takata M.; Fujita N.; Aida T. Manipulation of Discrete Nanostructures by Selective Modulation of Noncovalent Forces. Science 2014, 344, 499–504 10.1126/science.1252120. [DOI] [PubMed] [Google Scholar]

[ref257] Warren L. F. Jr.; Hawthorne M. F. The Chemistry of the Bis[π-(3)-1,2-dicarbollyl] Metalates of Nickel and Palladium. J. Am. Chem. Soc. 1970, 92, 1157–1173 10.1021/ja00708a009. [DOI] [Google Scholar]

[ref258] St. Clair D.; Zalkin A.; Templeton D. H. The Crystal Structure of 3,3′-commo-Bis[undecahydro-1,2-dicarba-3-nickela-closo-dodecaborane], a Nickel(IV) Complex of the Dicarbollide Ion. J. Am. Chem. Soc. 1970, 92, 1173–1179 10.1021/ja00708a010. [DOI] [Google Scholar]

[ref259] Gold K.; Churchill M. R. The Crystal Structure and Molecular Configuration of an Asymmetric 1,2-Dimethyl-1,2-dicarbollide Complex of Nickel, Racemic (3,4′)-[(CH₈)₂B₉C₂H₉]₂Ni. J. Am. Chem. Soc. 1970, 92, 1180–1187 10.1021/ja00708a011. [DOI] [Google Scholar]

[ref260] Hawthorne M. F.; Dunks G. B. Metallocarboranes That Exhibit Novel Chemical Features: A Virtually Unlimited Variety of Structural and Dynamic Features are Observed in Metallocarborane Chemistry. Science 1972, 178, 462–471 10.1126/science.178.4060.462. [DOI] [PubMed] [Google Scholar]

[ref261] Hawthorne M. F.; Zink J. I.; Skelton J. M.; Bayer M. J.; Liu C.; Livshits E.; Baer R.; Neuhauser D. Electrical or Photocontrol of the Rotary Motion of a Metallacarborane. Science 2004, 303, 1849–1851 10.1126/science.1093846. [DOI] [PubMed] [Google Scholar]

[ref262] Rebek J. Binding Forces, Equilibria and Rates: New Models for Enzymic Catalysis. Acc. Chem. Res. 1984, 17, 258–264 10.1021/ar00103a006. [DOI] [Google Scholar]

[ref263] Rebek J.; Trend J. E.; Wattley R. V.; Chakravorti S. Allosteric Effects in Organic Chemistry. Site-specific Binding. J. Am. Chem. Soc. 1979, 101, 4333–4337 10.1021/ja00509a047. [DOI] [Google Scholar]

[ref264] Rebek J.; Wattley R. V. Allosteric Effects. Remote Control of Ion Transport Selectivity. J. Am. Chem. Soc. 1980, 102, 4853–4854 10.1021/ja00534a058. [DOI] [Google Scholar]

[ref265] Rebek J.; Costello T.; Marshall L.; Wattley R.; Gadwood R. C.; Onan K. Allosteric Effects in Organic Chemistry: Binding Cooperativity in a Model for Subunit Interactions. J. Am. Chem. Soc. 1985, 107, 7481–7487 10.1021/ja00311a043. [DOI] [Google Scholar]

[ref266] van Veggel F. C. J. M.; Verboom W.; Reinhoudt D. N. Metallomacrocycles: Supramolecular Chemistry with Hard and Soft Metal Cations in Action. Chem. Rev. 1994, 94, 279–299 10.1021/cr00026a001. [DOI] [Google Scholar]

[ref267] Linton B.; Hamilton A. D. Formation of Artificial Receptors by Metal-Templated Self-Assembly. Chem. Rev. 1997, 97, 1669–1680 10.1021/cr960375w. [DOI] [PubMed] [Google Scholar]

[ref268] Robertson A.; Shinkai S. Cooperative Binding in Selective Sensors, Catalysts and Actuators. Coord. Chem. Rev. 2000, 205, 157–199 10.1016/S0010-8545(00)00243-5. [DOI] [Google Scholar]

[ref269] Shinkai S.; Ikeda M.; Sugasaki A.; Takeuchi M. Positive Allosteric Systems Designed on Dynamic Supramolecular Scaffolds: Toward Switching and Amplification of Guest Affinity and Selectivity. Acc. Chem. Res. 2001, 34, 494–503 10.1021/ar000177y. [DOI] [PubMed] [Google Scholar]

[ref270] Kovbasyuk L.; Krämer R. Allosteric Supramolecular Receptors and Catalysts. Chem. Rev. 2004, 104, 3161–3188 10.1021/cr030673a. [DOI] [PubMed] [Google Scholar]

[ref271] Chong Y. S.; Smith M. D.; Shimizu K. D. A Conformationally Programmable Ligand. J. Am. Chem. Soc. 2001, 123, 7463–7464 10.1021/ja0158713. [DOI] [PubMed] [Google Scholar]

[ref272] Degenhardt C. F.; Lavin J. M.; Smith M. D.; Shimizu K. D. Conformationally Imprinted Receptors: Atropisomers with “Write”, “Save”, and “Erase” Recognition Properties. Org. Lett. 2005, 7, 4079–4081 10.1021/ol051325t. [DOI] [PubMed] [Google Scholar]

[ref273] Leighton P.; Sanders J. K. M. A Molecular Switch for Control of Conformation: Strained Intramolecular Co-ordination in 4,4′-Bipyridyl-capped Zinc Porphyrins. J. Chem. Soc., Chem. Commun. 1984, 854–856 10.1039/c39840000854. [DOI] [Google Scholar]

[ref274] Abraham R. J.; Leighton P.; Sanders J. K. M. = Coordination Chemistry and Geometries of Some 4,4′-Bipyridyl-capped Porphyrins. Proton- and Ligand-induced Switching of Conformations. J. Am. Chem. Soc. 1985, 107, 3472–3478 10.1021/ja00298a012. [DOI] [Google Scholar]

[ref275] Mendez-Arroyo J.; Barroso-Flores J.; Lifschitz A. M.; Sarjeant A. A.; Stern C. L.; Mirkin C. A. A Multi-state, Allosterically-regulated Molecular Receptor with Switchable Selectivity. J. Am. Chem. Soc. 2014, 136, 10340–10348 10.1021/ja503506a. [DOI] [PubMed] [Google Scholar]

[ref276] Kennedy R. D.; Machan C. W.; McGuirk C. M.; Rosen M. S.; Stern C. L.; Sarjeant A. A.; Mirkin C. A. General Strategy for the Synthesis of Rigid Weak-link Approach Platinum(II) Complexes: Tweezers, Triple-layer Complexes, and Macrocycles. Inorg. Chem. 2013, 52, 5876–5888 10.1021/ic302855f. [DOI] [PubMed] [Google Scholar]

[ref277] Kuwabara J.; Yoon H. J.; Mirkin C. A.; DiPasquale A. G.; Rheingold A. L. Pseudo-allosteric Regulation of the Anion Binding Affinity of a Macrocyclic Coordination Complex. Chem. Commun. 2009, 4557–4559 10.1039/b905150c. [DOI] [PubMed] [Google Scholar]

[ref278] Shinkai S.; Nakaji T.; Ogawa T.; Shigematsu K.; Manabe O. Photoresponsive Crown Ethers. 2. Photocontrol of Ion Extraction and Ion Transport by a Bis(crown ether) with a Butterfly-like Motion. J. Am. Chem. Soc. 1981, 103, 111–115 10.1021/ja00391a021. [DOI] [Google Scholar]

[ref279] Hunter C. A.; Anderson H. L. What is Cooperativity?. Angew. Chem., Int. Ed. 2009, 48, 7488–7499 10.1002/anie.200902490. [DOI] [PubMed] [Google Scholar]

[ref280] Klarner F. G.; Kahlert B. Molecular Tweezers and Clips as Synthetic Receptors. Molecular Recognition and Dynamics in Receptor-substrate Complexes. Acc. Chem. Res. 2003, 36, 919–932 10.1021/ar0200448. [DOI] [PubMed] [Google Scholar]

[ref281] Harmata M. Chiral Molecular Tweezers. Acc. Chem. Res. 2004, 37, 862–873 10.1021/ar030164v. [DOI] [PubMed] [Google Scholar]

[ref282] Poulsen T.; Nielsen K. A.; Bond A. D.; Jeppesen J. O. Bis(tetrathiafulvalene)-Calix[2]pyrrole[2]- thiophene and Its Complexation with TCNQ. Org. Lett. 2007, 9, 5485–5488 10.1021/ol7024235. [DOI] [PubMed] [Google Scholar]

[ref283] Sijbesma R. P.; Wijmenga S. S.; Nolte R. J. M. A Molecular Clip That Binds Aromatic Guests by an Induced-fit Mechanism. J. Am. Chem. Soc. 1992, 114, 9807–9813 10.1021/ja00051a013. [DOI] [Google Scholar]

[ref284] Rowan A. E.; Elemans J. A. A. W.; Nolte R. J. M. Molecular and Supramolecular Objects from Glycoluril. Acc. Chem. Res. 1999, 32, 995–1006 10.1021/ar9702684. [DOI] [Google Scholar]

[ref285] Reek J. N. H.; Engelkamp H.; Rowan A. E.; Elemans J. A. A. W.; Nolte R. J. M. Conformational Behavior and Binding Properties of Naphthalene-Walled Clips. Chem. - Eur. J. 1998, 4, 716–722. [DOI] [Google Scholar]

[ref286] Sijbesma R. P.; Nolte R. J. M. A Molecular Clip with Allosteric Binding Properties. J. Am. Chem. Soc. 1991, 113, 6695–6696 10.1021/ja00017a063. [DOI] [Google Scholar]

[ref287] Klarner F. G.; Benkhoff J.; Boese R.; Burkert U.; Kamieth M.; Naatz U. Molecular Tweezers as Synthetic Receptors in Host-guest Chemistry: Inclusion of Cyclohexane and Self-assembly of Aliphatic Side Chains. Angew. Chem., Int. Ed. Engl. 1996, 35, 1130–1133 10.1002/anie.199611301. [DOI] [Google Scholar]

[ref288] Petitjean A.; Khoury R. G.; Kyritsakas N.; Lehn J.-M. Dynamic Devices. Shape Switching and Substrate Binding in Ion-Controlled Nanomechanical Molecular Tweezers. J. Am. Chem. Soc. 2004, 126, 6637–6647 10.1021/ja031915r. [DOI] [PubMed] [Google Scholar]

[ref289] Hoffmann R. W. Flexible Molecules with Defined Shape—Conformational Design. Angew. Chem., Int. Ed. Engl. 1992, 31, 1124–1134 10.1002/anie.199211241. [DOI] [Google Scholar]

[ref290] Yuasa H.; Hashimoto H. Bending Trisaccharides by a Chelation-Induced Ring Flip of a Hinge-Like Monosaccharide Unit. J. Am. Chem. Soc. 1999, 121, 5089–5090 10.1021/ja984062p. [DOI] [Google Scholar]

[ref291] Izumi T.; Hashimoto H.; Yuasa H. Switching Extended 1,3-Diequatorial and Bent 1,3-Diaxial States of a Disubstituted Hinge Sugar by Ligand Exchange Reactions on Pt(II). Chem. Commun. 2004, 94–95 10.1039/b311811h. [DOI] [PubMed] [Google Scholar]

[ref292] Menger F. M.; Chicklo P. A.; Sherrod M. J. Ion-induced Conformational Changes in Kemp’s Triacid. Tetrahedron Lett. 1989, 30, 6943–6946 10.1016/S0040-4039(01)93393-3. [DOI] [Google Scholar]

[ref293] Shirodkar S. M.; Weisman G. R. Cyclohexane-based 1,3-Dipodands: Complexation and Conformational Biasing. J. Chem. Soc., Chem. Commun. 1989, 236–238 10.1039/c39890000236. [DOI] [Google Scholar]

[ref294] Raban M.; Burch D. L.; Hortelano E. R.; Durocher D.; Kost D. Complete Conformational Switching in a Calcium Ionophore. J. Org. Chem. 1994, 59, 1283–1287 10.1021/jo00085a014. [DOI] [Google Scholar]

[ref295] Kemp D. S.; Petrakis K. S. Synthesis and Conformational Analysis of cis,cis-1,3,5-Trimethylcyclohexane-1,3,5-tricarboxylic acid. J. Org. Chem. 1981, 46, 5140–5143 10.1021/jo00338a014. [DOI] [Google Scholar]

[ref296] Samoshin V. V.; Chertkov V. A.; Vatlina L. P.; Dobretsova E. K.; Simonov N. A.; Kastorsky L. P.; Gremyachinsky D. E.; Schneider H.-J. trans-1,2-Cyclohexanedicarboxylic Acid Derivatives as pH-Trigger for Conformationally Controlled Crowns. Tetrahedron Lett. 1996, 37, 3981–3984 10.1016/0040-4039(96)00761-7. [DOI] [Google Scholar]

[ref297] Gil de Oliveira Santos A.; Klute W.; Torode J.; P. W. Bohm V.; Cabrita E.; Runsink J.; W. Hoffmann R. Flexible Molecules with Defined Shape. X. Synthesis and Conformational Study of 1,5-Diaza-cis-decalin. New J. Chem. 1998, 22, 993–997 10.1039/a801160e. [DOI] [Google Scholar]

[ref298] Collin J.-P.; Durola F.; Heitz V.; Reviriego F.; Sauvage J.-P.; Trolez Y. A Cyclic [4]rotaxane that Behaves as a Switchable Molecular Receptor: Formation of a Rigid Scaffold from a Collapsed Structure by Complexation with Copper(I) Ions. Angew. Chem., Int. Ed. 2010, 49, 10172–10175 10.1002/anie.201004008. [DOI] [PubMed] [Google Scholar]

[ref299] Haberhauer G. Control of Planar Chirality: The Construction of a Copper-Ion-Controlled Chiral Molecular Hinge. Angew. Chem., Int. Ed. 2008, 47, 3635–3638 10.1002/anie.200800062. [DOI] [PubMed] [Google Scholar]

[ref300] Haberhauer G. A Metal-Ion-Driven Supramolecular Chirality Pendulum. Angew. Chem., Int. Ed. 2010, 49, 9286–9289 10.1002/anie.201004460. [DOI] [PubMed] [Google Scholar]

[ref301] Haberhauer G.; Kallweit C. A Bridged Azobenzene Derivative as a Reversible, Light-Induced Chirality Switch. Angew. Chem., Int. Ed. 2010, 49, 2418–2421 10.1002/anie.200906731. [DOI] [PubMed] [Google Scholar]

[ref302] Timmerman P.; Verboom W.; Reinhoudt D. N. Resorcinarenes. Tetrahedron 1996, 52, 2663–2704 10.1016/0040-4020(95)00984-1. [DOI] [Google Scholar]

[ref303] Moran J. R.; Ericson J. L.; Dalcanale E.; Bryant J. A.; Knobler C. B.; Cram D. J. Vases and Kites as Cavitands. J. Am. Chem. Soc. 1991, 113, 5707–5714 10.1021/ja00015a026. [DOI] [Google Scholar]

[ref304] Moran J. R.; Karbach S.; Cram D. J. Cavitands: Synthetic Molecular Vessels. J. Am. Chem. Soc. 1982, 104, 5826–5828 10.1021/ja00385a064. [DOI] [Google Scholar]

[ref305] Skinner P. J.; Cheetham A. G.; Beeby A.; Gramlich V.; Diederich F. Conformational Switching of Resorcin[4]arene Cavitands by Protonation, Preliminary Communication. Helv. Chim. Acta 2001, 84, 2146–2153. [DOI] [Google Scholar]

[ref306] Azov V. A.; Diederich F.; Lill Y.; Hecht B. Synthesis and Conformational Switching of Partially and Differentially Bridged Resorcin[4]arenes Bearing Fluorescent Dye Labels. Preliminary Communication. Helv. Chim. Acta 2003, 86, 2149–2155 10.1002/hlca.200390172. [DOI] [Google Scholar]

[ref307] Azov V. A.; Jaun B.; Diederich F. NMR Investigations into the Vase-Kite Conformational Switching of Resorcin[4]arene Cavitands. Helv. Chim. Acta 2004, 87, 449–462 10.1002/hlca.200490043. [DOI] [Google Scholar]

[ref308] Frei M.; Marotti F.; Diederich F. Zn^II-induced Conformational Control of Amphiphilic Cavitands in Langmuir Monolayers. Chem. Commun. 2004, 1362–1363 10.1039/b405331a. [DOI] [PubMed] [Google Scholar]

[ref309] Pochorovski I.; Ebert M.-O.; Gisselbrecht J.-P.; Boudon C.; Schweizer W. B.; Diederich F. Redox-Switchable Resorcin[4]arene Cavitands: Molecular Grippers. J. Am. Chem. Soc. 2012, 134, 14702–14705 10.1021/ja306473x. [DOI] [PubMed] [Google Scholar]

[ref310] Pochorovski I.; Milić J.; Kolarski D.; Gropp C.; Schweizer W. B.; Diederich F. Evaluation of Hydrogen-Bond Acceptors for Redox-Switchable Resorcin[4]arene Cavitands. J. Am. Chem. Soc. 2014, 136, 3852–3858 10.1021/ja411429b. [DOI] [PubMed] [Google Scholar]

[ref311] Rudkevich D. M.; Hilmersson G.; Rebek J. Intramolecular Hydrogen Bonding Controls the Exchange Rates of Guests in a Cavitand. J. Am. Chem. Soc. 1997, 119, 9911–9912 10.1021/ja971592x. [DOI] [Google Scholar]

[ref312] Rudkevich D. M.; Hilmersson G.; Rebek J. Self-Folding Cavitands. J. Am. Chem. Soc. 1998, 120, 12216–12225 10.1021/ja982970g. [DOI] [Google Scholar]

[ref313] Ma S.; Rudkevich D. M.; Rebek J. J. Supramolecular Isomerism in Caviplexes. Angew. Chem., Int. Ed. 1999, 38, 2600–2602. [DOI] [PubMed] [Google Scholar]

[ref314] Tucci F. C.; Rudkevich D. M.; Rebek J. J. Velcrands with Snaps and Their Conformational Control. Chem. - Eur. J. 2000, 6, 1007–1016. [DOI] [PubMed] [Google Scholar]

[ref315] Haino T.; Rudkevich D. M.; Shivanyuk A.; Rissanen K.; Rebek J. J. Induced-Fit Molecular Recognition with Water-Soluble Cavitands. Chem. - Eur. J. 2000, 6, 3797–3805. [DOI] [PubMed] [Google Scholar]

[ref316] Far A. R.; Shivanyuk A.; Rebek J. Water-Stabilized Cavitands. J. Am. Chem. Soc. 2002, 124, 2854–2855 10.1021/ja012453p. [DOI] [PubMed] [Google Scholar]

[ref317] Amrhein P.; Wash P. L.; Shivanyuk A.; Rebek J. Metal Ligation Regulates Conformational Equilibria and Binding Properties of Cavitands. Org. Lett. 2002, 4, 319–321 10.1021/ol0167661. [DOI] [PubMed] [Google Scholar]

[ref318] Tucker J. A.; Knobler C. B.; Trueblood K. N.; Cram D. J. Host-guest Complexation. 49. Cavitands Containing Two Binding Cavities. J. Am. Chem. Soc. 1989, 111, 3688–3699 10.1021/ja00192a028. [DOI] [Google Scholar]

[ref319] Amrhein P.; Shivanyuk A.; Johnson D. W.; Rebek J. Metal-Switching and Self-Inclusion of Functional Cavitands. J. Am. Chem. Soc. 2002, 124, 10349–10358 10.1021/ja0204269. [DOI] [PubMed] [Google Scholar]

[ref320] Ikeda A.; Shinkai S. Novel Cavity Design Using Calix[n]arene Skeletons: Toward Molecular Recognition and Metal Binding. Chem. Rev. 1997, 97, 1713–1734 10.1021/cr960385x. [DOI] [PubMed] [Google Scholar]

[ref321] Ashton P. R.; Ballardini R.; Balzani V.; Boyd S. E.; Credi A.; Gandolfi M. T.; Gómez-López M.; Iqbal S.; Philp D.; Preece J. A. Simple Mechanical Molecular and Supramolecular Machines: Photochemical and Electrochemical Control of Switching Processes. Chem. - Eur. J. 1997, 3, 152–170 10.1002/chem.19970030123. [DOI] [Google Scholar]

[ref322] Ashton P. R.; Gómez-López M.; Iqbal S.; Preece J. A.; Stoddart J. F. A Self-Complexing Macrocycle Acting as a Chromophoric Receptor. Tetrahedron Lett. 1997, 38, 3635–3638 10.1016/S0040-4039(97)00688-6. [DOI] [Google Scholar]

[ref323] Brondsted Nielsen M.; Becher J. ’Self-complexing’ Tetrathiafulvalene Macrocycles; A Tetrathiafulvalene Switch. Chem. Commun. 1998, 475–476 10.1039/a707026h. [DOI] [Google Scholar]

[ref324] Brøndsted Nielsen M.; Hansen J. G.; Becher J. Self-Complexing Tetrathiafulvalene-Based Donor–Acceptor Macrocycles. Eur. J. Org. Chem. 1999, 1999, 2807–2815. [DOI] [Google Scholar]

[ref325] Balzani V.; Ceroni P.; Credi A.; Gomez-Lopez M.; Hamers C.; Stoddart J. F.; Wolf R. Controlled Dethreading/rethreading of a Scorpion-like Pseudorotaxane and a Related Macrobicyclic Self-complexing System. New J. Chem. 2001, 25, 25–31 10.1039/b004934o. [DOI] [Google Scholar]

[ref326] Liu Y.; Flood A. H.; Stoddart J. F. Thermally and Electrochemically Controllable Self-Complexing Molecular Switches. J. Am. Chem. Soc. 2004, 126, 9150–9151 10.1021/ja048164t. [DOI] [PubMed] [Google Scholar]

[ref327] Qu D.-H.; Feringa B. L. Controlling Molecular Rotary Motion with a Self-Complexing Lock. Angew. Chem., Int. Ed. 2010, 49, 1107–1110 10.1002/anie.200906064. [DOI] [PubMed] [Google Scholar]

[ref328] Jones I. M.; Lingard H.; Hamilton A. D. pH-Dependent Conformational Switching in 2,6-Benzamidodiphenylacetylenes. Angew. Chem., Int. Ed. 2011, 50, 12569–12571 10.1002/anie.201106241. [DOI] [PubMed] [Google Scholar]

[ref329] Pramanik S.; De S.; Schmittel M. Bidirectional Chemical Communication between Nanomechanical Switches. Angew. Chem., Int. Ed. 2014, 53, 4709–4713 10.1002/anie.201400804. [DOI] [PubMed] [Google Scholar]

[ref330] Dolain C.; Maurizot V.; Huc I. Protonation-Induced Transition between Two Distinct Helical Conformations of a Synthetic Oligomer via a Linear Intermediate. Angew. Chem., Int. Ed. 2003, 42, 2738–2740 10.1002/anie.200351080. [DOI] [PubMed] [Google Scholar]

[ref331] Piguet C.; Bernardinelli G.; Hopfgartner G. Helicates as Versatile Supramolecular Complexes. Chem. Rev. 1997, 97, 2005–2062 10.1021/cr960053s. [DOI] [PubMed] [Google Scholar]

[ref332] Hill D. J.; Mio M. J.; Prince R. B.; Hughes T. S.; Moore J. S. A Field Guide to Foldamers. Chem. Rev. 2001, 101, 3893–4012 10.1021/cr990120t. [DOI] [PubMed] [Google Scholar]

[ref333] Cheng R. P.; Gellman S. H.; DeGrado W. F. β-Peptides: From Structure to Function. Chem. Rev. 2001, 101, 3219–3232 10.1021/cr000045i. [DOI] [PubMed] [Google Scholar]

[ref334] Albrecht M. Let’s Twist Again”Double-Stranded, Triple-Stranded, and Circular Helicates. Chem. Rev. 2001, 101, 3457–3498 10.1021/cr0103672. [DOI] [PubMed] [Google Scholar]

[ref335] Williams A. Helical Complexes and Beyond. Chem. - Eur. J. 1997, 3, 15–19 10.1002/chem.19970030104. [DOI] [Google Scholar]

[ref336] Gellman S. H. Foldamers: A Manifesto. Acc. Chem. Res. 1998, 31, 173–180 10.1021/ar960298r. [DOI] [Google Scholar]

[ref337] Rowan A. E.; Nolte R. J. M. Helical Molecular Programming. Angew. Chem., Int. Ed. 1998, 37, 63–68. [DOI] [Google Scholar]

[ref338] Cubberley M. S.; Iverson B. L. Models of Higher-order Structure: Foldamers and Beyond. Curr. Opin. Chem. Biol. 2001, 5, 650–653 10.1016/S1367-5931(01)00261-7. [DOI] [PubMed] [Google Scholar]

[ref339] Schmuck C. Molecules with Helical Structure: How To Build a Molecular Spiral Staircase. Angew. Chem., Int. Ed. 2003, 42, 2448–2452 10.1002/anie.200201625. [DOI] [PubMed] [Google Scholar]

[ref340] Albrecht M. Artificial Molecular Double-Stranded Helices. Angew. Chem., Int. Ed. 2005, 44, 6448–6451 10.1002/anie.200501472. [DOI] [PubMed] [Google Scholar]

[ref341] Gong B. Crescent Oligoamides: From Acyclic “Macrocycles” to Folding Nanotubes. Chem. - Eur. J. 2001, 7, 4336–4342. [DOI] [PubMed] [Google Scholar]

[ref342] Sanford A. R.; Yamato K.; Yang X.; Yuan L.; Han Y.; Gong B. Well-defined Secondary Structures. Eur. J. Biochem. 2004, 271, 1416–1425 10.1111/j.1432-1033.2004.04062.x. [DOI] [PubMed] [Google Scholar]

[ref343] Huc I. Aromatic Oligoamide Foldamers. Eur. J. Org. Chem. 2004, 2004, 17–29 10.1002/ejoc.200300495. [DOI] [Google Scholar]

[ref344] Constable E. C. Oligopyridines as Helicating Ligands. Tetrahedron 1992, 48, 10013–10059 10.1016/S0040-4020(01)89035-9. [DOI] [Google Scholar]

[ref345] Seebach D.; Matthews J. β-Peptides: A Surprise at Every Turn. Chem. Commun. 1997, 2015–2022 10.1039/a704933a. [DOI] [Google Scholar]

[ref346] Nielsen P. E.; Haaima G. Peptide Nucleic Acid (PNA). A DNA Mimic with a Pseudopeptide Backbone. Chem. Soc. Rev. 1997, 26, 73–78 10.1039/cs9972600073. [DOI] [Google Scholar]

[ref347] Nowick J. S. Chemical Models of Protein β-Sheets. Acc. Chem. Res. 1999, 32, 287–296 10.1021/ar970204t. [DOI] [Google Scholar]

[ref348] Stigers K. D.; Soth M. J.; Nowick J. S. Designed Molecules that Fold to Mimic Protein Secondary Structures. Curr. Opin. Chem. Biol. 1999, 3, 714–723 10.1016/S1367-5931(99)00030-7. [DOI] [PubMed] [Google Scholar]

[ref349] Nielsen P. E. Peptide Nucleic Acid. A Molecule with Two Identities. Acc. Chem. Res. 1999, 32, 624–630 10.1021/ar980010t. [DOI] [Google Scholar]

[ref350] Kirshenbaum K.; Zuckermann R. N.; Dill K. A. Designing Polymers That Mimic Biomolecules. Curr. Opin. Struct. Biol. 1999, 9, 530–535 10.1016/S0959-440X(99)80075-X. [DOI] [PubMed] [Google Scholar]

[ref351] Herdewijn P. Conformationally Restricted Carbohydrate-modified Nucleic Acids and Antisense Technology. Biochim. Biophys. Acta, Gene Struct. Expression 1999, 1489, 167–179 10.1016/S0167-4781(99)00152-9. [DOI] [PubMed] [Google Scholar]

[ref352] Patch J. A.; Barron A. E. Mimicry of Bioactive Peptides via Non-natural, Sequence-specific Peptidomimetic Oligomers. Curr. Opin. Chem. Biol. 2002, 6, 872–877 10.1016/S1367-5931(02)00385-X. [DOI] [PubMed] [Google Scholar]

[ref353] Martinek T. A.; Fülöp F. Side-chain Control of β-Peptide Secondary Structures. Eur. J. Biochem. 2003, 270, 3657–3666 10.1046/j.1432-1033.2003.03756.x. [DOI] [PubMed] [Google Scholar]

[ref354] Cheng R. P. Beyond de novo Protein Design — de novo Design of Non-natural Folded Oligomers. Curr. Opin. Struct. Biol. 2004, 14, 512–520 10.1016/j.sbi.2004.07.001. [DOI] [PubMed] [Google Scholar]

[ref355] Licini G.; Prins L. J.; Scrimin P. Oligopeptide Foldamers: From Structure to Function. Eur. J. Org. Chem. 2005, 2005, 969–977 10.1002/ejoc.200400521. [DOI] [Google Scholar]

[ref356] Nelson J. C.; Saven J. G.; Moore J. S.; Wolynes P. G. Solvophobically Driven Folding of Nonbiological Oligomers. Science 1997, 277, 1793–1796 10.1126/science.277.5333.1793. [DOI] [PubMed] [Google Scholar]

[ref357] Prince R. B.; Saven J. G.; Wolynes P. G.; Moore J. S. Cooperative Conformational Transitions in Phenylene Ethynylene Oligomers: Chain-Length Dependence. J. Am. Chem. Soc. 1999, 121, 3114–3121 10.1021/ja983995i. [DOI] [Google Scholar]

[ref358] Lahiri S.; Thompson J. L.; Moore J. S. Solvophobically Driven π-Stacking of Phenylene Ethynylene Macrocycles and Oligomers. J. Am. Chem. Soc. 2000, 122, 11315–11319 10.1021/ja002129e. [DOI] [Google Scholar]

[ref359] Hill D. J.; Moore J. S. Helicogenicity of Solvents in the Conformational Equilibrium of Oligo(m-phenylene ethynylene)s: Implications for Foldamer Research. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 5053–5057 10.1073/pnas.072642799. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref360] Hofacker A. L.; Parquette J. R. Dendrimer Folding in Aqueous Media: An Example of Solvent-Mediated Chirality Switching. Angew. Chem., Int. Ed. 2005, 44, 1053–1057 10.1002/anie.200460943. [DOI] [PubMed] [Google Scholar]

[ref361] Berl V.; Huc I.; Khoury R. G.; Krische M. J.; Lehn J.-M. Interconversion of Single and Double Helices Formed from Synthetic Molecular Strands. Nature 2000, 407, 720–723 10.1038/35037545. [DOI] [PubMed] [Google Scholar]

[ref362] Berl V.; Huc I.; Khoury R. G.; Lehn J.-M. Helical Molecular Programming: Folding of Oligopyridine-dicarboxamides into Molecular Single Helices. Chem. - Eur. J. 2001, 7, 2798–2809. [DOI] [PubMed] [Google Scholar]

[ref363] Berl V.; Huc I.; Khoury R. G.; Lehn J.-M. Helical Molecular Programming: Supramolecular Double Helices by Dimerization of Helical Oligopyridine-dicarboxamide Strands. Chem. - Eur. J. 2001, 7, 2810–2820. [DOI] [PubMed] [Google Scholar]

[ref364] Hanan G. S.; Lehn J.-M.; Kyritsakas N.; Fischer J. Molecular Helicity: A General Approach for Helicity Induction in a Polyheterocyclic Molecular Strand. J. Chem. Soc., Chem. Commun. 1995, 765–766 10.1039/c39950000765. [DOI] [Google Scholar]

[ref365] Bassani D. M.; Lehn J.-M.; Baum G.; Fenske D. Designed Self-Generation of an Extended Helical Structure From an Achiral Polyheterocylic Strand. Angew. Chem., Int. Ed. Engl. 1997, 36, 1845–1847 10.1002/anie.199718451. [DOI] [Google Scholar]

[ref366] Ohkita M.; Lehn J.-M.; Baum G.; Fenske D. Helicity Coding: Programmed Molecular Self-Organization of Achiral Nonbiological Strands into Multiturn Helical Superstructures: Synthesis and Characterization of Alternating Pyridine–Pyrimidine Oligomers. Chem. - Eur. J. 1999, 5, 3471–3481. [DOI] [Google Scholar]

[ref367] Stadler A.-M.; Kyritsakas N.; Lehn J.-M. Reversible Folding/unfolding of Linear Molecular Strands into Helical Channel-like Complexes upon Proton-modulated Binding and Release of Metal Ions. Chem. Commun. 2004, 2024–2025 10.1039/b407168a. [DOI] [PubMed] [Google Scholar]

[ref368] Kolomiets E.; Berl V.; Odriozola I.; Stadler A.-M.; Kyritsakas N.; Lehn J.-M. Contraction/extension Molecular Motion by Protonation/deprotonation Induced Structural Switching of Pyridine Derived Oligoamides. Chem. Commun. 2003, 2868–2869 10.1039/b311578j. [DOI] [PubMed] [Google Scholar]

[ref369] Barboiu M.; Lehn J.-M. Dynamic Chemical Devices: Modulation of Contraction/extension Molecular Motion by Coupled-ion Binding/pH Change-induced Structural Switching. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 5201–5206 10.1073/pnas.082099199. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref370] Barboiu M.; Vaughan G.; Kyritsakas N.; Lehn J.-M. Dynamic Chemical Devices: Generation of Reversible Extension/Contraction Molecular Motion by Ion-Triggered Single/Double Helix Interconversion. Chem. - Eur. J. 2003, 9, 763–769 10.1002/chem.200390085. [DOI] [PubMed] [Google Scholar]

[ref371] Stadler A.-M.; Lehn J.-M. P. Coupled Nanomechanical Motions: Metal-Ion-Effected, pH-Modulated, Simultaneous Extension/Contraction Motions of Double-Domain Helical/Linear Molecular Strands. J. Am. Chem. Soc. 2014, 136, 3400–3409 10.1021/ja408752m. [DOI] [PubMed] [Google Scholar]

[ref372] Dugave C.; Demange L. cis-trans Isomerization of Organic Molecules and Biomolecules: Implications and Applications. Chem. Rev. 2003, 103, 2475–2532 10.1021/cr0104375. [DOI] [PubMed] [Google Scholar]

[ref373] Waldeck D. H. Photoisomerization Dynamics of Stilbenes. Chem. Rev. 1991, 91, 415–436 10.1021/cr00003a007. [DOI] [Google Scholar]

[ref374] Bandara H. M.; Burdette S. C. Photoisomerization in Different Classes of Azobenzene. Chem. Soc. Rev. 2012, 41, 1809–1825 10.1039/C1CS15179G. [DOI] [PubMed] [Google Scholar]

[ref375] Cheetham A. G.; Hutchings M. G.; Claridge T. D. W.; Anderson H. L. Enzymatic Synthesis and Photoswitchable Enzymatic Cleavage of a Peptide-linked Rotaxane. Angew. Chem., Int. Ed. 2006, 45, 1596–1599 10.1002/anie.200504064. [DOI] [PubMed] [Google Scholar]

[ref376] Haberhauer G.; Kallweit C.; Wölper C.; Bläser D. An Azobenzene Unit Embedded in a Cyclopeptide as a Type-Specific and Spatially Directed Switch. Angew. Chem., Int. Ed. 2013, 52, 7879–7882 10.1002/anie.201301516. [DOI] [PubMed] [Google Scholar]

[ref377] Clever G. H.; Tashiro S.; Shionoya M. Light-Triggered Crystallization of a Molecular Host-Guest Complex. J. Am. Chem. Soc. 2010, 132, 9973–9975 10.1021/ja103620z. [DOI] [PubMed] [Google Scholar]

[ref378] Irie M. Diarylethenes for Memories and Switches. Chem. Rev. 2000, 100, 1685–1716 10.1021/cr980069d. [DOI] [PubMed] [Google Scholar]

[ref379] Irie M. Photochromism: Memories and Switches - Introduction. Chem. Rev. 2000, 100, 1683–1683 10.1021/cr980068l. [DOI] [PubMed] [Google Scholar]

[ref380] van Herpt J. T.; Areephong J.; Stuart M. C.; Browne W. R.; Feringa B. L. Light-controlled Formation of Vesicles and Supramolecular Organogels by a Cholesterol-bearing Amphiphilic Molecular Switch. Chem. - Eur. J. 2014, 20, 1737–1742 10.1002/chem.201302902. [DOI] [PubMed] [Google Scholar]

[ref381] Hou L.; Zhang X.; Pijper T. C.; Browne W. R.; Feringa B. L. Reversible Photochemical Control of Singlet Oxygen Generation Using Diarylethene Photochromic Switches. J. Am. Chem. Soc. 2014, 136, 910–913 10.1021/ja4122473. [DOI] [PubMed] [Google Scholar]

[ref382] Kudernac T.; Kobayashi T.; Uyama A.; Uchida K.; Nakamura S.; Feringa B. L. Tuning the Temperature Dependence for Switching in Dithienylethene Photochromic Switches. J. Phys. Chem. A 2013, 117, 8222–8229 10.1021/jp404924q. [DOI] [PubMed] [Google Scholar]

[ref383] Yokoyama Y. Fulgides for Memories and Switches. Chem. Rev. 2000, 100, 1717–1739 10.1021/cr980070c. [DOI] [PubMed] [Google Scholar]

[ref384] Santiago A.; Becker R. S. Photochromic Fulgides - Spectroscopy and Mechanism of Photoreactions. J. Am. Chem. Soc. 1968, 90, 3654–3658 10.1021/ja01016a009. [DOI] [Google Scholar]

[ref385] Berkovic G.; Weiss V. Spiropyrans and Spirooxazines for Memories and Switches. Chem. Rev. 2000, 100, 1741–1753 10.1021/cr9800715. [DOI] [PubMed] [Google Scholar]

[ref386] Feringa B. L.; Huck N. P. M.; Schoevaars A. M. Chiroptical Molecular Switches. Adv. Mater. 1996, 8, 681–684 10.1002/adma.19960080819. [DOI] [Google Scholar]

[ref387] Feringa B. L.; van Delden R. A.; Koumura N.; Geertsema E. M. Chiroptical Molecular Switches. Chem. Rev. 2000, 100, 1789–1816 10.1021/cr9900228. [DOI] [PubMed] [Google Scholar]

[ref388] Browne B. L. F. a. W.Molecular Switches, 2nd ed.; Wiley-VCH: Weinheim, 2011. [Google Scholar]

[ref389] Shinkai S.; Honda Y.; Kusano Y.; Manabe O. A Photoresponsive Cylindrical Ionophore. J. Chem. Soc., Chem. Commun. 1982, 848–850 10.1039/c39820000848. [DOI] [Google Scholar]

[ref390] Feringa B. L.; Jager W. F.; de Lange B. Organic Materials for Reversible Optical Data Storage. Tetrahedron 1993, 49, 8267–8310 10.1016/S0040-4020(01)81913-X. [DOI] [Google Scholar]

[ref391] Momotake A.; Arai T. Synthesis, Excited State Properties, and Dynamic Structural Change of Photoresponsive Dendrimers. Polymer 2004, 45, 5369–5390 10.1016/j.polymer.2004.05.075. [DOI] [Google Scholar]

[ref392] Momotake A.; Arai T. Photochemistry and Photophysics of Stilbene Dendrimers and Related Compounds. J. Photochem. Photobiol., C 2004, 5, 1–25 10.1016/j.jphotochemrev.2004.01.001. [DOI] [Google Scholar]

[ref393] Tie C.; Gallucci J. C.; Parquette J. R. Helical Conformational Dynamics and Photoisomerism of Alternating Pyridinedicarboxamide/m-(Phenylazo)azobenzene Oligomers. J. Am. Chem. Soc. 2006, 128, 1162–1171 10.1021/ja0547228. [DOI] [PubMed] [Google Scholar]

[ref394] Yager K. G.; Barrett C. J. Novel Photo-switching Using Azobenzene Functional Materials. J. Photochem. Photobiol., A 2006, 182, 250–261 10.1016/j.jphotochem.2006.04.021. [DOI] [Google Scholar]

[ref395] Russew M. M.; Hecht S. Photoswitches: From Molecules to Materials. Adv. Mater. 2010, 22, 3348–3360 10.1002/adma.200904102. [DOI] [PubMed] [Google Scholar]

[ref396] Fischer G. Peptidyl-Prolyl cis/trans Isomerases and Their Effectors. Angew. Chem., Int. Ed. Engl. 1994, 33, 1415–1436 10.1002/anie.199414151. [DOI] [Google Scholar]

[ref397] Fischer G. Chemical Aspects of Peptide Bond Isomerization. Chem. Soc. Rev. 2000, 29, 119–127 10.1039/a803742f. [DOI] [Google Scholar]

[ref398] Beharry A. A.; Woolley G. A. Azobenzene Photoswitches for Biomolecules. Chem. Soc. Rev. 2011, 40, 4422–4437 10.1039/c1cs15023e. [DOI] [PubMed] [Google Scholar]

[ref399] Beharry A. A.; Wong L.; Tropepe V.; Woolley G. A. Fluorescence Imaging of Azobenzene Photoswitching In Vivo. Angew. Chem., Int. Ed. 2011, 50, 1325–1327 10.1002/anie.201006506. [DOI] [PubMed] [Google Scholar]

[ref400] Szymanski W.; Beierle J. M.; Kistemaker H. A.; Velema W. A.; Feringa B. L. Reversible Photocontrol of Biological Systems by the Incorporation of Molecular Photoswitches. Chem. Rev. 2013, 113, 6114–6178 10.1021/cr300179f. [DOI] [PubMed] [Google Scholar]

[ref401] Kienzler M. A.; Reiner A.; Trautman E.; Yoo S.; Trauner D.; Isacoff E. Y. A Red-Shifted, Fast-Relaxing Azobenzene Photoswitch for Visible Light Control of an Ionotropic Glutamate Receptor. J. Am. Chem. Soc. 2013, 135, 17683–17686 10.1021/ja408104w. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref402] Kamiya Y.; Asanuma H. Light-Driven DNA Nanomachine with a Photoresponsive Molecular Engine. Acc. Chem. Res. 2014, 47, 1663–1672 10.1021/ar400308f. [DOI] [PubMed] [Google Scholar]

[ref403] Velema W. A.; Szymanski W.; Feringa B. L. Photopharmacology: Beyond Proof of Principle. J. Am. Chem. Soc. 2014, 136, 2178–2191 10.1021/ja413063e. [DOI] [PubMed] [Google Scholar]

[ref404] Velema W. A.; van der Berg J. P.; Hansen M. J.; Szymanski W.; Driessen A. J.; Feringa B. L. Optical Control of Antibacterial Activity. Nat. Chem. 2013, 5, 924–928 10.1038/nchem.1750. [DOI] [PubMed] [Google Scholar]

[ref405] Szymanski W.; Yilmaz D.; Kocer A.; Feringa B. L. Bright Ion Channels and Lipid Bilayers. Acc. Chem. Res. 2013, 46, 2910–2923 10.1021/ar4000357. [DOI] [PubMed] [Google Scholar]

[ref406] Kocer A.; Walko M.; Meijberg W.; Feringa B. L. A Light-actuated Nanovalve Derived from a Channel Protein. Science 2005, 309, 755–758 10.1126/science.1114760. [DOI] [PubMed] [Google Scholar]

[ref407] Muraoka T.; Kinbara K.; Aida T. Mechanical Twisting of a Guest by a Photoresponsive Host. Nature 2006, 440, 512–515 10.1038/nature04635. [DOI] [PubMed] [Google Scholar]

[ref408] Muraoka T.; Kinbara K.; Aida T. Reversible Operation of Chiral Molecular Scissors by Redox and UV Light. Chem. Commun. 2007, 1441–1443 10.1039/b618248h. [DOI] [PubMed] [Google Scholar]

[ref409] Merino E.; Ribagorda M. Control Over Molecular Motion Using the cis-trans Photoisomerization of the Azo Group. Beilstein J. Org. Chem. 2012, 8, 1071–1090 10.3762/bjoc.8.119. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref410] Marchi E.; Baroncini M.; Bergamini G.; Van Heyst J.; Vogtle F.; Ceroni P. Photoswitchable Metal Coordinating Tweezers Operated by Light-harvesting Dendrimers. J. Am. Chem. Soc. 2012, 134, 15277–15280 10.1021/ja307522f. [DOI] [PubMed] [Google Scholar]

[ref411] Raymo F. M. Intermolecular Coupling of Motion Under Photochemical Control. Angew. Chem., Int. Ed. 2006, 45, 5249–5251 10.1002/anie.200602516. [DOI] [PubMed] [Google Scholar]

[ref412] Kai H.; Nara S.; Kinbara K.; Aida T. Toward Long-distance Mechanical Communication: Studies on a Ternary Complex Interconnected by a Bridging Rotary Module. J. Am. Chem. Soc. 2008, 130, 6725–6727 10.1021/ja801646b. [DOI] [PubMed] [Google Scholar]

[ref413] Muraoka T.; Kinbara K.; Kobayashi Y.; Aida T. Light-Driven Open-Close Motion of Chiral Molecular Scissors. J. Am. Chem. Soc. 2003, 125, 5612–5613 10.1021/ja034994f. [DOI] [PubMed] [Google Scholar]

[ref414] Norikane Y.; Tamaoki N. Light-Driven Molecular Hinge: A New Molecular Machine Showing a Light-Intensity-Dependent Photoresponse that Utilizes the Trans-Cis Isomerization of Azobenzene. Org. Lett. 2004, 6, 2595–2598 10.1021/ol049082c. [DOI] [PubMed] [Google Scholar]

[ref415] Muraoka T.; Kinbara K. Development of Photoresponsive Supramolecular Machines Inspired by Biological Molecular Systems. J. Photochem. Photobiol., C 2012, 13, 136–147 10.1016/j.jphotochemrev.2012.04.001. [DOI] [Google Scholar]

[ref416] Li Z.; Liang J.; Xue W.; Liu G.; Liu S. H.; Yin J. Switchable Azo-macrocycles: From Molecules to Functionalisation. Supramol. Chem. 2014, 26, 54–65 10.1080/10610278.2013.822970. [DOI] [Google Scholar]

[ref417] Basheer M. C.; Oka Y.; Mathews M.; Tamaoki N. A Light-controlled Molecular Brake with Complete ON-OFF Rotation. Chem. - Eur. J. 2010, 16, 3489–3496 10.1002/chem.200902123. [DOI] [PubMed] [Google Scholar]

[ref418] Hashim P. K.; Thomas R.; Tamaoki N. Induction of Molecular Chirality by Circularly Polarized Light in Cyclic Azobenzene with a Photoswitchable Benzene Rotor. Chem. - Eur. J. 2011, 17, 7304–7312 10.1002/chem.201003526. [DOI] [PubMed] [Google Scholar]

[ref419] Baroncini M.; Silvi S.; Venturi M.; Credi A. Reversible Photoswitching of Rotaxane Character and Interplay of Thermodynamic Stability and Kinetic Lability in a Self-assembling Ring-axle Molecular System. Chem. - Eur. J. 2010, 16, 11580–11587 10.1002/chem.201001409. [DOI] [PubMed] [Google Scholar]

[ref420] Liu F.; Morokuma K. Computational Study on the Working Mechanism of a Stilbene Light-Driven Molecular Rotary Motor: Sloped Minimal Energy Path and Unidirectional Nonadiabatic Photoisomerization. J. Am. Chem. Soc. 2012, 134, 4864–4876 10.1021/ja211441n. [DOI] [PubMed] [Google Scholar]

[ref421] Pospíšil L.; Bednárová L.; Štěpánek P.; Slavíček P.; Vávra J.; Hromadová M.; Dlouhá H.; Tarábek J.; Teplý F. Intense Chiroptical Switching in a Dicationic Helicene-Like Derivative: Exploration of a Viologen-Type Redox Manifold of a Non-Racemic Helquat. J. Am. Chem. Soc. 2014, 136, 10826–10829 10.1021/ja500220j. [DOI] [PubMed] [Google Scholar]

[ref422] Ruangsupapichat N.; Pollard M. M.; Harutyunyan S. R.; Feringa B. L. Reversing the Direction in a Light-driven Rotary Molecular Motor. Nat. Chem. 2011, 3, 53–60 10.1038/nchem.872. [DOI] [PubMed] [Google Scholar]

[ref423] Feringa B. L. In Control of Motion: From Molecular Switches to Molecular Motors. Acc. Chem. Res. 2001, 34, 504–513 10.1021/ar0001721. [DOI] [PubMed] [Google Scholar]

[ref424] Feringa B. L.; van Delden R. A.; ter Wiel M. K. J. In Control of Switching, Motion, and Organization. Pure Appl. Chem. 2003, 75, 563–575 10.1351/pac200375050563. [DOI] [Google Scholar]

[ref425] Feringa B. L. The Art of Building Small: From Molecular Switches to Molecular Motors. J. Org. Chem. 2007, 72, 6635–6652 10.1021/jo070394d. [DOI] [PubMed] [Google Scholar]

[ref426] Feringa B. L.; Koumura N.; van Delden R. A.; ter Wiel M. K. J. Light-driven Molecular Switches and Motors. Appl. Phys. A: Mater. Sci. Process. 2002, 75, 301–308 10.1007/s003390201338. [DOI] [Google Scholar]

[ref427] Feringa B. L. Molecular Switches and Motors. AIP Conf. Proc. 2013, 1519, 73–75 10.1063/1.4794713. [DOI] [Google Scholar]

[ref428] Cnossen A.; Browne W. R.; Feringa B. L. Unidirectional Light-Driven Molecular Motors Based on Overcrowded Alkenes. Top. Curr. Chem. 2014, 354, 139–162 10.1007/128_2013_512. [DOI] [PubMed] [Google Scholar]

[ref429] Koumura N.; Zijlstra R. W. J.; van Delden R. A.; Harada N.; Feringa B. L. Light-driven Monodirectional Molecualr Rotor. Nature 1999, 401, 152–155 10.1038/43646. [DOI] [PubMed] [Google Scholar]

[ref430] Harada N.; Koumura N.; Feringa B. L. Chemistry of Unique Chiral Olefins. 3. synthesis and Absolute Stereochemistry of trans-and cis-1,1′,2,2′3,3′,4,4′-Octahydro-3,3′-dimethyl-4,4′-biphenanthrylidenes. J. Am. Chem. Soc. 1997, 119, 7256–7264 10.1021/ja970669e. [DOI] [Google Scholar]

[ref431] Harada N.; Saito A.; Koumura N.; Uda H.; deLange B.; Jager W. F.; Wynberg H.; Feringa B. L. Chemistry of Unique Chiral Olefins 0.1. Synthesis, Enantioresolution, Circular Dichroism, and Theoretical Determination of the Absolute Stereochemistry of trans- and cis-1,1′,2,2′,3,3′,4,4′-octahydro-4,4′-biphenanthrylidenes. J. Am. Chem. Soc. 1997, 119, 7241–7248 10.1021/ja970667u. [DOI] [Google Scholar]

[ref432] Harada N.; Saito A.; Koumura N.; Roe D. C.; Jager W. F.; Zijlstra R. W. J.; deLange B.; Feringa B. L. Chemistry of Unique Chiral Olefins 0.2. Unexpected Thermal Racemization of cis-1,1′,2,2′,3,3′,4,4′-octahydro-4,4′-biphenanthrylidene. J. Am. Chem. Soc. 1997, 119, 7249–7255 10.1021/ja970668m. [DOI] [Google Scholar]

[ref433] Zijlstra R. W. J.; van Duijnen P. T.; Feringa B. L.; Steffen T.; Duppen K.; Wiersma D. A. Excited-State Dynamics of Tetraphenylethylene: Ultrafast Stokes Shift, Isomerization, and Charge Separation. J. Phys. Chem. A 1997, 101, 9828–9836 10.1021/jp971763k. [DOI] [Google Scholar]

[ref434] Koumura N.; Harada N. Photochemistry and Absolute Stereochemistry of Unique Chiral Olefins, trans- and cis-1,1′,2,2′,3,3′,4,4′-Octahydro-3,3′-dimethyl-4,4′-biphenanthrylidenes. Chem. Lett. 1998, 1151–1152 10.1246/cl.1998.1151. [DOI] [Google Scholar]

[ref435] Zijlstra R. W. J.; Jager W. F.; de Lange B.; van Duijnen P. Th.; Feringa B. L.; Goto H.; Saito A.; Koumura N.; Harada N. Chemistry of Unique Chiral Olefins. 4. Theoretical Studies of the Racemization Mechanism of trans- and cis-1,1′,2,2′,3,3′,4,4′-Octahydro-4,4′-biphenanthrylidenes. J. Org. Chem. 1999, 64, 1667–1674 10.1021/jo982381t. [DOI] [PubMed] [Google Scholar]

[ref436] Zijlstra R. W. J.; Jager W. F.; de Lange B.; van Duijnen P. T.; Feringa B. L.; Goto H.; Saito A.; Koumura N.; Harada N. Chemistry of Unique Chiral Olefins. 4. Theoretical Studies of the Racemization Mechanism of trans- and cis-1,1 ′,2,2 ′,3,3 ′,4,4 ′-octahydro-4,4 ′-biphenanthrylidenes. J. Org. Chem. 1999, 64, 1667–1674 10.1021/jo982381t. [DOI] [PubMed] [Google Scholar]

[ref437] ter Wiel M. K. J.; Koumura N.; Van Delden R. A.; Meetsma A.; Harada N.; Feringa B. L. Chiral Overcrowded Alkenes; Asymmetric Synthesis of (3S,3′S)-(M,M)-(E)-(+)-1,1′,2,2′,3,3′,4,4′-octahydro-3,3′,7,7′-Tetramethyl-4,4′-biphenanthrylidenes. Chirality 2000, 12, 734–741. [DOI] [PubMed] [Google Scholar]

[ref438] ter Wiel M. K. J.; van Delden R. A.; Meetsma A.; Feringa B. L. Increased Speed of Rotation for The Smallest Light-Driven Molecular Motor. J. Am. Chem. Soc. 2003, 125, 15076–15086 10.1021/ja036782o. [DOI] [PubMed] [Google Scholar]

[ref439] ter Wiel M. K. J.; van Delden R. A.; Meetsma A.; Feringa B. L. Light-Driven Molecular Motors: Stepwise Thermal Helix Inversion during Unidirectional Rotation of sterically Overcrowded Biphenanthrylidenes. J. Am. Chem. Soc. 2005, 127, 14208–14222 10.1021/ja052201e. [DOI] [PubMed] [Google Scholar]

[ref440] Kuwahara S.; Fujita T.; Harada N. A New Model of Light-Powered Chiral Molecular Motor with Higher Speed of Rotation, Part 2 - Dynamics of Motor Rotation. Eur. J. Org. Chem. 2005, 2005, 4544–4556 10.1002/ejoc.200500323. [DOI] [Google Scholar]

[ref441] Klok M.; Walko M.; Geertsema E. M.; Ruangsupapichat N.; Kistemaker J. C. M.; Meetsma A.; Feringa B. L. New Mechanistic Insight in the Thermal Helix Inversion of Second - Second Generation Moelcular Motors. Chem. - Eur. J. 2008, 14, 11183–11193 10.1002/chem.200800969. [DOI] [PubMed] [Google Scholar]

[ref442] ter Wiel M. K.; Kwit M. G.; Meetsma A.; Feringa B. L. Synthesis, Stereochemistry, and Photochemical and Thermal Behavior of Bis-tert-butyl Substituted Overcrowded Alkenes. Org. Biomol. Chem. 2007, 5, 87–96 10.1039/B611070C. [DOI] [PubMed] [Google Scholar]

[ref443] Pollard M. M.; Meetsma A.; Feringa B. L. A Redesign of Light-driven Rotary Molecular Motors. Org. Biomol. Chem. 2008, 6, 507–512 10.1039/B715652A. [DOI] [PubMed] [Google Scholar]

[ref444] Caroli G.; Kwit M. G.; Feringa B. L. Photochemical and Thermal Behavior of Light-driven Unidirectional Molecular Motor with Long Alkyl Chains. Tetrahedron 2008, 64, 5956–5962 10.1016/j.tet.2008.03.098. [DOI] [Google Scholar]

[ref445] Koumura N.; Geertsma E. M.; Meetsma A.; Feringa B. L. Light-Driven Molecular Rotor: Unidirectional Rotation Controlled by a Single Stereogenic Center. J. Am. Chem. Soc. 2000, 122, 12005–12006 10.1021/ja002755b. [DOI] [PubMed] [Google Scholar]

[ref446] Pollard M. M.; ter Wiel M. K. J.; van Delden R. A.; Vicario J.; Koumura N.; van den Brom J. R.; Meetsma A.; Feringa B. L. Light-Driven Rotary Molecular Motors on Gold Nanoparticles. Chem. - Eur. J. 2008, 14, 11610–11622 10.1002/chem.200800814. [DOI] [PubMed] [Google Scholar]

[ref447] van Delden R. A.; Koumura N.; Schoevaars A.; Meetsma A.; Feringa B. L. A Donor–acceptor Substituted Molecular Motor: Unidirectional Rotation Driven by Visible Light. Org. Biomol. Chem. 2003, 1, 33–35 10.1039/b209378b. [DOI] [PubMed] [Google Scholar]

[ref448] Geertsema E. M.; Koumura N.; ter Wiel M. K. J.; Meetsma A.; Feringa B. L. In Control of the Speed of Rotation in Molecular Motors. Unexpected Retardation of Rotary Motion. Chem. Commun. 2002, 2962–2963 10.1039/b208323j. [DOI] [PubMed] [Google Scholar]

[ref449] Koumura N.; Geertsema E. M.; van Gelder M. B.; Meetsma A.; Feringa B. L. Second Generation Light-Driven Molecular Motors. Unidirectional Rotation Controlled by a Single Stereogenic Center with Near-Perfect Photoequilibria and Acceleration of the Speed of Rotation by Structural Modification. J. Am. Chem. Soc. 2002, 124, 5037–5051 10.1021/ja012499i. [DOI] [PubMed] [Google Scholar]

[ref450] ter Wiel M. K.; van Delden R. A.; Meetsma A.; Feringa B. L. Increased Speed of Rotation for the Smallest Light-Driven Molecular Motor. J. Am. Chem. Soc. 2003, 125, 15076–15086 10.1021/ja036782o. [DOI] [PubMed] [Google Scholar]

[ref451] Pijper D.; van Delden R. A.; Meetsma A.; Feringa B. L. Acceleration of a Nanomotor: Electronic Control of the Rotary Speed of a Light-Driven Molecular Rotor. J. Am. Chem. Soc. 2005, 127, 17612–17613 10.1021/ja054499e. [DOI] [PubMed] [Google Scholar]

[ref452] Vicario J.; Walko M.; Meetsma A.; Feringa B. L. Fine Tuning of the Rotary Motion by Structural Modification in Light-driven Unidirectional Molecular Motors. J. Am. Chem. Soc. 2006, 128, 5127–5135 10.1021/ja058303m. [DOI] [PubMed] [Google Scholar]

[ref453] Conyard J.; Addison K.; Heisler I. A.; Cnossen A.; Browne W. R.; Feringa B. L.; Meech S. R. Ultrafast Dynamics in the Power Stroke of a Molecular Rotary Motor. Nat. Chem. 2012, 4, 547–551 10.1038/nchem.1343. [DOI] [PubMed] [Google Scholar]

[ref454] Schoevaars A. M.; Kruizinga W.; Zijlstra R. W. J.; Veldman N.; Spek A. L.; Feringa B. L. Toward a Switchable Molecular Rotor. Unexpected Dynamic Behavior of Functionalized Overcrowded Alkenes. J. Org. Chem. 1997, 62, 4943–4948 10.1021/jo962210t. [DOI] [Google Scholar]

[ref455] ter Wiel M. K.; van Delden R. A.; Meetsma A.; Feringa B. L. Control of Rotor Motion in a Light-driven Molecular Motor: Towards a Molecular Gearbox. Org. Biomol. Chem. 2005, 3, 4071–4076 10.1039/b510641a. [DOI] [PubMed] [Google Scholar]

[ref456] Greb L.; Lehn J.-M. Light-Driven Molecular Motors: Imines as Four-Step or Two-Step Unidirectional Rotors. J. Am. Chem. Soc. 2014, 136, 13114–13117 10.1021/ja506034n. [DOI] [PubMed] [Google Scholar]

[ref457] Padwa A. Photochemistry of the Crbon-Nitrogen Double Bond. Chem. Rev. 1977, 77, 37–68 10.1021/cr60305a004. [DOI] [Google Scholar]

[ref458] Pratt A. C. The Photochemistry of Imines. Chem. Soc. Rev. 1977, 6, 63–81 10.1039/cs9770600063. [DOI] [Google Scholar]

[ref459] Pierre Courot R. P.; le Saint Jaques Photochromisme par Isomerization Syn-anti de Phenylhydrazones-2 de Tricetones-1,2,3 et de Dicetones-1,2 Substituees. Tetrahedron Lett. 1976, 17, 1181–1184 10.1016/S0040-4039(00)78012-9. [DOI] [Google Scholar]

[ref460] Pichon R.; le Saint J.; Courtot P. Photoisomerization d’Arylhydrazones-2 de Dicetones-1,2 Substituees en 2 Mecanisme d’Isomerization Thermique de la Double Liaison C=N. Tetrahedron 1981, 37, 1517–1524 10.1016/S0040-4020(01)92091-5. [DOI] [Google Scholar]

[ref461] Chaur M. N.; Collado D.; Lehn J.-M. Configurational and Constitutional Information Storage: Multiple Dynamics in Systems Based on Pyridyl and Acyl Hydrazones. Chem. - Eur. J. 2011, 17, 248–258 10.1002/chem.201002308. [DOI] [PubMed] [Google Scholar]

[ref462] Burdette S. C. Molecular Switches: Hydrazones Double Down on Zinc. Nat. Chem. 2012, 4, 695–696 10.1038/nchem.1438. [DOI] [PubMed] [Google Scholar]

[ref463] Tatum L. A.; Su X.; Aprahamian I. Simple Hydrazone Building Blocks for Complicated Functional Materials. Acc. Chem. Res. 2014, 47, 2141–2149 10.1021/ar500111f. [DOI] [PubMed] [Google Scholar]

[ref464] Su X.; Aprahamian I. Hydrazone-based Switches, Metallo-assemblies and Sensors. Chem. Soc. Rev. 2014, 43, 1963–1981 10.1039/c3cs60385g. [DOI] [PubMed] [Google Scholar]

[ref465] Su X.; Aprahamian I. Zinc(II)-Regulation of Hydrazone Switch Isomerization Kinetics. Org. Lett. 2013, 15, 5952–5955 10.1021/ol402789y. [DOI] [PubMed] [Google Scholar]

[ref466] Croteau M. L.; Su X.; Wilcox D. E.; Aprahamian I. Metal Coordination and Isomerization of a Hydrazone Switch. ChemPlusChem 2014, 79, 1214–1224 10.1002/cplu.201402134. [DOI] [Google Scholar]

[ref467] Foy J. T.; Ray D.; Aprahamian I. Regulating Signal Enhancement with Coordination-coupled Deprotonation of a Hydrazone Switch. Chem. Sci. 2015, 6, 209–213 10.1039/C4SC02882A. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref468] Langde S. M.; Aprahamian I. A ph Activated Configurational Rotary Switch: Controlling the E/Z Isomerization in Hydrazones. J. Am. Chem. Soc. 2009, 131, 18269–18271 10.1021/ja909149z. [DOI] [PubMed] [Google Scholar]

[ref469] Su X.; Robbins T. F.; Aprahamian I. Switching Through Coordination-coupled Proton Transfer. Angew. Chem., Int. Ed. 2011, 50, 1841–1844 10.1002/anie.201006982. [DOI] [PubMed] [Google Scholar]

[ref470] Landge S. M.; Tkatchouk E.; Benitez D.; Lanfranchi D. A.; Elhabiri M.; Goddard W. A. III; Aprahamian I. Isomerization Mechanism in Hydrazone-based Rotary Switches: Lateral Shift, Rotation, or Tautomerization?. J. Am. Chem. Soc. 2011, 133, 9812–9823 10.1021/ja200699v. [DOI] [PubMed] [Google Scholar]

[ref471] Ray D.; Foy J. T.; Hughes R. P.; Aprahamian I. A Switching Cascade of Hydrazone-based Rotary Switches Through Coordination-coupled Proton Relays. Nat. Chem. 2012, 4, 757–762 10.1038/nchem.1408. [DOI] [PubMed] [Google Scholar]

[ref472] Su X.; Voskian S.; Hughes R. P.; Aprahamian I. Manipulating Liquid-Crystal Properties Using a pH Activated Hydrazone Switch. Angew. Chem., Int. Ed. 2013, 52, 10734–10739 10.1002/anie.201305514. [DOI] [PubMed] [Google Scholar]

[ref473] Siegel J. S. Supramolecular Chemistry. Concepts and Perspectives - Lehn, J. -M. Science 1996, 271, 949–949 10.1126/science.271.5251.949. [DOI] [Google Scholar]

[ref474] Amendola V.; Fabbrizzi L.; Mangano C.; Pallavicini P. Molecular Movements and Translocations Controlled by Transition Metals and Signaled by Light Emission. Struct. Bonding (Berlin) 2001, 99, 79–115. [Google Scholar]

[ref475] Miyazawa A.; Fujiyoshi Y.; Unwin N. Structure and Gating Mechanism of the Acetylcholine Receptor Pore. Nature 2003, 423, 949–955 10.1038/nature01748. [DOI] [PubMed] [Google Scholar]

[ref476] Kaempfer R. Ribosomal Subunit Exchange during Protein Synthesis. Proc. Natl. Acad. Sci. U. S. A. 1968, 61, 106–113 10.1073/pnas.61.1.106. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref477] Nakahata M.; Takashima Y.; Hashidzume A.; Harada A. Redox-Generated Mechanical Motion of a Supramolecular Polymeric Actuator Based on Host-Guest Interactions. Angew. Chem., Int. Ed. 2013, 52, 5731–5735 10.1002/anie.201300862. [DOI] [PubMed] [Google Scholar]

[ref478] De Santis G.; Fabbrizzi L.; Iacopino D.; Pallavicini P.; Perotti A.; Poggi A. Electrochemically Switched Anion Translocation in a Multicomponent Coordination Compound. Inorg. Chem. 1997, 36, 827–832 10.1021/ic960892x. [DOI] [Google Scholar]

[ref479] Akutagawa T.; Koshinaka H.; Sato D.; Takeda S.; Noro S. I.; Takahashi H.; Kumai R.; Tokura Y.; Nakamura T. Ferroelectricity and Polarity Control in Solid-state Flip-flop Supramolecular Rotators. Nat. Mater. 2009, 8, 342–347 10.1038/nmat2377. [DOI] [PubMed] [Google Scholar]

[ref480] Ikeda A.; Tsudera T.; Shinkai S. Molecular Design of a ’’Molecular Syringe’’ Mimic for Metal Cations Using a 1,3-Alternate Calix[4]arene Cavity. J. Org. Chem. 1997, 62, 3568–3574 10.1021/jo962040k. [DOI] [PubMed] [Google Scholar]

[ref481] Knipe P. C.; Thompson S.; Hamilton A. D. Ion-mediated Conformational Switches. Chem. Sci. 2015, 6, 1630–1639 10.1039/C4SC03525A. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref482] Su X.; Robbins T. F.; Aprahamian I. Switching Through Coordination-Coupled Proton Transfer. Angew. Chem., Int. Ed. 2011, 50, 1841–1844 10.1002/anie.201006982. [DOI] [PubMed] [Google Scholar]

[ref483] Su X.; Voskian S.; Hughes R. P.; Aprahamian I. Manipulating Liquid-Crystal Properties Using a pH Activated Hydrazone Switch. Angew. Chem., Int. Ed. 2013, 52, 10734–10739 10.1002/anie.201305514. [DOI] [PubMed] [Google Scholar]

[ref484] Su X.; Lessing T.; Aprahamian I. The Importance of the Rotor in Hydrazone-based Molecular Switches. Beilstein J. Org. Chem. 2012, 8, 872–876 10.3762/bjoc.8.98. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref485] Su X.; Aprahamian I. Switching Around Two Axles: Controlling the Configuration and Conformation of a Hydrazone-Based Switch. Org. Lett. 2011, 13, 30–33 10.1021/ol102422h. [DOI] [PubMed] [Google Scholar]

[ref486] del Barrio J.; Horton P. N.; Lairez D.; Lloyd G. O.; Toprakcioglu C.; Scherman O. A. Photocontrol over Cucurbit[8]uril Complexes: Stoichiometry and Supramolecular Polymers. J. Am. Chem. Soc. 2013, 135, 11760–11763 10.1021/ja406556h. [DOI] [PubMed] [Google Scholar]

[ref487] Lan Y.; Wu Y. C.; Karas A.; Scherman O. A. Photoresponsive Hybrid Raspberry-Like Colloids Based on Cucurbit[8]uril Host-Guest Interactions. Angew. Chem., Int. Ed. 2014, 53, 2166–2169 10.1002/anie.201309204. [DOI] [PubMed] [Google Scholar]

[ref488] Ashton P. R.; Campbell P. J.; Chrystal E. J. T.; Glink P. T.; Menzer S.; Philp D.; Spencer N.; Stoddart J. F.; Tasker P. A.; Williams D. J. Dialkylammonium Ion Crown-Ether Complexes - the Forerunners of a New Family of Interlocked Molecules. Angew. Chem., Int. Ed. Engl. 1995, 34, 1865–1869 10.1002/anie.199518651. [DOI] [Google Scholar]

[ref489] Ashton P. R.; Chrystal E. J. T.; Glink P. T.; Menzer S.; Schiavo C.; Stoddart J. F.; Tasker P. A.; Williams D. J. Doubly Encircled and Double-Stranded Pseudorotaxanes. Angew. Chem., Int. Ed. Engl. 1995, 34, 1869–1871 10.1002/anie.199518691. [DOI] [Google Scholar]

[ref490] Ashton P. R.; Chrystal E. J. T.; Glink P. T.; Menzer S.; Schiavo C.; Spencer N.; Stoddart J. F.; Tasker P. A.; White A. J. P.; Williams D. J. Pseudorotaxanes Formed Between Secondary Dialkylammonium Salts and Crown Ethers. Chem. - Eur. J. 1996, 2, 709–728 10.1002/chem.19960020616. [DOI] [Google Scholar]

[ref491] Ashton P. R.; Fyfe M. C. T.; Glink P. T.; Menzer S.; Stoddart J. F.; White A. J. P.; Williams D. J. Molecular Meccano, Part 24. Multiply Stranded and Multiply Encircled Pseudorotaxanes. J. Am. Chem. Soc. 1997, 119, 12514–12524 10.1021/ja9714806. [DOI] [Google Scholar]

[ref492] Ashton P. R.; Fyfe M. C. T.; Martinez-Diaz M. V.; Menzer S.; Schiavo C.; Stoddart J. F.; White A. J. P.; Williams D. J. Molecular Meccano. Part 39 - Doubly Docked Pseudorotaxanes. Chem. - Eur. J. 1998, 4, 1523–1534. [DOI] [Google Scholar]

[ref493] Loeb S. J.; Tiburcio J.; Vella S. J. [2]Pseudorotaxane Formation with N-benzylanilinium Axles and 24-Crown-8 Ether Wheels. Org. Lett. 2005, 7, 4923–4926 10.1021/ol051786e. [DOI] [PubMed] [Google Scholar]

[ref494] Baroncini M.; Gao C.; Carboni V.; Credi A.; Previtera E.; Semeraro M.; Venturi M.; Silvi S. Light Control of Stoichiometry and Motion in Pseudorotaxanes Comprising a Cucurbit[7]uril Wheel and an Azobenzene-Bipyridinium Axle. Chem. - Eur. J. 2014, 20, 10737–10744 10.1002/chem.201402821. [DOI] [PubMed] [Google Scholar]

[ref495] Credi A.; Dumas S.; Silvi S.; Venturi M.; Arduini A.; Pochini A.; Secchi A. Viologen-calix[6]arene Pseudorotaxanes. Ion-pair Recognition and Threading/dethreading Molecular Motions. J. Org. Chem. 2004, 69, 5881–5887 10.1021/jo0494127. [DOI] [PubMed] [Google Scholar]

[ref496] Balzani V.; Credi A.; Marchioni F.; Stoddart J. F. Artificial Molecular-level Machines. Dethreading-rethreading of a Pseudorotaxane Powered Exclusively by Light Energy. Chem. Commun. 2001, 1860–1861 10.1039/b105160c. [DOI] [PubMed] [Google Scholar]

[ref497] Baroncini M.A Simple Molecular Machine Operated by Photoinduced Proton Transfer. Springer Theses; Springer: New York, 2011; Chapter 7, pp 71–76; 10.1007/978-3-642-19285-2_7. [DOI] [PubMed] [Google Scholar]

[ref498] Jeppesen J. O.; Becher J.; Stoddart J. F. Poised on the Brink Between a Bistable Complex and a Compound. Org. Lett. 2002, 4, 557–560 10.1021/ol0171362. [DOI] [PubMed] [Google Scholar]

[ref499] Rekharsky M. V.; Yamamura H.; Kawai M.; Osaka I.; Arakawa R.; Sato A.; Ko Y. H.; Selvapalam N.; Kim K.; Inoue Y. Sequential Formation of a Ternary Complex Among Dihexylammonium, Cucurbit[6]uril, and Cyclodextrin with Positive Cooperativity. Org. Lett. 2006, 8, 815–818 10.1021/ol0528742. [DOI] [PubMed] [Google Scholar]

[ref500] Balzani V.; Credi A.; Venturi M. Controlled Disassembling of Self-assembling Systems: Toward Artificial Molecular-level Devices and Machines. Proc. Natl. Acad. Sci. U. S. A. 2002, 99, 4814–4817 10.1073/pnas.022631599. [DOI] [PMC free article] [PubMed] [Google Scholar]

[ref501] Huang F.; Fronczek F. R.; Gibson H. W. A Cryptand/bisparaquat [3]Pseudorotaxane by Cooperative Complexation. J. Am. Chem. Soc. 2003, 125, 9272–9273 10.1021/ja0355877. [DOI] [PubMed] [Google Scholar]

PERMALINK

Artificial Molecular Machines

Sundus Erbas-Cakmak

David A Leigh

Charlie T McTernan

Alina L Nussbaumer

1. Introduction

1.1. The Language Used To Describe Molecular Machines

1.2. The Effects of Scale

1.3. Thought Machines Exploring Brownian Motion

Figure 1.

Figure 2.

1.4. Inspiration from Nature

1.5. Directional Transport and Work under Brownian Motion

1.6. Ratchet Mechanisms

1.6.1. Pulsating Ratchets

Figure 3.

Figure 4.

1.6.2. Tilting Ratchets

Figure 5.

Figure 6.

1.6.3. Information Ratchets

Figure 7.

1.6.4. Language Necessary To Describe the Operation of Molecular Machines

2. Controlling Motion in Covalently Bonded Molecular Systems

2.1. Controlling Conformational Changes

2.1.1. Correlated Motion through Nonbonded Interactions

Figure 8.

Figure 9.

Figure 10.

Figure 11.

2.1.2. Stimuli-Induced Control of Conformation about a Single Bond

Scheme 1. Molecular Brakes Operated by (a) Hg2+ Binding and (b) Sulfur Oxidation; and (c) Proposed Transition State Stabilization in Shimizu’s System203,206,207.

Scheme 2. A Molecular Switch Flipped by Singlet Oxygen211.

Figure 12.

Scheme 3. Chemically Driven Directional 120° Rotation of Kelly’s Triptycene Rotor 11(216).

Scheme 4. Directional 360° Rotation about a Single Bond via Four States A–D.

2.1.3. Stimuli-Induced Conformational Control in Organometallic Systems

Figure 13.

Figure 14.

Scheme 5. Control of Rotation in Ferrocene Complex 19 through Protonation253.

Figure 15.

2.1.4. Stimuli-Induced Conformational Control over Several Covalent Bonds

Scheme 6. (a) Negative Allosteric Receptor 21, Where Binding of Tungsten Forces Ring Contraction and Steric Clash of the 3- and 3′-Substituents of the Bipyridyl Unit; and (b) Positive Allosteric Receptor 22(263,264).

Figure 16.

Scheme 7. (a) Prevention of Organic Guest Binding on Complexation of Copper to 27; and (b) Organic Guest Is Only Bound in the Zinc-Complexed Form of 28(288).

Scheme 8. Chelation Control of Equatorial/Axial Conformers and Haberhauer’s Molecular Hinge290,299,

Scheme 9. Resorcin[4]arene 31, Vase and Kite Conformers, Stoddart’s Self-Complexing Lock 32, and Feringa’s Self-Complexing Rotor 33(98,321,322,327),

Scheme 10. Hamilton’s Acid Sensitive Switch328.

Scheme 45. Schematic Representation of the Reversible Locking and Unlocking of Switchable Catalyst 143(1439).

Scheme 11. pH-Driven Conformational Change in Oligomeric System 35(330).

Scheme 12. Large-Scale Extension of a Ligand Strand upon Pb(II) Complexation369,370.

2.2. Controlling Configurational Changes

Scheme 13. (a) Molecular Scissors 38; and (b) Structure of Molecular Hinge 39(414).

Figure 17.

Scheme 14. Minimization of Steric Interactions between Aromatic Groups and Substituent Results in (P,P)-(trans)-41-Stable Ground-State Conformation, with Axial Substituents.

Figure 18.

Figure 19.

Scheme 15. Hydrazone-Based Switches.

Scheme 16. Switching Cascade of Hydrazone Rotary Switches471.

3. Controlling Motion in Supramolecular Systems

3.1. Guest Binding Generating, or Assisted by, Large-Scale Intramolecular Motion

Scheme 17. Light-Operated Molecular Tweezers575.

Scheme 18. Decreased Drug Binding Affinity by a pH-Induced Conformational Change573.

Figure 20.

Figure 21.

Figure 22.

3.2. Intramolecular Ion Translocation

Scheme 19. Excited-State Intramolecular Proton Transfer in HBT607,608.

Scheme 20. Intramolecular Anion Translocation Mediated by (a) Redox609 and (b) Ligand Exchange610.

Scheme 21. Redox-Mediated Intramolecular Ion Translocation611.

Scheme 22. Redox-Mediated Pd Translocation in an Aromatic Sandwich Complex616.

4. Shuttling in Rotaxanes: Inherent Dynamics

4.1. Shuttling in Degenerate, Two-Station, Molecular Shuttles

Scheme 23. (a) The First “Molecular Shuttle”, 61;690 and (b) Degenerate Peptide-Based Molecular Shuttles 62–64 of Varying Linker Length693.

Figure 23.

Scheme 24. Complexation of Copper Leads to the Introduction of a Large Kinetic Barrier to Shuttling701.

4.2. Physical Models of Degenerate, Two-Station Rotaxanes

Figure 24.

4.3. Stimuli Responsive Molecular Shuttles

Scheme 1. Molecular Brakes Operated by (a) Hg²⁺ Binding and (b) Sulfur Oxidation; and (c) Proposed Transition State Stabilization in Shimizu’s System^203,206,207.

Scheme 2. A Molecular Switch Flipped by Singlet Oxygen²¹¹.

Scheme 5. Control of Rotation in Ferrocene Complex 19 through Protonation²⁵³.

Scheme 8. Chelation Control of Equatorial/Axial Conformers and Haberhauer’s Molecular Hinge^290,299^,

Scheme 9. Resorcin[4]arene 31, Vase and Kite Conformers, Stoddart’s Self-Complexing Lock 32, and Feringa’s Self-Complexing Rotor 33(98,321,322,327)^,

Scheme 10. Hamilton’s Acid Sensitive Switch³²⁸.

Scheme 12. Large-Scale Extension of a Ligand Strand upon Pb(II) Complexation^369,370.

Scheme 16. Switching Cascade of Hydrazone Rotary Switches⁴⁷¹.

Scheme 17. Light-Operated Molecular Tweezers⁵⁷⁵.

Scheme 18. Decreased Drug Binding Affinity by a pH-Induced Conformational Change⁵⁷³.

Scheme 19. Excited-State Intramolecular Proton Transfer in HBT^607,608.

Scheme 20. Intramolecular Anion Translocation Mediated by (a) Redox⁶⁰⁹ and (b) Ligand Exchange⁶¹⁰.

Scheme 21. Redox-Mediated Intramolecular Ion Translocation⁶¹¹.

Scheme 22. Redox-Mediated Pd Translocation in an Aromatic Sandwich Complex⁶¹⁶.

Scheme 23. (a) The First “Molecular Shuttle”, 61;⁶⁹⁰ and (b) Degenerate Peptide-Based Molecular Shuttles 62–64 of Varying Linker Length⁶⁹³.

Scheme 24. Complexation of Copper Leads to the Introduction of a Large Kinetic Barrier to Shuttling⁷⁰¹.

Scheme 25. Light-Driven Directional CD Shuttling in a [2]Rotaxane⁷¹².

Scheme 26. Solvent-Dependent Shuttling and Induced CD Response in a [2]Rotaxane⁷¹⁵.

Scheme 27. A pH-Driven Molecular Shuttle⁷¹⁸.

Scheme 28. A Redox-Driven Molecular Shuttle^757,758.

Scheme 29. Chloride-Induced Molecular Shuttling in a [2]Rotaxane⁷⁸³.

Scheme 30. Hydrolytic or Entropically Driven Restriction of Shuttling in a [2]Rotaxane⁷⁹².

Scheme 31. Chemically Driven Shuttling in a [2]Rotaxane⁷⁹³.

Scheme 33. Chemically Driven Molecular Information Ratchet⁸⁰⁹.