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. 1986 Aug;83(15):5355–5359. doi: 10.1073/pnas.83.15.5355

Molecular devices: Caroviologens as an approach to molecular wires—synthesis and incorporation into vesicle membranes

Thomas S Arrhenius *, Mireille Blanchard-Desce †, Maya Dvolaitzky †,‡, Jean-Marie Lehn *,†, Jacques Malthete †
PMCID: PMC386284  PMID: 16593731

Abstract

Molecular wires, which would allow electron flow to take place between different components, are important elements in the design of molecular devices. An approach to such species would be molecules possessing an electron-conducting conjugated chain, terminal electroactive polar groups, and a length sufficient to span a lipid membrane. To this end, bispyridinium polyenes of different lengths have been synthesized and their incorporation into the bilayer membrane of sodium dihexadecyl phosphate vesicles has been studied. Since they combine the features of carotenoids and of viologens, they may be termed caroviologens. Vesicles containing the caroviologen whose length approximately corresponds to the thickness of the sodium dihexadecyl phosphate bilayer display temperature-dependent changes of its absorption spectrum reflecting the gel → liquid-crystal phase transition of the membrane. The data agree with a structural model in which the caroviologens of sufficient length span the bilayer membrane, the pyridinium sites being close to the negatively charged outer and inner surfaces of the sodium dihexadecyl phosphate vesicles and the polyene chain crossing the lipidic interior of the membrane. These membranes may now be tested in processes in which the caroviologen would function as a continuous, transmembrane electron channel—i.e., as a molecular wire. Various further developments may be envisaged along these lines.

Keywords: carotenoids, bispyridinium polyenes, electron channel

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Selected References

These references are in PubMed. This may not be the complete list of references from this article.

  1. Bart J. C., MacGillavry C. H. The crystal and molecular structure of canthaxanthin. Acta Crystallogr B. 1968 Dec 15;24(12):1587–1606. doi: 10.1107/s056774086800470x. [DOI] [PubMed] [Google Scholar]
  2. Bisseret P., Wolff G., Albrecht A. M., Tanaka T., Nakatani Y., Ourisson G. A direct study of the cohesion of lecithin bilayers: the effect of hopanoids and alpha, omega-dihydroxycarotenoids. Biochem Biophys Res Commun. 1983 Jan 14;110(1):320–324. doi: 10.1016/0006-291x(83)91298-6. [DOI] [PubMed] [Google Scholar]
  3. Buchwald M., Jencks W. P. Optical properties of astaxanthin solutions and aggregates. Biochemistry. 1968 Feb;7(2):834–843. doi: 10.1021/bi00842a042. [DOI] [PubMed] [Google Scholar]
  4. Deamer D., Bangham A. D. Large volume liposomes by an ether vaporization method. Biochim Biophys Acta. 1976 Sep 7;443(3):629–634. doi: 10.1016/0005-2736(76)90483-1. [DOI] [PubMed] [Google Scholar]
  5. Drexler K. E. Molecular engineering: An approach to the development of general capabilities for molecular manipulation. Proc Natl Acad Sci U S A. 1981 Sep;78(9):5275–5278. doi: 10.1073/pnas.78.9.5275. [DOI] [PMC free article] [PubMed] [Google Scholar]
  6. Gaffney B. J., Mich R. J. Letter: A new measurement of surface charge in model and biological lipid membranes. J Am Chem Soc. 1976 May 12;98(10):3044–3045. doi: 10.1021/ja00426a076. [DOI] [PubMed] [Google Scholar]
  7. Haddon R. C., Lamola A. A. The molecular electronic device and the biochip computer: present status. Proc Natl Acad Sci U S A. 1985 Apr;82(7):1874–1878. doi: 10.1073/pnas.82.7.1874. [DOI] [PMC free article] [PubMed] [Google Scholar]
  8. Hubbell W. L., McConnell H. M. Molecular motion in spin-labeled phospholipids and membranes. J Am Chem Soc. 1971 Jan 27;93(2):314–326. doi: 10.1021/ja00731a005. [DOI] [PubMed] [Google Scholar]
  9. Lehn J. M. Supramolecular chemistry: receptors, catalysts, and carriers. Science. 1985 Feb 22;227(4689):849–856. doi: 10.1126/science.227.4689.849. [DOI] [PubMed] [Google Scholar]
  10. Mendelsohn R., Van Holten R. W. Zeaxanthin ([3R,3'R]-beta, beta-carotene-3-3'diol) as a resonance Raman and visible absorption probe of membrane structure. Biophys J. 1979 Aug;27(2):221–235. doi: 10.1016/S0006-3495(79)85213-3. [DOI] [PMC free article] [PubMed] [Google Scholar]
  11. Platt J. R. Carotene-Donor-Acceptor Complexes in Photosynthesis: The predicted lowering of the excited states of carotenoids may offer a new photosynthetic pathway. Science. 1959 Feb 13;129(3346):372–374. doi: 10.1126/science.129.3346.372. [DOI] [PubMed] [Google Scholar]
  12. Seelig A., Seelig J. The dynamic structure of fatty acyl chains in a phospholipid bilayer measured by deuterium magnetic resonance. Biochemistry. 1974 Nov 5;13(23):4839–4845. doi: 10.1021/bi00720a024. [DOI] [PubMed] [Google Scholar]

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