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. 2023 Jul 3;8(28):25432–25440. doi: 10.1021/acsomega.3c02955

Synthesis of Bis-tetraphenylethene as a Novel Turn-On Selective Zinc Sensor

Abdullah Saleh Hussein †,‡, Ferruh Lafzi §,*, Haydar Kilic §, Sinan Bayindir †,*
PMCID: PMC10357583  PMID: 37483257

Abstract

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The main purpose of this study is the synthesis of novel fluorescent Bis-TPE and the investigation of its wide range of photochemical behaviors. For this purpose, initially, Bis-TPE was synthesized. Following this, the interactions of Bis-TPE with a wide range of ions were studied in EtOH using ultraviolet–visible (UV–vis) and fluorescence spectroscopy. As a result of all UV–vis and fluorescence studies, it was determined that Bis-TPE showed turn-on sensor features against Zn2+ ions. Moreover, the limit of detection (LOD) and Ka values of Bis-TPE/Zn2+ were calculated as 0.97 μM (970 nM) and 3.76 × 105 M–1, respectively. Moreover, all reversal studies resulted in switchable on/off variation of the alternative addition of ZnCl2 and [Bu4N]OH to Bis-TPE. This result also implies that the probe Bis-TPE also exhibits specific OH– sensor properties in the presence of zinc.

Introduction

Nowadays, instead of methods that require expensive instrumentation and large volumes of samples, such as voltammetry, plasma mass, and atomic emission spectrometry, colorimetric and fluorometric detection of ions is of great interest due to its simplicity and sensitivity.1−10 Various metal particles take up an essential part of our daily physiological life. Zinc (Zn) ions, one of these metals, are the second most abundant element in the human body after iron ions.11−13 Various biological catalysts found in living systems contain zinc.14 For example, zinc is an abundant trace element in red blood cells as a key component of the enzyme carbonic anhydrase (hCAs), which aids in carbon dioxide metabolism pathways.15,16 In addition, the brain, muscles, bones, prostate, retina, kidneys, and liver are also organs that contain the most zinc.17,18 However, both the deficiency and excess of zinc ingredients in the living body need to be controlled carefully. Because abnormal excess levels of zinc, such as deficiency of zinc, can cause various diseases including Alzheimer’s disease, brain diseases, Parkinson’s disease, hair loss, etc.19−21 Hence, monitoring zinc specifically at all levels (especially μM) is of great importance in terms of living healthily, and the generation of efficient chemosensors specific for zinc detection is an important scientific necessity. Speaking of the importance of the specific detection of ions, nowadays, another technologically important and quite remarkable issue is aggregation-induced emission (AIE).22 In this context, tetraphenylethene (TPE) as an effective fluorophore has received much attention since the beginning of this century. The TPE unit can also function as an energy donor part in combination with some other fluorophores reported in many pieces of literature. In addition, organics containing TPE units have been used as effective organic sensors in recent years.23−34 In this context, we primarily synthesized novel bis-tetraphenylethene (Bis-TPE). Following synthesis, the AIE studies and detection properties against a wide range of metals and anions of Bis-TPE were investigated by colorimetric and spectroscopic techniques (Figure 1).

Figure 1.

Figure 1

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Strategies for examination of recognition properties of Bis-TPE.

Results and Discussion

Chemistry

The synthesis of TPE-based organic probes and investigation of ion sensor properties is a popular phenomenon from the past to the present. For this purpose, we synthesized novel Bis-TPE over multistep reaction routes (Figure 2). In this context, initially, output compounds TPE-(OMe) (3), TPE-(OH) (4), and TPE-(OH)-CHO (5) were obtained, as stated in the related literature (Figure 2A–C).35,36 Following the synthesis of output molecules 3, 4, and 5, the target organic probe novel Bis-TPE was synthesized from the reaction of TPE-(OH)-CHO (5) with N1-(2-aminoethyl)ethane-1,2-diamine (6) in ethanol at the reflux temperature of ethanol (Figure 2D).

Figure 2.

Figure 2

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Synthesis strategy of Bis-TPE.

Ultraviolet–Visible (UV–Vis) and Fluorescence Response of Bis-TPE to Various Ions

Following the synthesis of Bis-TPE, to clearly investigate the interaction of the probe with a variety of ions (cations and/or anions), the ultraviolet–visible (UV–vis) and fluorescence studies of Bis-TPE were first performed in a variety of solvent systems such as MeOH, EtOH, CH3CN, dimethyl sulfoxide (DMSO), and tetrahydrofuran (THF) and their aqua solvent systems (Figure S5). While no interaction was observed in aqueous solutions, similar results were obtained from studies performed in other organic solvents such as CH3CN, DMSO, and THF. On the other hand, although similar results were obtained with EtOH in the studies carried out in MeOH, ethanol was preferred as a solvent, considering both the lower fluorescence intensity and the harmful effect of methanol on health (Figure S5). In this context, studies were carried out in EtOH, which is relatively less harmful in related solvents. The UV–vis spectra for all ions were recorded after about 10 min of the addition of 2 equiv of each mentioned ion, and the UV–vis spectra were obtained as given in Figure 3A. As illustrated in Figure 3A, the UV–vis spectrum of Bis-TPE exhibited a broad band at 305 nm and also a strong band at about 231 nm. The interaction of Bis-TPE with varieties ions of metals (Al3+, Ca2+, Cd2+, Co2+, Cu2+, Fe2+, Fe3+, Hg2+, Mg2+, Mn2+, Ni2+, Pb2+, and Zn2+ as their chloride salts) and anions ([Bu4N]F, [Bu4N]Cl, [Bu4N]Br, [Bu4N]I, [Bu4N]AcO, [Bu4N]BnO, [Bu4N]HSO4, [Bu4N]ClO4, [Bu4N]CN, [Bu4N]SCN, [Bu4N]H2PO4, [Bu4N]OH) was investigated in EtOH. Except for minor changes, no significant changes were observed from the absorption studies of Bis-TPE with anions (Figure S6). According to UV–vis studies in EtOH, in the presence of Zn2+, the absorption band of Bis-TPE at 231/305 nm decreased to 240/310 nm with red shifts. On the other hand, in UV–vis studies of Bis-TPE with other metal ions in EtOH, it was observed that the absorption band of Bis-TPE at 231/305 nm increased to 225–230/301–310 nm with blue–red shifts (Figure 3A). In addition to UV–vis studies, fluorescence spectroscopy studies were also carried out in order to measure the ability of Bis-TPE (10 μM) as a fluorescent ion (cation and/or anion) sensor. In parallel with the UV–vis studies, no significant and specific changes were observed from the interaction of Bis-TPE with anions (Figure 3B). From fluorescence studies with cations, a specific spectral change was observed against Zn2+ ions, again in agreement with UV–vis studies. Thus, to gain further insight into the selective and sensitive Zn2+ binding ability of Bis-TPE (10 μM) toward a series of cations were evaluated by observing changes in their fluorescence emission spectra in ethanol (Figure 3B). As illustrated in Figure 3B, Bis-TPE alone exhibited two fluorescence peaks at 382 and 570 nm in EtOH with an excitation of 280 nm (Figures 3B and S7A). Under the same conditions, the fluorescence spectra of the interactions of Bis-TPE with metal ions were also measured within about 10 min after the addition of ions. As a result of Bis-TPE interactions with metal ions, very small changes (approximately 1 nm) were observed in other metal ions except for Zn2+ ions, while important changes were observed due to the interaction of Bis-TPE with Zn2+ ions. That is, it was determined that the fluorescence peaks of Bis-TPE at 503 nm increased in the presence of Zn2+ (Figure 3B, red). Consistent with UV–vis studies, it is seen that the fluorescence peak of Bis-TPE at 503 nm increased with Zn2+ and decreased due to interactions with others. As a result of the studies, it can be said that Bis-TPE can be a specific turn-on fluorescent sensor at 503 nm for Zn2+ ions. Another point worth noting here is the nature of the fluorescence peak around 570 nm. Namely, whether this peak is a fluorescence signal or a 2nd-order diffraction of the excitation light. So here, the aggregated particles enhance the light scattering reasonably, and this may be checked by excitation wavelength dependency. The wavelengths of the monochromatic light from the monochromator for excitation were set at 280, 300, 320, 340, 360, 380, 420, 440, and 460 nm (Figure S7B). Fluorescence is most efficiently excited at 280 nm, and the fluorescence intensity decreases continuously to λex of 460 nm. The blue fluorescence intensity clearly decreases significantly as the excitation wavelength increases, and this is consistent with numerous previously reported fluorescence intensity results.37−39 Following extensive anion studies, in this stage, AIE studies of Bis-TPE were also carried out with increasing water content in ethanol. The colorimetric studies show that the color change shifted from colorless to bright orange with increasing water content. Additionally, the fluorescence intensity of the TPE-based organic probe Bis-TPE started to increase in small intervals with the addition of 10% of H2O and reached its maximum value at 70–90% of H2O. That is, the fluorescence intensity at 575 nm of Bis-TPE in EtOH/H2O (v/v) has increased with increasing water percentage. This may be essentially a clear indication that Bis-TPE exhibits an AIE feature. However, the fact that Bis-TPE excited at 280 nm gave fluorescence intensity at 575 nm suggests that this is not a fluorescence signal, as in anion studies, but may instead be a 2nd-order diffraction. Indeed, it is thought-provoking what could be the reason why it does not give significant results in terms of fluorescence but gives a visible color change with the increasing water ratio. Here, it is thought that the AIE behavior of Bis-TPE, which contains nucleophilic groups such as nitrogen (N) and oxygen (O), is the suppression of the photoinduced electron transfer due to the increased aggregation of Bis-TPE (Figures 3C and S8). Additionally, the excited state intramolecular proton transfer (ESIPT) process is influenced by the acidity of the proton donor and the alkalinity of the proton receptor, which depends on the charge distribution of the donor and receptor atoms. In this context, the UV–vis and fluorescence properties of Bis-TPE suggest that it undergoes the ESIPT process more readily due to a significant change in electron density in its excited state. The fluorescence emission phenomenon may be caused by the tautomerization of Bis-TPE through the ESIPT process, where a proton from the OH group shifts to the CH=N group via an intramolecular hydrogen bond in the excited state (Scheme S1).40

Figure 3.

Figure 3

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UV–Vis (A) and fluorescence (B) spectra of Bis-TPE in the absence and presence of metal ions in EtOH and (C) the photographic images of Bis-TPE in the various H2O ratios.

In addition to UV–vis and fluorescence experiments, the individual interactions of probes with ions and the specific spectral changes as a result of these interactions are also important due to the fact that it is unlikely that a single metal will always be present in samples. In this context, at this stage, following UV–vis and fluorescence experiments (Figure 3), to study the influence of other metal ions on Zn2+ ions binding with Bis-TPE, competitive experiments in the presence of ZnCl2 with other metals were performed in ethanol (Figures 4 and S9). The results of experiments showed that fluorescence reduction induced by the mixture of Zn2+ with all other metal ions was like that induced by zinc alone in EtOH (Figure 4). Thus, as a result of all of these studies, none of the other tested metal ions were found to interfere with the interaction of Bis-TPE with Zn2+ in ethanol.

Figure 4.

Figure 4

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Selectivity of Bis-TPE for zinc in the presence of other metal ions.

Following the experimental UV–vis studies, the band-gap energy (Eg) values of Bis-TPE and Bis-TPE-Zn2+ were also determined experimentally (Figure 5). For this, first, the absorption coefficient (α) was calculated using the formula 1. Here, d indicates the film thickness and T indicates the percent optical transmittance value.

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Then, the Eg range of Bis-TPE and Bis-TPE-Zn2+ were calculated using the formula 2. Here, (hν) is the photon energy and K is the material constant.41

graphic file with name ao3c02955_m002.jpg 2

Moreover, the Eg can be correlated with electrical conductivity42 and kinetic stability. An organic molecule with a wide highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gap is considered to have high chemical hardness and good stability, while a molecule with a narrow HOMO–LUMO energy gap is considered to have good chemical reactivity. For this purpose, at this stage, the experimental calculation of Eg values was calculated. The Eg values of Bis-TPE and Bis-TPE-Zn2+ were calculated as 3.55 and 3.48 eV, respectively. Although the numerical values are different, the experimental and theoretical results are proportionally compatible with each other. Additionally, according to the experimental Eg values and the obtained absorbance (240/310 nm) measurements, Bis-TPE can also be used in photovoltaic applications were predicted.

Figure 5.

Figure 5

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Band-gap energies of Bis-TPE and Bis-TPE-Zn2+.

Following general UV–vis and fluorescence experiments of Bis-TPE with selected ions to study the sensitivity of Bis-TPE toward Zn2+ ion sensing, the fluorescence reply of the interaction of Bis-TPE with increasing ZnCl2 with excitation at 280 nm in EtOH was examined (Figure 6A). Upon the progressive addition of ZnCl2, the fluorescence intensity gradually increased. In the presence of about 16 μM of ZnCl2, the fluorescence difference between Bis-TPE and the Bis-TPE-Zn2+ ion was more than three times of Bis-TPE. As more ZnCl2 was added, the fluorescence intensity of Bis-TPE increased with the concentration of Zn2+ ions. Following this, the limit of detection (LOD) and the limit of quantitation (LOQ) values of Bis-TPE for Zn2+ ions were calculated by the fluorescence titration results. The LOD and LOQ values were calculated from the relevant formulas (Figure 6B), and the LOD and LOQ values of Bis-TPE for Zn2+ ion were calculated as 0.97 μM (970 nM) and 2.96 μM in EtOH, respectively (Figure 6B).

Figure 6.

Figure 6

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(A) Fluorescence spectra of Bis-TPE in the presence of Zn2+ and (B) the change in the fluorescence intensity of Bis-TPE with the increasing concentration of Zn2+.

The calculation of the binding constant (Ka) value is also a very important parameter for characterizing sensor candidates. To calculate Ka values, first, the stoichiometry of the binding between the zinc and the organic probe Bis-TPE needs to be determined. To determine the binding modes and stoichiometry of Bis-TPE with ZnCl2, the Job’s plot analysis was carried out (Figure S10) as in the Supporting Data file, and the interaction ratio between zinc and Bis-TPE was calculated to be 1:1 (Figure 7A). Following this, the Ka value of Bis-TPE for Zn2+ was calculated by the fluorescence titration results and relevant formula, as mentioned in Figure 6B. According to the calculation, the Ka value of Bis-TPE with Zn2+ was calculated to be 3.76 × 105 M–1 (Figure 7B), and this result implies that there is a relatively strong binding between the probe Bis-TPE and zinc ions. Similarly, the pH and time studies are also important for the characterization of sensor candidate organic probes. First, pH studies were performed in ethanol over a wide range from 3 to 12 (Figures 7C and S11). As a result of pH studies, it was observed that Bis-TPE had maximum fluorescence values at pH 6–12, while it had relatively lower fluorescence values at pH 3–5 (Figure 7C, pink). Additionally, no significant difference is observed except for minor changes at different pH values of Bis-TPE (Figure 7C, blue). On the other hand, the fluorescence intensity of Bis-TPE exposed to Zn2+ was monitored as a function of exposure time (Figures 7D and S12). As can be seen in Figure 7D, the initial fluorescence intensity of Bis-TPE at 503 nm decreased dramatically upon exposing (about 2 min) Bis-TPE to the Zn2+ ions at room temperature.

Figure 7.

Figure 7

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(A) Job’s plot of Bis-TPE with ZnCl2, (B) the Benesi–Hildebrand plot based on a 1:1 association stoichiometry between Bis-TPE and Zn2+, (C) the fluorescence values of Bis-TPE with [ZnCl2] at different pH (3–12) values, and (D) the exposure times of Bis-TPE with ZnCl2.

On the other hand, the switchable or reversible sensing properties of chemosensor candidates are another master feature of organic probes. In reversal studies, the alternative addition of ZnCl2 and [Bu4N]OH to Bis-TPE results in switchable on/off variation in the emission intensity at 503 nm (Figures 8A and S13). The studies have shown that Bis-TPE could be easily reused for Zn2+ and OH– sensing for up to about five cycles (Figure 8A). Moreover, the molecular logic function was built based on the optical behavior of Bis-TPE with zinc and hydroxide as inputs. Here, to set up a logic gate, OUTPUT logics 1 and 0 were assigned to turn “on” and “off” fluorescence, respectively. Considering this information, when the data is customized, Bis-TPE as a chemosensor remains turned off in the absence of the INPUTS Zn2+ (In1) and OH– (In2). When Zn2+ (In1) was added to Bis-TPE, an increase in emission intensity at 503 nm was noted, resulting in output logic 1, which is a turn-on. On the contrary, when only OH– (In2) ions were added to Bis-TPE, the decrease observed in the emission peak at 503 nm was noted, resulting in output logic 0 (Figure 8B).

Figure 8.

Figure 8

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(A) Reversible switching of the fluorescence intensity and (B) the “IMPLICATION” logic gate.

Within the scope of this study, Bis-TPE showed a turn-on fluorescence sensor feature against Zn2+ ions in the ethanol solvent were determined. The practical feasibility of the existing Bis-TPE is compared with some of the previous reports on Zn2+ sensors specifically for detection methods and LOD values. When the values in Table 1 are compared, we can say that the values obtained as a result of this study are as acceptable as the values obtained for zinc sensing probes in the literature.43−47

Table 1. Comparison of Some Zn2+ Selective Chemosensors.

refs detection method sensing ions LOD (μM)
(39) fluorescent Zn2+ 0.62
(40) fluorescent Zn2+ 0.07
(41) fluorescent Zn2+ 0.10
(42) fluorescent Zn2+ 0.10
(43) fluorescent Zn2+ 0.09
this study fluorescent Zn2+ 0.97
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Interaction morphology holds significance in sensor studies, and based on the existing literature,6 there are three potential binding sites in Bis-TPE associated with zinc ions. These sites include the double N (Schiff base) and OH groups of the TPE group and the NH core of the linker (Figure 9A). For this purpose, to understand the interaction mechanism between zinc ions and Bis-TPE, 1H NMR, and Fourier transform infrared (FT-IR) spectra were utilized (Figures S14B and S15). Initially, a comparison was made between the 1H NMR spectra of Bis-TPE with and without Zn2+ ions (Figure S14A). Accordingly, it can be observed that the proton signals of OH, aliphatic CH2, and N=CH experienced some shifts toward the low field. The presence of all functional groups with minor shifts in the FT-IR spectrum also suggests interactions (Figure S15). On the other hand, to gain insight into the structural and electronic properties of Bis-TPE and Bis-TPE-Zn2+ complexes, density functional theory (DFT) calculations were carried out by using B3LYP in combination with the 6-311G(d,p) basis set for H, C, N, and O atoms and the LANL2DZ basis set for the zinc atom (Gaussian 09).48 The corresponding frontier molecular orbitals (MOs) results were obtained from the time-dependent DFT (TD-DFT) computations at the same level. Figure 9B shows the ground-state optimized structures of Bis-TPE and Bis-TPE-Zn2+. The highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) of Bis-TPE and Bis-TPE-Zn2+ are calculated in the gas phase for the singlet spin and doublet spin, respectively. For compound Bis-TPE, the HOMO is delocalized on the TPE center and extends onto the OH–phenyl moieties and the LUMO is mainly localized on the TPE-center moieties with a 2.732 eV band gap. Electron density distribution on Bis-TPE-Zn2+ from α-spin HOMO to α-spin LUMO and β-spin HOMO to β-spin LUMO is delocalized on the TPE center and extends onto the OH–phenyl moieties with 1.227 and 1.216 eV band gaps (Figure 9C). Electron density distribution on Bis-TPE-Zn2+ from α-spin HOMO – 1 to α-spin LUMO + 1 and β-spin HOMO – 1 to β-spin LUMO + 1 is shown in Figure S16. The band gap reduces from 2.732 to 1.227 and 1.216 eV, which is consistent with the red shift in the absorption spectra.

Figure 9.

Figure 9

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(A) Principle of a “turn-on/off” sensing for Zn2+ and OH– detection under UV–vis radiation, (B) ground-state optimized structures of Bis-TPE and Bis-TPE-Zn2+, and (C) frontier molecular orbitals of Bis-TPE in singlet spin and Bis-TPE-Zn2+ doublet spin.

Experimental Section

Synthesis of Bis-TPE

The output molecules (2-(4-methoxyphenyl)ethene-1,1,2-triyl)tribenzene (3), 4-(1,2,2-triphenylvinyl)phenol (4), and 2-hydroxy-5-(1,2,2-triphenylvinyl)benzaldehyde (5) were synthesized following the literature.43,44 The detailed experimental procedure and spectroscopic data are given in the Supporting Data file (Figures 2A–C and S1–S3). Following the synthesis of output molecules, the target novel Bis-TPE was synthesized as follows. 2-Hydroxy-5-(1,2,2-triphenylvinyl)benzaldehyde (5) (500 mg, 1.33 mmol) was dissolved in ethanol (15 mL). To this, a solution of diethylenetriamine (69 mg, 0.66 mmol), also dissolved in the same solvent (5 mL), was added dropwise at room temperature. The reaction mixture was then heated under reflux for 8 h and allowed to cool at room temperature. After the removal of the solvent under reduced pressure, the crude product was purified by recrystallization over ethanol to obtain Bis-TPE (500 mg, 92%) as a yellow solid. 1H NMR (400 MHz, CDCl3) δ 13.27 (bs, 2H), 8.08 (s, 2H), 7.36–6.92 (m, 34H), 6.90 (s, 2H), 6.67 (d, J = 8.4 Hz, 2H), 4.01–3.44 (m, 4H), 3.10–2.58 (m, 4H). 13C NMR (100 MHz, CDCl3) δ 166.4, 166.3, 160.2, 144.0, 143.9, 140.6, 140.1, 135.9, 134.5, 134.4, 131.7, 131.6, 128.1, 128.0, 127.9, 126.8, 126.7, 126.6, 118.28, 118.27, 116.6, 59.5, 49.9 (Figure S4).

Procedures of Measurement of Photophysical Properties

The UV–vis and fluorescence studies of Bis-TPE with various ions were recorded following the introduction of the ions (1 equiv) at room temperature each time in ethanol. The fluorescence titration study of Bis-TPE with ZnCl2 was recorded by adding corresponding concentrations of ZnCl2 to a solution of Bis-TPE in EtOH. Each measurement was repeated at least twice until consistent values were obtained. In addition, the Job’s plot measurement was performed, and following this, the LOD, LOQ, and Ka values were calculated with related formulas. The detailed experimental procedures are given in the Supporting Data.

Conclusions

In conclusion, novel Bis-TPE was synthesized and its wide range of photochemical properties was investigated. For this purpose, the interactions of Bis-TPE with a wide range of ions were studied in a variety of solvent systems, and Bis-TPE showed turn-on sensor features against Zn2+ in ethanol. Moreover, the Bis-TPE-Zn2+ system showed specific turn-off fluorescence features against hydroxide ions. This also means reversible sensing properties and reusable Bis-TPE after the interaction with zinc. The LOD, LOQ, and Ka values of Bis-TPE-Zn2+ were calculated as 0.97 (970 nm) μM, 2.96 μM, and 3.76 × 105 M–1, respectively. Ultimately, effective processes were established for the synthesis of Bis-TPE and the detection of zinc and hydroxide in ethanol.

Acknowledgments

The authors are thankful for the financial support of Bingöl and Atatürk Universities and also wish to express their sincerest gratitude to Dr. Barış Anıl for their kind contributions to NMR spectra.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.3c02955.

  • General experimental methods and characterizations of the materials (PDF)

Author Contributions

A.S.H.: investigation; F.L.: investigation, writing & editing, and supervision; H.K.: investigation; and S.B.: investigation and supervision.

The authors declare no competing financial interest.

Supplementary Material

ao3c02955_si_001.pdf (1,014.9KB, pdf)

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