Intramolecular Proton Transfer Research Articles

Effect of Silyl Ether Bulk on Excited-State Intramolecular Proton Transfer-Based Sensing of Extant Hydrogen Fluoride for G-Series Nerve Agent Detection.

Luminescence-based sensing provides a method for the rapid detection of nerve agents. Previous approaches have generally focused on sensing materials containing a nucleophilic group that can react with the electrophilic phosphorus atom found in nerve agents. Herein we report an alternative approach for the detection of phosphonofluoridate-based G-series nerve agents that utilizes the fact they contain hydrogen fluoride. We have developed silylated sensing materials based on an excited-state intramolecular proton transfer (ESIPT) reporter compound, 2-[benzo[d]thiazol-2-yl]phenol. Thin films of differently silylated 2-[benzo[d]thiazol-2-yl]phenol were found to react with the hydrogen fluoride found in di-iso-propyl fluorophosphate (DFP), a simulant of sarin (G-series nerve agent), and turn on the ESIPT emission of the reporter compound. The use of the ESIPT emission reduced the impact of background fluorescence and improved the sensitivity of the detection. The effectiveness of the approach was dependent on the stability of the silyl protecting group used, with the least sterically hindered (trimethylsilyl) found to be too unstable to the ambient environment while the most sterically hindered, e.g., tri-iso-propylsilyl and tert-butyldiphenylsilyl were found to be insufficiently reactive to be useful in a real detection scenario. The sensing material composed of the tert-butyl dimethylsilyl protected 2-[benzo[d]thiazol-2-yl]phenol was found to have the best balance between stability under ambient conditions, and reactivity and selectivity to hydrogen fluoride. In a 3s exposure, it could detect hydrogen fluoride down to a concentration of around 23 ppm in DFP with 99% purity.

Synthesis of anthraquinone-based azo-metal(II) complexes as potent anti-oxidizing agents

The 3-diethylaminophenol (3-DEAP) incorporated anthraquinone mono-azo dye derivative [(E)-1-((4-(diethylamino)-2-hydroxyphenyl)diazenyl)anthracene-9,10-dione] DAAD was synthesized through an electrophilic substitution reaction. The interaction between the -OH functional group and the nitrogen atom of the azo moiety may result in intramolecular proton transfer in the DAAD. DAAD was treated with metal ions such as Co(II), Ni(II), and Cu(II) acetates in a ratio of 2 : 1 revealing an octahedral structure. Many analytical and spectroscopic methods, including UV-vis, FT-IR, (1H and 13C) NMR, HRMS, TGA, VSM, ESR, and powder XRD methods, were used to verify the structural characteristics of the compounds. Additionally, the potency of the in-vitro antioxidant properties of the ligand and its Cu(II), Ni(II), and Co(II) complexes were evaluated; the results revealed that the Co(II) complex showed a maximum percent inhibition of 85 μM against the standard ascorbic acid.

Excited-State Intramolecular Proton Transfer toward Conical Intersections in Indigo, Epindolidione, and Indirubin.

Indigo exhibits a high degree of photostability, experimentally supported by observations such as quenching of fluorescence and an exceptionally short excited-state lifetime. Epindolidione, a structural isomer of indigo, is highly fluorescent in contrast to indigo, while indirubin, another structural isomer, exhibits weak fluorescence similar to that of indigo. To elucidate the origin of the difference in photophysical and photochemical behavior, potential energy profiles of the excited-state intramolecular proton transfer in indigo, epindolidione, and indirubin are computationally studied by quantum chemical calculations using the TDDFT and extended MS-CASPT2 (XMS-CASPT2) methods. As a result, it is found that indigo and indirubin exhibit little energy barrier for the single proton transfer (SPT) in the S1(ππ*) state from the diketo to keto-enol form and low energy of the S1/S0 conical intersection (CI) in the latter form with a planar molecular structure. Epindolidione, on the other hand, exhibits much higher barriers for SPT and access to CI. These results suggest that the excited-state SPT and subsequent nonradiative deactivation via CI are more likely to occur in indigo and indirubin than in epindolidione, which is consistent with the experimental observations described above. For indigo and epindolidione, the deactivation channels via the second SPT from the keto-enol to dienol form are also compared.

FTIR study of light-induced proton transfer and Ca2+ binding in T82D mutant of TAT rhodopsin

Proton transfer reactions play important functional roles in many proteins, such as enzymes and transporters, which is also the case in rhodopsins. In fact, functional expression of rhodopsins accompanies intramolecular proton transfer reactions in many cases. One of the exceptional cases can be seen in the protonated form of marine bacterial TAT rhodopsin, which isomerizes the retinal by light but returns to the original state within 10−5 s. Thus, light energy is converted into heat without any function. In contrast, the T82D mutant of TAT rhodopsin conducts the light-induced deprotonation of the Schiff base at high pH. In this article, we report the structural analysis of T82D by means of difference Fourier transform infrared (FTIR) spectroscopy. In the light-induced difference FTIR spectra at 77 K, we observed little hydrogen out-of-plane vibrations for T82D as well as the wild-type (WT), suggesting that the planar chromophore structure itself is not the origin of the reversion from the K intermediate in WT TAT rhodopsin. Upon relaxation of the K intermediate, T82D forms the following intermediate, such as M, whereas K of WT returns to the original state. Present FTIR analysis revealed the proton transfer from the Schiff base to D82 in T82D upon formation of the M intermediate. It is accompanied by the second proton transfer from E54 to the Schiff base, forming the N intermediate, particularly in membranes. The equilibrium between the M and N intermediates corresponds to the protonation equilibrium between E54 and the Schiff base. We also found that Ca2+ binding takes place in T82D as well as WT but with 6 times lower affinity. An altered hydrogen-bonding network would be the origin of low affinity in T82D, where deprotonation of E54 is involved in the Ca2+ binding.

Photo-isomerization enabled reversible wavelength switching in fiber random laser for color image encryption

Random lasers owing the functionality of generating random spectra facilitate the chaotic encrypted systems essential for cryptography in the current information epoch. Nevertheless, single wavelength bands of random lasers provide an unsuitable key for image encryption that causes outline interpretation and a fragile complex dual chaotic encryption demanding secured image encryption. This research presents an inevitable development of a reversible switchable wavelength fiber random laser composed of the mixture of highly polarized intramolecular charge transfer dye molecules and the optimum concentration of titanium dioxide acting as gain and efficient scattering mediums respectively within a polyvinyl alcohol matrix. This mixture with a certain ratio is coated on a fiber employing a dip coated method, followed by a layer of polydimethylsiloxane to facilitate with high coefficient of thermal expansion. Random laser emission is enabled with dynamically switchable wavelengths obeying the excited state intramolecular proton transfer phenomenon under the photo-isomerization. The optimum scatters concentration yields a lower threshold of 32 µJ/cm2 with full width at half maximum of 0.4 nm and dual emission reversible switchable wavelength bands centered around 443 nm and 464 nm attributed to inter charge transfer feature of the dye molecules. Thereby, the dual reversible switchable wavelength bands feed as input for a dual chaotic color image encryption system. Further, in this integrated system, beam divergence of random laser emissions remains less than 20° during both situations of with- and without irradiation. This delicate approach paves the way in laying the foundation about the applicability of fiber random lasers in an information security system.

“AIE+ESIPT” based naphthothiazole fluorescent probes for live cell imaging

Dual-functional organic fluorophores with aggregation induced emission (AIE) behavior and excited-state intramolecular proton transfer (ESIPT) behavior are of great significance to the design of imaging probes to bioimage systems. However, the pursuit of probes exhibiting dual AIE+ESIPT effects for live cell imaging remains an ongoing research challeng. Herein, we have successfully developed naphthothiazole fluorescent probes, HNBT-H and HNBT-G, based on the "AIE+ESIPT" effect. These probes were designed by incorporating responsive units for β-galactosidase (β-gal) and H2O2 into the pre-existing "AIE+ESIPT" HNBT fluorophore framework. The HNBT-H probe demonstrated the capability to distinguish various levels of H2O2. Furthermore, the applicability of HNBT-H and HNBT-G have been examined in living systems. These probes exhibit a good biocompatibility and low toxicity, the cell imaging experiments demonstrate the capability of HNBT-H and HNBT-G for fluorescence visualization in response to β-gal and H2O2 in RAW264.7 cells and PC12 cells.

Theoretical insights from computational analyses: solvent-polarity-associated excited state behaviours for the novel NP-BSD chemosensor

Given the potential luminous advantages of salicylideneaniline (SA) derivatives, in this work, the phenyl π-extension-bis(salicylidene)-1,5-diaminonaphthalene (NP-BSD) fluorophore is explored on its photo-induced reactional behaviours in solvents theoretically. Given solvent surroundings with different polarities, we studied the hydrogen-bonding interactions in different solvents and their influences on excited state proton transfer (ESPT) reaction by photoexcitation for NP-BSD fluorophore. First, photo-induced geometrical variations related to dual hydrogen bonds (O1-H2···N3 and O4-H5···N6) and infrared (IR) vibrational changes and qualitative chemical bond strength reveal excited-state hydrogen bonding enhancement. Probing into the photo-induced excitation process, the charge redistribution derived from vertical excitation confirms the tendency of ESIPT reaction for NP-BSD fluorophore. By constructing potential energy surfaces (PESs) in three aprotic polar solvents, the excited-state intramolecular double proton transfer (ESIDPT) mechanism of NP-BSD could be verified that could be regulated by solvent polarity. We clarify and present the solvent-polarity-associated ESIDPT behaviours for NP-BSD fluorophore.

Effects of atomic electronegativity on the ESIPT process and photophysical properties of naphthalene derivatives

The effect of atomic electronegativity on the excited state intramolecular proton transfer (ESIPT) and photophysical properties of naphthalene derivatives containing DNHP, DPHP and DAHP have been researched through the density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. The potential energy curve (PEC) calculated shows that DNHP, DPHP and DAHP can generate ESIPT process and the ESIPT rate increases with the decrease of atomic electronegativity. Subsequently, we further explain the influence of atomic electronegativity on the ESIPT mechanism and photophysical properties of these molecules by electron-hole analysis. Eventually, we sincerely hope that these studies can be helpful in their application.

A multi-stimuli-responsive fluorescence material based on 1,8-naphthalimide.

A pair of 1,8-naphthalimides (NPIs) were designed and successfully synthesized through embellishing amino-containing NPI with 4-diethylaminosalicyladehyde and 4-diethylaminobenzaldehyde, respectively. Their structures were fully confirmed by 1H/13C NMR, HR-MS and FT-IR spectroscopic studies. Their photophysical properties were systematically investigated in different solvents of varied polarity, in THF/water mixtures with varying water fractions (fw), and in THF solvent with varying concentrations of NPIs. It inferred that the distinct differences in emission between two NPIs during self-assembled process could be ascribed that the hydroxyl-containing NPI allowed the excited-state intramolecular proton transfer process between -OH and CH=N units in the aggregation state. Interestingly, the solid of 4-diethylaminosalicyladehyde-functionalized NPI exhibited multi-stimuli-responsive fluorescence changes involving mechanofluorochromism and HCl/NH3 vapor stimulus-induced conversion. However, no remarkable change was observed in the photoluminescence (PL) spectra for the solid of 4-diethylaminobenzaldehyde-functionalized NPI under the stimuli of mechanical force and organic solvent.

Theoretical study on the effect of different positions of -CN group on photophysical properties and forward-reverse ESIPT behaviours of 2,5-bis(benzo[d]thiazol-2-yl)phenol derivatives

Excited state intramolecular proton transfer (ESIPT) compounds have been widely used in many fields due to its unique photophysical properties, but they are strongly affected by substituents. There are many studies on the effect of substituents at the same position on the ESIPT process, but there are few studies on the effects of substituents at different positions on the proton transfer process. In this work, a strong electron-withdrawing cyano group ( – CN) was introduced into different positions of 2,5-bis(benzo[d]thiazol-2-yl)phenol. The effect of different substituted positions on intramolecular hydrogen bond (IHB), photophysical properties and forward-reverse energy barrier of ESIPT reaction have been systematically investigated adopting density functional theory (DFT) and time-dependent DFT. The result showed that the introduction of – CN group at different positions led to a slight red-shift of absorption, and intramolecular charger transfer is the intrinsic reason for this photophysical phenomenon. The position of – CN group obviously influenced the excited state IHB, and then had an effect on ESIPT process. The substitution positions in the left benzo[d]thiazole ring and phenol ring respectively hinder and promote the ESIPT process, while the substitution in the right benzo[d]thiazole ring not only impetus the ESIPT process, but also increase the tautomer fluorescence.

CPL of Mellein and Related Natural Compounds: Analysis of the ESIPT Phenomenon.

(R)-(-)-Mellein, (3R,4R)-4-hydroxymellein and (3R,4S)-4-hydroxymellein obtained from fungi, i. e. from Diplodia globulosa, were investigated as a class of natural products presenting ESIPT (excited state intramolecular proton transfer) phenomenon, through fluorescence and CPL (circularly polarized luminescence). The study was preceded by the assessment of the absolute configuration through ECD and VCD (electronic and vibrational circular dichroism) spectroscopies in addition to NMR spectra. It is found that ESIPT takes place in these systems very rapidly, and no dual fluorescence has been observed. The experimental study is backed up by TD-DFT calculations of ECD and CPL spectra, plus MD calculations to follow proton transfer in the excited state and careful analysis of the puckering dynamics of the lactone ring. Deprotonated forms of the three compounds were also investigated by the same chiroptical experimental and theoretical methods, showing how one can find in natural compounds not only biological activity but also biologically compatible sensing probes.

Solvent polarity dependent photo-induced excited state intramolecular proton transfer for triphenylamine centered bis unsymmetrical azine (TPOV): A computational study

The exquisite, regulated characteristics of triphenylamine (TPA) derivatives have served as a profound inspiration in the photochemical field. Herein, the novel TPA-centered bis unsymmetrical azine (i.e., 3-methoxysalicylaldehyde substituted 4-((E)-hydrazonomethyl)-N-(4-((E)-hydrazonomethyl)phenyl)-N-phenylaniline (TPOV)) is investigated regarding its photo-induced behaviors and excited state intramolecular proton transfer (ESIPT) mechanisms. Solvent polar-dependent hydrogen bonding interactions and charge recombination, which is induced by photoexcitation, can greatly promote the ESIPT reactions of the TPOV chemosensor. In order to unveil the detailed excited state reaction mechanism, we theoretically construct the S0-state and S1-state of potential energy surfaces (PESs). Based on the S1-state PESs for TPOV in toluene, chloroform, and acetonitrile solvents, we unveil the single ESIPT reaction of TPOV that happens along with alternative dual intramolecular hydrogen bonds (O1-H2···N3 and O4-H5···N6). The solvent polarity-regulated excited state might clear the path for the creation of innovative luminescent materials.

Effect of number of intramolecular double bonds on photophysical properties and ESIPT processes for Cha-NH2 and its derivatives: A theoretical study

In recent years, the research on excited-state intramolecular proton transfer (ESIPT) reactions has aroused increasingly attention theoretically and experimentally. For a deep exploration, we designed three derivatives of Cha-NH2 with different numbers of carbon–carbon double bonds: Cha-NH2-1, Cha-NH2-2, and Cha-NH2-3. Using density functional theory and time-dependent density functional theory methods, we systematically studied the photophysical properties and ESIPT processes of Cha-NH2 and its derivatives. Detailed analysis revealed that the number of carbon–carbon double bonds within the molecule has a significant impact on the ESIPT behavior and spectral properties of Cha-NH2 and its derivatives. Specifically, as the number of carbon–carbon double bonds increases, the strength of intramolecular hydrogen bond is gradually weakened, leading to a red shift in the spectrum and a increase in the forward energy barrier for ESIPT, which is unfavorable for the occurrence of the ESIPT reaction. Therefore, this finding opens up broad application prospects for the adjustment and optimization of future ESIPT process.

Stationary External Electric Field-Mimicking the Solvent Effect on the Ground-State Tautomerism and Excited-State Proton Transfer in 8-(Benzo[d]thiazol-2-yl)quinolin-7-ol.

The effect of the external electric field on the ground-state tautomerism in 8-(benzo[d]thiazol-2-yl)quinolin-7-ol has been studied by using density functional theory. The compound exists as an enol tautomer (off state) and under the influence of the external electric field a long-range intramolecular proton transfer can occur, placing the tautomeric proton at the quinolyl nitrogen atom (on state). This is a result of the much higher dipole moment of the end keto tautomer and indicates that the external electric field can be used to mimic the implicit solvent effect in tautomeric systems. In the excited state, the further stabilization of the most polar on state leads to a situation when the excited-state intramolecular proton transfer becomes impossible, limiting the intramolecular rotation to the conical intersection region.

Theoretical study of atomic electronegativity effects on the excited‐state behavior of fluorescent compounds of citrinin

AbstractThe present work focuses on the light‐induced behavior of citrinin derivatives in relation to atomic electronegativity. A detailed theoretical study on the photophysical properties and excited‐state behavior of fluorescent compounds of citrinin (Cit‐O, Cit‐S, and Cit‐Se, with different atomic electronegativity) has been conducted, and the effect of electronegativity on the proton transfer in this system has been explained. First, the relevant hydrogen bond parameters and infrared vibrational spectra of the optimized geometrical configurations have been insightfully investigated. It is elucidated that the hydrogen bond is strengthened after photoexcitation, and it provides a driving force for excited‐state intramolecular proton transfer (ESIPT). In addition, the frontier molecular orbitals were analyzed, and the intramolecular charge transfer process in all Cit systems, the phenomenon of charge redistribution, facilitates the ESIPT reaction. By constructing potential energy surfaces for different transfer paths, the atomic electronegativity impact on the ESIPT dynamical behavior of the Cit system was determined. This work clarifies the mechanism of the intramolecular proton transfer process in the excited state of citrinin molecules and complements the theoretical study of the atomic electronegativity‐regulated citrinin system, which provides a corresponding theoretical basis for the design and synthesis of new luminescence‐adjustable citrinin systems.

AIE paper shred for the detection of evolved amine vapor from putrefaction processes of fish

Seafood plays a major role in the human diet. During transportation, without proper storage and supply chain, its quality deteriorates easily. The post-harvesting processes such as the storage of food play a crucial role in human health. So it is highly imperative to have a technique for identifying food spoilage earlier to ensure the food safety and security of the consumers. Herein we have developed a highly selective and sensitive fluorescent ‘Turn-on’ probe 2-amino-5-nitrobenzo [d] thiazol-2-yl) imino)methylphenol ANT based on aggregation induced emission (AIE). ANT molecule possesses both restricted intramolecular rotation (RIR) and excited state intramolecular proton transfer (ESIPT) properties leading to fluorescent enhancement rather than aggregation caused quenching (ACQ). The probe shows high selectivity and sensitivity towards the NH3 vapor. This probe with the AIE property is employed for the real-time detection of NH3 in both aqueous and gaseous phases. ANT molecule is deposited on the paper shred by a physical method is utilized to monitor NH3 vapor from red snapper fish as a real-time sample during its degradation processes. After two days there is a ratiometric color change in the paper shred from yellow to orange for the fish stored at room temperature indicating its rotten and unpalatability nature. Paper shred is reused by immersing it into the tetrahydrofuran (THF), in which it retains its initial color due to deprotonation of NH3, keto to enol tautomerism discloses the reusability of the fluorescent probe. Studies carried out using UV–visible and fluorescence spectroscopy infer that the ANT probe has high affinity towards NH3 vapor.

Dual-State Fluorescence in Some Salicylaldehyde-triphenylene Discotic Liquid Crystal Derivatives Induced by Excited State Intramolecular Proton Transfer

Dual-State Fluorescence in Some Salicylaldehyde-triphenylene Discotic Liquid Crystal Derivatives Induced by Excited State Intramolecular Proton Transfer

Tactfully regulating the ESIPT and TICT mechanism in the AIE-active multifunctional triphenylamine Schiff-base compound (TPASB) by methyl substitution

The triphenylamine Schiff-base (TPASB) with dual proton transfer sites (N1…H1–O1 [R1] and N2…H2–O2 [R2]), which is crucial in the field of optoelectronic materials. Herein, a novel molecular design strategy for preparing of TPASB-1 and TPASB-2 via the selective methylation of the hydroxyl group at the R2 or R1 position was proposed. The analysis of electronic structures and potential energy surfaces revealed that a single excited state intramolecular proton transfer (ESIPT) process of TPASB occurs only at R1. Nevertheless, the ESIPT process of TPASB-2 was successfully turned on at R2. More noteworthy is that compared to TPASB, the methylation of hydroxyl group at the R2 position triggers the TICT process of TPASB-1, effectively reducing the potential barrier of ESIPT at the R1 position. This theoretical study explains the role of the substituent effect in regulating ESIPT behaviour, and provides valuable guidance for synthesising efficacious ESIPT-active compounds.

Dynamics of proton tunneling in Hydrogen-Bonded systems through Green's function formalism

This study proposes a new theoretical model based on Green's function formalism for studying proton tunneling via hydrogen bonding. This approach allows calculating the tunneling probability and the tunneling energy that proton transfer occurs along a given path inferred a priori. The method is extended to multiple protons tunneling, characterizing the behaviour of some biological molecules. Specifically, the cases of the proton transfer in the Fujicurin A molecule and the double proton tunneling in the Guanine-Cytosine base-pair are investigated. The new approach is an alternative to those present in the literature. It allows straightforwardly predicting the mechanisms of intramolecular and intermolecular proton transfers involving the rearrangement of conjugated electrons.

Theoretical study of the substituent effects on the ESIPT mechanism of salicylideneaniline and the TICT photochemistry reactions.

The study of salicylideneaniline (SA) and its derivatives is critical due to their special photophysical properties and environmental sensitivity. In this work, the density time-dependent functional theory (TDDFT) and complete-active-space self-consistent-field (CASSCF) methods were carried out to calculate the substituent effect on excited-state properties and dynamics of SA derivatives. We found the para-substitution triggers the excited-state intramolecular proton transfer (ESIPT) reaction, exhibiting the dual-fluorescent phenomena. However, the meta- and ortho-substitutions impel the non-radiative transition process along the minimum energy conical intersection (MECI), forming the twisted intramolecular charge transfer (TICT) state to prevent ESIPT. This investigation of substituent effects on the photochemical processes and photophysical properties will provide the benchmarks for the design of fluorescent materials.