Excited state proton transfer process

The 17r<7 states also dominate the photoinduced processes in hydrogen-bonded chromophore-solvent clusters. The photoinduced hydrogen transfer reaction is experimentally and computationally well documented in clusters of phenol and indole with ammonia [14,16,32], There is no clear evidence for the existence of an excited-state proton transfer process in these systems [14], The same conclusion applies to bi functional chromophores solvated in finite clusters, such as 7HQ-ammonia and 7HQ-water clusters [15]. In future work, the photochemistry of larger and biologically relevant chromophores (such as tyrosine, tryptophan, or the DNA bases) should be investigated in a finite solvent environment. 

The ground and excited state proton transfer processes of 4-methyl-2,6-diacetyl-phenol and the influence of polar solvents on the outcome of the photochemical transformation of 2,6-diformyl-4-methylphenol (10) has been evaluated" " . The results obtained from the study of 10 indicate that the CO- -HO hydrogen bond is stronger in... 

On-the-fly molecular dynamics simulations in the first excited state of 7AI(H20)i 5 complexes were carried out at RI-ADC(2)/SVP-SV(P) level. The following conclusions concerning the excited-state proton-transfer process and the effect of the second hydration shell on it can be drawn from our results ... 

Optical properties of 3-hydroxyflavone (3-HF) doped sol-gel derived glass were studied (Carturan, 2003). The intramolecular excited-state proton transfer process is strongly affected by the chemical environment. The main results are that the Stokes-shifted emission from 3-HF tautomeric form is enhanced at increasing trifunctional alkoxide amount and at decreasing polarity of the non-hydrolizable groups. 

The chemical and crystallographic literature contains a copious amount of structure determinations where X-ray diffraction analysis has been invoked to provide direct evidence of the tautomeric form of a particular compound in the solid state. Many systematic studies of both ground-state and excited-state proton transfer processes of a larger number of tautomeric compounds or of the same compound under varying conditions have also been reported. Rather than attempting to provide a comprehensive overview of all known examples of tautomeric systems characterized by X-rays, we have selected here a handful of cases that illustrate how the method can be applied to unravel details that are relevant to the identity... 

Figure 6. Jablonski diagram for the excited-state proton transfer and energy dissipation in TIN kSo s0> ks,s,-, kT,Tl- rate constants of proton-transfer processes in the ground state, first excited singlet state, and triplet state, respectively, and k,j rate constants of radiationless deactivations and k,- rate constants of intersyslem...

The occurrence of excited-state proton transfer during the lifetime of the excited state depends on the relative rates of de-excitation and proton transfer. The general equations will be presented first, but only for the most extensively studied case where the excited-state process is proton ejection (pK < pK) the proton donor is thus an acid, AH, and the proton acceptor is a water molecule. Methods for the determination of pK are then described and finally, the various cases of pH dependence of the absorption and fluorescence spectra are examined. 

The pK of tyrosine explains the absence of measurable excited-state proton transfer in water. The pK is the negative logarithm of the ratio of the deprotonation and the bimolecular reprotonation rates. Since reprotonation is diffusion-controlled, this rate will be the same for tyrosine and 2-naphthol. The difference of nearly two in their respective pK values means that the excited-state deprotonation rate of tyrosine is nearly two orders of magnitude slower than that of 2-naphthol.(26) This means that the rate of excited-state proton transfer by tyrosine to water is on the order of 105s 1. With a fluorescence lifetime near 3 ns for tyrosine, the combined rates for radiative and nonradiative processes approach 109s-1. Thus, the proton transfer reaction is too slow to compete effectively with the other deactivation pathways. 

One may consider the relaxation process to proceed in a similar manner to other reactions in electronic excited states (proton transfer, formation of exciplexes), and it may be described as a reaction between two discrete species initial and relaxed.1-7 90 1 In this case two processes proceeding simultaneously should be considered fluorescence emission with the rate constant kF= l/xF, and transition into the relaxed state with the rate constant kR=l/xR (Figure 2.5). The spectrum of the unrelaxed form can be recorded from solid solutions using steady-state methods, but it may be also observed in the presence of the relaxed form if time-resolved spectra are recorded at very short times. The spectrum of the relaxed form can be recorded using steady-state methods in liquid media (where the relaxation is complete) or using time-resolved methods at very long observation times, even as the relaxation proceeds. 

Photoinduced electron transfer from eosin and ethyl eosin to Fe(CN)g in AOT/heptane-RMs was studied and the Hfe time of the redox products in reverse micellar system was found to increase by about 300-fold compared to conventional photosystem [335]. The authors have presented a kinetic model for overall photochemical process. Kang et al. [336] reported photoinduced electron transfer from (alkoxyphenyl) triphenylporphyrines to water pool in RMs. Sarkar et al. [337] demonstrated the intramolecular excited state proton transfer and dual luminescence behavior of 3-hydroxyflavone in RMs. In combination with chemiluminescence, RMs were employed to determine gold in aqueous solutions of industrial samples containing silver alloy [338, 339]. Xie et al. [340] studied the a-naphthyl acetic acid sensitized room temperature phosphorescence of biacetyl in AOT-RMs. The intensity of phosphorescence was observed to be about 13 times higher than that seen in aqueous SDS micelles. 

This article will deal more with naphthol-ammonia clusters but the case of phenol-ammonia can be quickly summarized here. The dynamical process observed in the excited state of phenol has long been attributed to an excited state proton transfer [1-7] ... 

A third type of bimolecular reaction, summarized by equation (24), is that of excited state proton transfer where Q is now a proton acceptor. This type of process was proposed in the case of the OH" and CO32- quenching of emission from [RhCl(NH3)5]2+.48... 

The ESPT of naphthylammonium [190] and phenanthrylammonium [191] ions in their 18-crown-6 ether complexes in MeOH-H20 (9 1) solvent shows that the excited-state proton-transfer rate decreases markedly on complexing. The back-protonation rate in the excited state is negligibly small compared with those of the other decay processes, which essentially means that there is no excited-state protropic equilibrium in the crown complexes. The one-way proton-transfer reaction is elucidated by the presence of the excited neutral amine-crown complex (RNH2-crown) produced by deprotonation of (RN+H3-crown). There is a large steric effect on protonation to the amino group of the excited neutral complex. 

As in isolated phenol and in phenol-ammonia/water clusters, the OH bond is broken homolytically in 7HQ-A3, resulting in the transfer of a hydrogen atom rather than proton transfer. As found for phenol-A /W and naphthol-A /W clusters, ammonia is a better hydrogen acceptor than water. Excited-state hydrogen transfer processes are thus strongly favoured in an ammonia environment. 

Tunneling effects on the microsolvated SN2 reactions studied so far are small. Processes dominated by tunneling are excited state proton transfer in... 

Since coiled chains of proteins are known to uncurl because of ionic repulsions when ionization occurs, Reid (1957) suggested that excited state dissociation acts as a trigger in rapid biological processes. The 7-azaindole dimer, which undergoes photo-induced double proton transfer (see Section 4), has similarities to the adenine-thymine and guanine-cytosine base pairs of DNA. Its excited state proton transfers have been proposed as possible mechanisms of mutagenesis (Ingram and El-Bayoumi, 1974). 

Ionization reactions can occur under vacuum conditions at any time during this process but the origin of ions produced in MALDI is still not fully understood [27,28], Among the chemical and physical ionization pathways suggested for MALDI are gas-phase photoionization, excited state proton transfer, ion-molecule reactions, desorption of preformed ions, and so on. The most widely accepted ion formation mechanism involves proton transfer in the solid phase before desorption or gas-phase proton transfer in the expanding plume from photoionized matrix molecules. The ions in the gas phase are then accelerated by an electrostatic field towards the analyser. Figure 1.15 shows a diagram of the MALDI desorption ionization process. 

Quinone methides are frequently reported as intermediates from irradiation of arenes having a methyl or substituted methyl group in the 2-position to a carbonyl or nitro group (H-abstraction) or a hydroxy function (formal loss of water). The latter process has been studied with pyridoxine (201) and its derivatives (202) and (203), and the mechanism by which the loss occurs is found to depend upon the pH of the solution. In neutral solution, the formation of the quinone methide (204) from (201) arises either by excited state proton transfer to the aqueous methanol solvent and loss of OH from the phenoxide ion, or by intramolecular proton transfer and loss of water, while the reaction in alkaline solution involves dehydroxylation from the excited state of the phenoxide ion. 

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