Laser studies, proton transfer

Another situation in which an already well-studied proton transfer reaction serves as a probe of a physical phenomenon has been suggested by Knight, Goodall and Greenhow (43, 44). They ionized water with single photons of Nd glass laser infrared radiation and measured an ion recombination rate constant for the reaction... 

Hydrogen transfer in excited electronic states is being intensively studied with time-resolved spectroscopy. A typical scheme of electronic terms is shown in fig. 46. A vertical optical transition, induced by a picosecond laser pulse, populates the initial well of the excited Si state. The reverse optical transition, observed as the fluorescence band Fj, is accompanied by proton transfer to the second well with lower energy. This transfer is registered as the appearance of another fluorescence band, F2, with a large anti-Stokes shift. The rate constant is inferred from the time dependence of the relative intensities of these bands in dual fluorescence. The experimental data obtained by this method have been reviewed by Barbara et al. [1989]. We only quote the example of hydrogen transfer in the excited state of... 

Itoh, M. Adachi, T. Transient absorption and two-step laser excitation fluorescence studies of the excited-state proton transfer and relaxation in the methanol solution of 7-hydroxyflavone. J. Am. Chem. Soc. 1984, 106, 4320 -324. 

Itoh, M. Hasegawa, K. Fujiwara, Y. Two-step laser excitation fluorescence study of the ground- and excited-state proton transfer in alcohol solutions of 7-hydroxyisoflavone. J. Am. Chem. Soc. 1986, 108, 5853-5857. 

Mallik R, Udgaonkar JB, Krishnamoorthy G (2003) Kinetics of proton transfer in a green fluorescent protein a laser-induced pH jump study. Proc Indian Acad Sci-Chem Sci 115 307-317... 

Excited-state intramolecular proton transfer (ESIPT) processes are important for both practical and fundamental reasons. o-Hydroxybenzaldehyde (OHBA) is the simplest aromatic molecule displaying ESIPT and serves as a model system for comparison with theory. TRPES was used to study ESIPT in OHBA, monodeuterated ODBA and an analogous two-ring system hydroxyacetonaph-tone (HAN) as a function of pump laser wavelength, tuning over the entire enol... 

Deprotonation reaction of dipyrrole 179 was studied by nanosecond laser photolysis. The bimolecular rate constants of proton transfer to heterocyclic bases were determined. The inhibiting of the radical cation reaction by bases occurs during the radical cation formation (09CHE554). 

The dependence of intramolecular proton transfer on solvent friction has been established for 2-(2 -hydroxy-5-methylphenyl) benzotriazole in alcohol and other solvents. Excited-state proton transfer in 2-(2 -hydroxyphenyl) benzothiazole has also been studied 2 Photophysical properties and laser performance of w, w -bis ( oxazol-2-yl)- -oligophenylenes in dioxane have been measured at room temperature. +p increases with the number of phenyl rings between terminally positioned oxazoyl groups. 

The efficient photodecarboxylation of the keto acids (77) has been studied. The reactions involve the formation of the carbanions (78). Aqueous solutions of fenofibric acid (79) at pH 7.4 show the formation of two intermediates when subjected to laser excitation. The study has indicated that the triplet state of the acid in water is of a jtji type. Photoionization is an important process in the aqueous medium. New photoreactive phenylalanine analogues (80) and (81) have been prepared. These were incorporated into position 5 of the pentapeptide, thymopentin. The resultant derivatives were photolabile and underwent decomposition on irradiation at 365 nm. Computational methods have been used to analyse the photoreactivity of the tryptophan derivative (82). The calculations were directed towards an understanding of the quenching of the fluorescence. The results indicate that hydrogen transfer alone does not quench the fluorescence, but that an aborted decarboxylation path is involved. Proton transfer... 

Viappiani, C., Bonetti, G., Carelli, M., Ferrati, F., Sternieni A., Study of proton transfer processes in solutions using the laser induced pH jump A new experimental setup and an improved data analysis based on genetic algorithm. Rev. Sci. Instrum., 1998, 69, 270-276. 

Because of these reasons, my colleagues and I initiated a few years ago a detailed study of proton transfer in an aqueous system, where the event is synchronized by a laser pulse. This technique, using signal averaging, retains the temporal parameters of the event and allows the evaluation of the probabilities of finding a proton in putative environments assigned for it by the different bioenergetic models. 

During these studies, it became apparent that proton transfer is an extremely sharp instrument for gauging the water in the immediate environment surrounding the site of dissociation. It turned out that the general biological solvent, the water, acquires different properties at the site where biochemical reaction takes place—the surface of the enzyme. These local properties of the water can be measured through the technique of the laser-induced proton pulse, free of perturbation caused by the huge mass of the bulk water. 

By K. J. Kaufmann and M. R. Wasielewski Proton Transfer A Primary Picosecond Event By P. M. Rentzepis and P. F. Barbara Laser Studies of Proton Transfer... 

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