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91.
A time-resolved emission technique was employed to study the photoprotolytic cycle of two photoacids 2-naphtol-6-sulfonate (2N6S) and 2-naphtol-6,8-disulfonate (2N68DS) in ice in the presence of a low concentration of a weak base fluoride ion. We found that an additional proton-transfer process occurs in ice doped with F- ions. This reaction takes place between a mobile L-defect (created by static F- ions) and the photoacid. We used a diffusion assisted reaction model, based on the Debye-Smoluchowski equation, to account for the direct reaction of the L-defect with the excited photoacid.  相似文献   
92.
Steady-state and time-resolved emission techniques were employed to study the effect of acetate, a mild base, on the luminescence of curcumin in methanol and ethanol. We found that the steady-state emission intensity as well as the average fluorescence decay time are reduced by a factor of 5 when the acetate concentration is raised to about 1.8 M. We attribute this large effect to an excited-state proton transfer (ESPT) from the acidic groups of curcumin to the acetate anion. We analyze the experimental data in terms of an ESPT reaction occurring between a photoacid and a base.  相似文献   
93.
The aqueous phase of water/AOT reversed micelles having varying diameters was probed by a single free diffusing proton that was released form a hydrophilic photoacid molecule (2-naphthol-6,8-disulfonate). The fluorescence decay signals were reconstructed through the geminate recombination algorithm, accounting for the reversible nature of the proton-transfer reactions at the surface of the excited molecule and at the water/detergent interface. The radial diffusion of the proton inside the aqueous phase was calculated accounting for both the entropy of dilution and the total electrostatic energy of the ion pair, consisting of the pair-energy and self-energy of the ions. The analysis implied that micellar surface must be modeled with atomic resolution, assuming that the sulfono residue protrudes above the water/hydrocarbon interface by approximately 2 A. The analysis of the fluorescence decay curves implies that the molecule is located in a solvent with physical-chemical properties very similar to bulk water, except for the dielectric constant. For reversed micelles with r(max) > or = 16 A, the dielectric constant of the aqueous phase was approximately 70 and for smaller micelles, where approximately 60% of the water molecule is in contact with the van der Waals surface of the micelle, it is as low as 60. This reduction is a reflection of the increased fraction of water molecule that is in close interaction with the micelle surface.  相似文献   
94.
Steady-state and time-resolved emission techniques were employed to study the nonradiative process of Thioflavin-T (ThT) in 1-propanol as a function of temperature. We found that the nonradiative rate, k(nr), decreased by about 3 orders of magnitude when the temperature was lowered to 88 K. We found remarkably good correspondence between the temperature dependence of k(nr) of ThT and the dielectric relaxation times of the 1-propanol solvent.  相似文献   
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