Yuval Erez

Modeling the nonradiative decay rate of electronically excited thioflavin T.

A computational model of nonradiative decay is developed and applied to explain the time-dependent emission spectrum of thioflavin T (ThT). The computational model is based on a previous model developed by Glasbeek and co-workers (van der Meer, M. J.; Zhang, H.; Glasbeek, M. J. Chem. Phys. 2000, 112, 2878) for auramine O, a molecule that, like ThT, exhibits a high nonradiative rate. The nonradiative rates of both auramine O and ThT are inversely proportional to the solvent viscosity. The Glasbeek model assumes that the excited state consists of an adiabatic potential surface constructed by adiabatic coupling of emissive and dark states. For ThT, the twist angle between the benzothiazole and the aniline is responsible for the extensive mixing of the two excited states. At a twist angle of 90°, the S(1) state assumes a charge-transfer-state character with very small oscillator strength, which causes the emission intensity to be very small as well. In the ground state, the twist angle of ThT is rather small. The photoexcitation leads first to a strongly emissive state (small twist angle). As time progresses, the twist angle increases and the oscillator strength decreases. The fit of the experimental results by the model calculations is good for times longer than 3 ps. When a two-coordinate model is invoked or a solvation spectral-shift component is added, the fit to the experimental results is good at all times.

Excited-State Intermolecular Proton Transfer of the Firefly’s Chromophore d-Luciferin

Steady-state absorption and emission as well as time-resolved emission spectroscopies were employed to study the photophysics and photochemistry of D-luciferin, the firefly active bioluminescent compound. In aqueous solution the electronically excited-state protonated D-luciferin compound undergoes an efficient process of proton transfer to the solvent, with a rate constant k(PT) = 3.0 x 10(10) s(-1). We found a kinetic isotope effect of about 2.5 for this process. The deprotonated form of D-luciferin in the excited state recombines irreversibly with the geminate proton. Hence, the fluorescence decay of the deprotonated form is nonexponential, and the fluorescence quantum yield is low.

Temperature dependence of the fluorescence properties of thioflavin-T in propanol, a glass-forming liquid.

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.

Ultrafast Excited-State Intermolecular Proton Transfer of Cyanine Fluorochrome Dyes

Steady-state and time-resolved emission spectroscopy techniques were employed to study the excited-state proton transfer (ESPT) to water and D(2)O from QCy7, a recently synthesized near-infrared (NIR)-emissive dye with a fluorescence band maximum at 700 nm. We found that the ESPT rate constant, k(PT), of QCy7 excited from its protonated form, ROH, is ~1.5 × 10(12) s(-1). This is the highest ever reported value in the literature thus far, and it is comparable to the reciprocal of the longest solvation dynamics time component in water, τ(S) = 0.8 ps. We found a kinetic isotope effect (KIE) on the ESPT rate of ~1.7. This value is lower than that of weaker photoacids, which usually have KIE value of ~3, but comparable to the KIE on proton diffusion in water of ~1.45, for which the average time of proton transfer between adjacent water molecules is similar to that of QCy7.

Comparative study of the photoprotolytic reactions of D-luciferin and oxyluciferin.

Optical steady-state and time-resolved spectroscopic methods were used to study the photoprotolytic reaction of oxyluciferin, the active bioluminescence chromophore of the fireflys luciferase-catalyzed reaction. We found that like D-luciferin, the substrate of the firefly bioluminescence reaction, oxyluciferin is a photoacid with pK(a)* value of ∼0.5, whereas the excited-state proton transfer (ESPT) rate coefficient is 2.2 × 10(10) s(-1), which is somewhat slower than that of D-luciferin. The kinetic isotope effect (KIE) on the fluorescence decay of oxyluciferin is 2.5 ± 0.1, the same value as that of D-luciferin. Both chromophores undergo fluorescence quenching in solutions with a pH value below 3.

Temperature Dependence of the Fluorescence Properties of Curcumin

Steady-state and time-resolved techniques were employed to study the nonradiative process of curcumin dissolved in ethanol and 1-propanol in a wide range of temperatures. We found that the nonradiative rate constants at temperatures between 175-250 K qualitatively follow the same trend as the dielectric relaxation times of both neat solvents. We attribute the nonradiative process to solvent-controlled proton transfer. We also found a kinetic isotope effect on the nonradiative process rate constant of ~2. We propose a model in which the excited-state proton transfer breaks the planar hexagonal structure of the keto-enol center of the molecule. This, in turn, enhances the nonradiative process driven by the twist angle between the two phenol moieties.

Pressure effect on the nonradiative process of thioflavin-T.

Time-resolved emission techniques were employed to study the nonradiative process of thioflavin-T (ThT) in 1-propanol, 1-butanol, and 1-pentanol as a function of the hydrostatic pressure. Elevated hydrostatic pressure increases the alcohol viscosity, which in turn strongly influences the nonradiative rate of ThT. A diamond-anvil cell was used to increase the pressure up to 2.4 GPa. We found that the nonradiative rate constant, k(nr), decreases with pressure. We further found a remarkable linear correlation between a decrease in k(nr) (increase in the nonradiative lifetime, τ(nr)) and an increase in the solvent viscosity. The viscosity was varied by a factor of 1000 and k(nr) was measured at high pressures, at which the nonradiative rate constant of the molecules decreased from (7 ps)(-1) to (13 ns)(-1), (13 ps)(-1) to (17 ns)(-1) and (17 ps)(-1) to (15 ns)(-1) for 1-propanol, 1-butanol, and 1-pentanol, respectively. The viscosity-dependence of k(nr) is explained by the excited-state rotation rate of the two-ring systems, with respect to each other.

Excited-state intermolecular proton transfer of the firefly's chromophore D-luciferin. 2. Water-methanol mixtures.

Steady-state emission and time-resolved techniques were employed to study the photoprotolytic processes d-luciferin undergoes in water-methanol mixtures over a wide range of molar fractions (chi(MeOH)) of methanol. We found that in the concentration range of 0 < chi(MeOH) < 0.8 the rate constant of the excited-state proton transfer (ESPT) to the solvent decreases nearly exponentially with increasing chi(MeOH). At chi(MeOH) > 0.8 the proton transfer rate constant decreases with an even steeper slope. The kinetic isotope effect (KIE) maintains a constant value of 2.4 +/- 0.2 at all the mixtures compositions.

Ultrafast proton transfer of three novel quinone cyanine photoacids.

Steady-state and time-resolved emission techniques were used to study the photoprotolytic properties of three recently synthesized strong quinone cyanine photoacids (QCy7 and its sulfonated derivatives). The rate coefficient of the excited-state proton transfer (ESPT), k(PT), of the three dyes is roughly 1.5 × 10(12) s(-1), a high value that is comparable to the solvation dynamics rate of large polar organic molecules in H(2)O and D(2)O. It is twice as fast as the proton transfer rate between two adjacent water molecules in liquid water. We found that, as expected, two of the sulfonated photoacids geminately recombines with the proton at an elevated rate. The accelerated geminate recombination process of the sulfonated derivatives is different from a simple diffusion process of protons. The ESPT rate coefficient of these molecules is the highest recorded thus far.

The Effect of a Mild Base on Curcumin in Methanol and Ethanol

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.