Excited-State Photophysics of Hypericin and Its Hexamethoxy Analog: Intramolecular Proton Transfer as a Nonradiative Process in Hypericin

The excited-state photophysics of the light induced antiviral agent, hypericin, are compared with those of its methylated analog, hexamethoxyhypericin. This comparison is instructive in understanding both the ground- and the excited-state properties of hypericin. That the hexamethoxy analog has no labile protons that can be transferred, that it cannot protonate its own carbonyl groups, that it has a reduced fluorescence quantum yield and lifetime with respect to hypericin, and that it exhibits no stimulated emission or, more specifically, rise time in stimulated emission completely support our emerging model of the hypericin photophysics. The results are consistent with the presence of intramolecular excited-state proton transfer in hypericin but not in its methylated analog

Interaction of Glutathione S-Transferase with Hypericin: A Photophysical Study

The photophysics of hypericin have been studied in its complex with two different isoforms, A1-1 and P1-1, of the protein glutathione S-transferase (GST). One molecule of hypericin binds to each of the two GST subunits. Comparisons are made with our previous results for the hypericin/human serum albumin complex (Photochem. Photobiol. 1999, 69, 633−645). Hypericin binds with high affinity to the GSTs:  0.65 μM for the A1-1 isoform and 0.51 μM for the P1-1 isoform (Biochemistry 2004, 43, 12761−12769). The photophysics and activity of hypericin are strongly modulated by the binding protein. Intramolecular hydrogen-atom transfer is suppressed in both cases. Most importantly, while there is significant singlet oxygen generation from hypericin bound to GST A1-1, binding to GST P1-1 suppresses singlet oxygen generation to almost negligible levels. The data are rationalized in terms of a simple model in which the hypericin photophysics depends entirely upon the decay of the triplet state by two competing processes, quenching by oxygen to yield singlet oxygen and ionization, the latter of these two are proposed to be modulated by A1-1 and P1-1

Hypericin, Hypocrellin, and Model Compounds: Primary Photoprocesses of Light-Induced Antiviral Agents

The excited-state photophysics of the light-induced antiviral agents hypericin and hypocrellin are compared with those of the hexa- and tetramethoxy analogues of hypericin. The results are consistent with the interpretation of the primary photoprocess in hypericin and hypocrellin as that of excited-state intramolecular proton or atom transfer

Dynamic Solvation in Room-Temperature Ionic Liquids

The dynamic solvation of the fluorescent probe, coumarin 153, is measured in five room-temperature ionic liquids using different experimental techniques and methods of data analysis. With time-resolved stimulated-emission and time-correlated single-photon counting techniques, it is found that the solvation is comprised of an initial rapid component of ∼55 ps. In all the solvents, half or more of the solvation is completed within 100 ps. The remainder of the solvation occurs on a much longer time scale. The emission spectra of coumarin 153 are nearly superimposable at all temperatures in a given solvent unless they are obtained using the supercooled liquid, suggesting that the solvents have an essentially glassy nature. The physical origin of the two components is discussed in terms of the polarizability of the organic cation for the faster one and the relative diffusional motion of the cations and the anions for the slower one. A comparison of the solvation response functions obtained from single-wavelength and from spectral-reconstruction measurements is provided. Preliminary fluorescence-upconversion measurements are presented against which the appropriateness of the single-wavelength method for constructing solvation correlation functions and the use of stimulated-emission measurements is considered. These measurements are consistent with the trends mentioned above, but a comparison indicates that the presence of one or more excited states distorts the stimulated-emission kinetics such that they do not perfectly reproduce the spontaneous emission data. Fluorescence-upconversion results indicate an initial solvation component on the order of ∼7 ps