PHOTOINDUCED ELECTRON-TRANSFER REACTIONS OF ROSE-BENGAL AND SELECTED ELECTRON-DONORS

The photoinduced electron transfer reactions of the triplet state of rose bengal (RB) and several electron donors were investigated by the complementary techniques of steady state and time-resolved electron paramagnetic resonance (EPR) and laser flash photolysis (LEP). The yield of radicals varied with the light fluence rate, RB concentration and, in particular, the electron donor used. Thus for L-dopa (dopa, dihydroxyphenylalanine) only 10% of RB anion radical (RB.-) was produced, with double the yield observed with NADH (NAD, nicotinamide adenine dinucleotide) as quencher and more than three times the yield observed with ascorbate as quencher. Quenching of the RB triplet was both reactive and physical with total quenching rate constants of 4 x 10(8) mol-1 dm3 s-1 and 8.5 x 10(8) mol-1 dm3 s-1 for ascorbate and NADH respectively. The rate constant for the photoinduced electron transfer from ascorbate to RB triplet was 1.4 x 10(8) mol-1 dm3 s-1 as determined by Fourier transform EPR (FT EPR). FT EPR spectra were spin polarized in emission at early times indicating a radical pair mechanism for the chemically induced dynamic electron polarization. Subsequent to the initial electron transfer production of radicals, a complex series of reactions was observed, which were dominated by processes such as recombination, disproportionation and secondary (bleaching) reactions. It was observed that back electron transfer reactions could be prevented by mild oxidants such as ferric compounds and duroquinone, which were efficiently reduced by RB.-.