Electron Transfer Quenching of the Rose Bengal Triplet State

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Abstract
— The potential for electron transfer quenching of rose bengal triplet (3RB2‐) to compete with energy transfer quenching by oxygen was evaluated. Rate constants for oxidative and reductive quenching were measured in buffered aqueous solution, acetonitrile and in small unilamellar liposomes using laser flash photolysis. Biologically relevant quenchers were used that varied widely in structure, reduction potential and charge. Radical ion yields (Øi) were measured by monitoring the absorption of the rose bengal semireduced (RB*3‐) and semioxidized (RB*‐) radicals. The results in solution were analyzed as a function of the free energy for electron transfer (δG) calculated using the Weller equation including electrostatic terms. Exothermic oxidative quenching was about 10‐fold faster than exothermic reductive quenching in aqueous solution. The quenching rate constants decreased as δG approached zero in both aqueous and acetonitrile solution. Exceptions to these generalizations were observed that could be rationalized by specific steric or electrostatic effects or by a change in mechanism. The results suggest that electron transfer reactions with some potential quenchers in cells could compete with formation of singlet oxygen [O2(1δg)]. Values of Øi were generally greater for reductive quenching and, for oxidative quenching, greater in acetonitrile than in buffer. Electron transfer quenching of 3RB2‐ in liposomes, below the phase transition temperature was slower than in solution for both lipid‐soluble and water‐soluble quenchers indicating that these reactions may not compete with formation of O2(1δg) during cell photosensitization.

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