The Reduction and Quenching of Photoexcited Flavins by Edta

Riboflavin was irradiated anaerobically in aqueous EDTA solutions over the pH range 2.5–10. In other dye systems (Bonneau and Pereyre, 1975), only the trivalent anion of EDTA was found to have significant reactivity for photoreduction. For riboflavin, the reactivity begins with monoanionic EDTA, and the reactivity is markedly increased as the charge increases. This suggests that the charge on the reductant is more important to the electron transfer process for riboflavin than the formation of a nonhydrogen bonded nitrogen site on EDTA. At high concentrations of EDTA in the pH range 4–8, quenching of the photoreduction occurs, which can be explained by an energy transfer between the excited singlet state of riboflavin and trianionic EDTA, possibly as an association complex. The rate constants for the photoreduction of riboflavin by the monovalent, divalent, and trivalent anions of EDTA are 1.0 times 10 7 M ‐1 s ‐l , 4.8 times 10′ M ‐1 s ‐l , and 2.0 times 10 8 M ‐1 s ‐1 , respectively. The rate constant for the singlet state quenching by trianionic EDTA is 3 times 10 9 M ‐l s ‐1 , and the limiting quantum yield for intersystem crossing for riboflavin in aqueous solution is 0.50 ± 0.05.