Thiyl free radicals: direct observations of electron transfer reactions with phenothiazines and ascorbate

Abstract

Absolute rate constants for the reaction of the thiyl radicals derived from cysteamine, cysteine, glutathione, penicillamine, and 2-mercaptopropionylglycine (Thiola) with the phenothiazines, promethazine and chlorpromazine and with ascorbate ion, have been measured by pulse radiolysis and have been found to lie in the range 0.03–1.3 × 10⁹ I mol^–1 s^–1. The reactions are considered to occur by an electron transfer mechanism. The possibility that, in biochemical systems, glutathione can act as a catalyst linking hydrogen atom and electron transfer reactions is suggested.