Plastoquinol generates and scavenges reactive oxygen species in organic solvent: Potential relevance for thylakoids

Abstract

The present work reports reactions of plastoquinol (PQH₂-9) and plastoquinone (PQ-9) in organic solvents and summarizes the literature to understand similar reactions in thylakoids. In thylakoids, PQH₂-9 is oxidized by the cytochrome b₆/f complex (Cyt b₆/f) but some PQH₂-9 is also oxidized by reactions in which oxygen acts as an electron acceptor and is converted to reactive oxygen species (ROS). Furthermore, PQH₂-9 reacts with ROS. Light enhances oxygen-dependent oxidation of PQH₂-9. We examined the oxidation of PQH₂-9 via dismutation of PQH₂-9 and PQ-9 and scavenging of the superoxide anion radical (O₂^-) and hydrogen peroxide (H₂O₂) by PQH₂-9. Oxidation of PQH₂-9 via dismutation to semiquinone was slow and independent of pH in organic solvents and in solvent/buffer systems, suggesting that intramembraneous oxidation of PQH₂-9 in darkness mainly proceeds via reactions catalyzed by the plastid terminal oxidase and cytochrome b₅₅₉. In the light, oxidation of PQH₂-9 by singlet oxygen and by O₂^- formed in PSI contribute significantly. In addition, Cyt b_6/f forms H₂O₂ with a PQH₂-9 dependent mechanism. Measurements of the reaction of O₂^- with PQH₂-9 and PQ-9 in acetonitrile showed that O₂^- oxidizes PQH₂-9, forming PQ-9 and several PQ-9-derived products. The rate constant of the reaction between PQH₂-9 and O₂^- was found to be 10⁴ M^-1 s^-1. H₂O₂ was found to oxidize PQH₂-9 to PQ-9, but failed to oxidize all PQH₂-9, suggesting that the oxidation of PQH₂-9 by H₂O₂ proceeds via deprotonation mechanisms producing PQH^--9, PQ^2--9 and the protonated hydrogen peroxide cation, H₃O₂⁺.

Keywords: Hydrogen peroxide; Plastoquinone; Singlet oxygen; Superoxide anion radical; Thylakoid membrane.