Reactivities of Hydroxycinnamic Acid Derivatives Involving Caffeic Acid toward Electrogenerated Superoxide in N,N-Dimethylformamide

Abstract

Reactivity of (2E)-3-(3,4-dihydroxyphenyl)prop-2-enoic acid (caffeic acid), classified as a hydroxycinnamic acid (HCA) derivative, toward electrogenerated superoxide radical anion (O2•−) was investigated through cyclic voltammetry, in situ electrolytic electron spin resonance spectrometry, and in situ electrolytic ultraviolet–visible spectrometry in N,N-dimethylformamide (DMF), aided by density functional theory (DFT) calculations. The quasi-reversible redox of dioxygen/O2•− is modified in the presence of caffeic acid, suggesting that O2•− is scavenged by caffeic acid through proton-coupled electron transfer. The reactivities of caffeic acid toward O2•− are mediated by the ortho-diphenol (catechol) moiety rather than by the acryloyl group, as experimentally confirmed in comparative analyses with other HCAs. The electrochemical and DFT results in DMF suggested that a concerted two-proton-coupled electron transfer mechanism proceeds via the catechol moiety. This mechanism embodies the superior kinetics of O2•− scavenging by caffeic acid.