Mutual Activation of Two Radical Trapping Agents: Unusual "Win-Win Synergy" of Resveratrol and TEMPO during Scavenging of dpph• Radical in Methanol

Abstract

The reaction of the 2,2'-diphenyl-1-picrylhydrazyl radical (dpph^•) with resveratrol in methanol (k^MeOH = 192 M^-1 s^-1) is greatly accelerated in the presence of stable nitroxyl radical TEMPO^• (k_mix^MeOH = 1.4 × 10³ M^-1 s^-1). This synergistic effect is surprising because TEMPO^• alone reacts with dpph^• relatively slowly (k^S = 31 M^-1 s^-1 in methanol and 0.03 M^-1 s^-1 in nonpolar ethyl acetate). We propose a putative mechanism in which a mutual activation occurs within the acid-base pair TEMPO^•/RSV to the resveratrol (RSV) anion and TEMPOH^•+ radical cation, both being extremely fast scavengers of the dpph^• radical. The fast initial reaction is followed by a much slower but continuous decay of dpph^• because a nitroxyl radical is recovered from the TEMPOnium cation, which is reduced directly by RSV/RSV^- to TEMPO^• or recovered indirectly via a reaction with methanol, producing TEMPOH subsequently oxidized by dpph^• to TEMPO^•.