DFT Study of the Direct Radical Scavenging Potency of Two Natural Catecholic Compounds

To ascertain quercetin’s and rooperol’s potency of H-atom donation to CH3OO• and HOO•, thermodynamics, kinetics and tunnelling, three forms of chemical reaction control, were theoretically examined. In lipid media, H-atom donation from quercetin’s catecholic OH groups via the proton-coupled electron transfer (PCET) mechanism, is more relevant than from C-ring enolic moiety. Amongst rooperol’s two catecholic moieties, H-atom donation from A-ring OH groups is favored. Allylic hydrogens of rooperol are poorly abstractable via the hydrogen atom transfer (HAT) mechanism. Kinetic analysis including tunnelling enables a more reliable prediction of the H-atom donation potency of quercetin and rooperol, avoiding the pitfalls of a solely thermodynamic approach. Obtained results contradict the increasing number of misleading statements about the high impact of C–H bond breaking on polyphenols’ antioxidant potency. In an aqueous environment at pH = 7.4, the 3-O− phenoxide anion of quercetin and rooperol’s 4′-O− phenoxide anion are preferred sites for CH3OO• and HOO• inactivation via the single electron transfer (SET) mechanism