The relationship between radical-scavenging rate constants (k) in an aprotic medium and thermodynamic parameters calculated by density functional theory (DFT) was investigated for 7 flavonols, which are myricetin (Myr), quercetin (Que), morin (Mor), kaempferol (Kae), 2'-methylquercetin (2'-MeQue), 5'-methylquercetin (5'-MeQue), and 2',5'-dimethylquercetin (Me2Que). The k values were determined for the reaction between the flavonols and galvinoxyl radical used as a reactivity model of reactive oxygen species in deaerated acetonitrile at 298 K. The energy difference values (D HT, HT: hydrogen transfer) between the flavonols and the corresponding radicals, which equal to the relative O-H bond dissociation energies of the OH groups in the flavonols and ionisation potentials (IP) were calculated by DFT at the B3LYP/6-31++G(d) level with C-PCM solvation model parameterised for acetonitrile. Among the 7 flavonols used in this study, calculated IP values of 4 flavonols exhibited a linear correlation with log k, suggesting that the radical-scavenging reaction of these flavonols may proceed via an electron transfer as the rate determining step.
Keywords: Antioxidant; density functional theory; flavonol; radical; reaction mechanism.