Theoretical Calculation on Antioxidative Activity and Solvation Effect of Phenolic Acids

In this study, 12 phenolic acids were theoretically calculated using the M06-2X functional. To explain their antioxidant and solvation effects, bond dissociation enthalpy (BDE), ionization potential (IP), proton dissociation enthalpy (PDE), proton affinity (PA) and electron transfer enthalpy (ETE) were calculated for each phenolic acid in the gas phase and solvents. The results showed that the BDE of gentianic acid (C5) in the gas phase was the lowest. In terms of BDE, caffeic acid (C6) had the strongest antioxidant effect in benzene, gentianic acid (C5) in acetone, and 3,4-dihydroxybenzyl alcohol (C2) in ethanol and water. In terms of IP, resveratrol had the best antioxidant activity in 4 solvents and in the gas phase. The antioxidant mechanism of phenolic acids was mainly related to hydrogen atom transfer (HAT). It was found that the ability of dehydrogenated anions and cations of phenolic acids to generate dehydrogenated free radicals was consistent with the influence of solvent polarity on IP, BDE, PDE, PA and ETE. In general, the antioxidant capacity of phenolic acids was the strongest in the weakly polar solvent acetone, followed by the strongly polar solvents water and ethanol, and phenolic acids had the weakest antioxidant capacity in non-polar solvents.