Antioxidant properties of phenolic compounds: H-atom versus electron transfer mechanism

Density functional theory (DFT) calculations were performed to evaluate the antioxidant activity of molecules commonly present in many Mediterranean foods. A series of interesting systems, including tyrosol, hydroxytyrosol, gallic, and caffeic acids, belonging to the family of phenols, resveratrol of the stilbenes family, epicatechin, kaempferol, and cianidin as examples of flavonoids and, at last, a simplified model of α-tocopherol (6-hydroxy-2,2,5,7,8-pentamethylchroman (HPMC)) were studied. Conformational behavior was examined at the B3LYP/6-311++G(3df,2p) level of theory, in the gas phase and in two solvents with different polarity (water and benzene), with the aim to compute the bond dissociation enthalpy (BDE) for the O−H bonds and the adiabatic ionization potentials (IP). BDE and IP for these systems do not follow the same trends in gas and solution phases:  the major differences with respect to vacuum are found as when water computations are performed. On the basis of the computed BDE and IP values, the most active systems able to transfer an H-atom seem to be α-tocopherol followed by hydroxytyrosol, gallic acid, caffeic acid, and epicatechin. Instead, kaempferol and resveratrol appear to be the best candidates for an electron-transfer mechanism.