The influence of stereochemistry on the antioxidant properties of catechin epimers

The influence of stereochemistry on the radical scavenging activity of catechins was investigated by studying the effect of pH on the antioxidant properties of catechin epimers. The difference in the pH-dependent Trolox equivalent antioxidant capacity (TEAC) profiles was observed only in case of gallocatechin gallate (GCG) and epigallocatechin gallate (EGCG), indicating the influence of steric structure on the TEAC antioxidant activity of these galloyl moiety-containing catechins. Based on comparison of the pH-dependent TEAC values to theoretically calculated parameters, including homolytic OH bond dissociation energy and ionization potential (IP) as well as theoretically predicted structures of the most stable monoanions of GCG and EGCG, it was concluded that due to steric hindrance in GCG molecule, the IP value of GCG monoanion increases reflecting lower radical scavenging capacity of GCG in comparison with EGCG. It results in the difference in the pH-dependent TEAC profiles of these two catechin epimers at pH above 3.5. This effect does not occur for other pairs of catechin epimers of this study.