Structure-activity relationship of the tocopherol-regeneration reaction by catechins

The reaction rates (k(r)) of 5,7-diisopropyl-tocopheroxyl radical (Toc(center dot)) with catechins (epicatechin (EC), epicatechin gallate (ECG), epigallocatechin (EGC), epigoallocatechin gallate (EGCG)) and related compounds (methyl gallate (MG), 4-methyleatechol (MC), and 5-Foethoxyresorcinol (MR)) have been measured by stopped-flow spectrophotorneter. The k(r), values increased in the order of MR << MG < EC < MC similar to ECG < FGC < EGCG in ethanol and 2-propanol/H2O (5/1, v/v) solutions, indicating that the reactivity of the OH groups in catechins increased in the order of resorcinol A-ring << gallate G-ring < catechol B-ring < pyrogallol B-ring. The catechins which have lower oxidation potentials show higher reactivities. The rate constants for catechins in micellar solution showed notable pH dependence with one or two peaks around pH 9-11, because of the dissociation of various phenolic hydroxyl protons in catechins. The Structure-activity relationship in the free-radical-scaveril-ing reaction by catechins has been clarified by the detailed analyses of the pH dependence of kr values. The reaction rates increased remarkably with increasing the anionic character of catechins, that is, the electron-donating capacity of catechins. The mono anion form at catechol B-and resorcinol A-rings and dianion form at pyrogallol B-and gallate G-rings show the highest activity for free-radical-scavenging. It was found that catechins (EC, ECG, EGC, and EGCG) have activity similar to or higher than that of vitamin C in vitamin E regeneration at pH 7-12 in micellar solution. (c) 2005 Elsevier Inc. All rights reserved.