Isolation and characterization of addition products of alpha-tocopherol with peroxyl radicals of dilinoleoylphosphatidylcholine in liposomes.

alpha-Tocopherol was reacted with peroxyl radicals of phosphatidylcholine at 37 degrees C in liposomes. The phospholipid-peroxyl radicals were generated by the reaction of 1,2-dilinoleoyl-3-sn-phosphatidylcholine with a free radical initiator, 2,2'-azobis(2,4-di-methylvaleronitrile), under air. One peak corresponding to the reaction products of alpha-tocopherol with phosphatidylcholine-peroxyl radicals was isolated by reversed-phase high-performance liquid chromatography. Its structure was identified as a mixture of 8a-(phosphatidylcholine-peroxy)-alpha-tocopherones: 1-[9-(8a-peroxy-alpha-tocopherone)-10,12-octadecadienoyl]-2- linoleoyl-3-sn-phosphatidylcholine,1-[13-(8a-peroxy-alpha-tocopherone )-9,11-octadecadienoyl]-2-linoleoyl-3-sn-phosphatidylcholine, 1-linoleoyl-2-[9-(8a, peroxy-alpha-tocopherone)-10,12-octadecadienoyl]-3-sn-pho sph atidylcholine and 1-linoleoyl-2-[13-(8a-peroxy-alpha-tocopherone)-9,11-octadecadi enoyl]-3-sn- phosphatidylcholine. The results indicate that each alpha-tocopherol can trap two peroxyl radicals during the peroxidation of unsaturated phospholipid in liposomes.