Autoxidation of dilinoleoylphosphatidylcholine (DLPC) bilayers photoinitiated by benzophenone takes place by a free radical chain mechanism according to product studies of the cis, trans and trans, trans-9- and -13-linoleate hydroperoxides formed and kinetic studies of the reaction order as a function of light intensity. The absolute rate constant for hydrogen abstraction from DLPC bilayers by peroxyl radicals is found to be 36.1 M−1 s−1 at 37 °C. Preliminary measurements of activities of phenolic antioxidants, α-tocopherol (α-T), 2,2,5,7,8-pentamethyl-6-hydroxychroman (PMHC), 2,5,7,8-tetramethyl-6-hydroxychroman-2-carboxylate (Trolox), and 2,6-di-tert-butyl-4-methylphenol (BHT) by oxygen uptake studies during inhibition periods using photoinitiation gave uncorrected inhibition rate constants, Kinh, for α-T, PMHC, and Trolox several orders of magnitude lower than observed earlier in chlorobenzene. Three series of phenolic antioxidants, (a) polyalkyl-6-hydroxychromans, (b) polyalkyl-4-methoxyphenols, and (c) trialkylphenols, were examined for their antioxidant activities in DLPC membranes during thermally initiated autoxidation by azobis-2,4-dimethylvaleronitrile (DMVN). The corrected inhibition rate constants, kinh, observed in (a), α-T (5.8 × 103), PMHC (17.8 × 103), Trolox (5.8 × 103), 2,2-dimethyl-5,7-diisopropyl-6-hydroxychroman, 4a (55 × 103), and 2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman, 5a (61 × 103) M−1 s−1, are dramatically lower, by several orders of magnitude, than those measured earlier in chlorobenzene and significantly lower (about 1/40–1/10) than those measured in solution in tert-butyl alcohol and less than kinh measurements (1/2–1/5) in aqueous SDS micelles. The kinh values for series (b) were 2,3,5,6-tetramethyl-4-methoxyphenol (TTMMP) (2.1 × 103), 2,3,6-trimethyl-4-methoxyphenol (TMMP) (10.4 × 103), and 2,6-di-tert-butyl-4-methoxyphenol (DBHA) (27.5 × 103) M−1 s−1 and for (c) were 2,6-di-tert-butyl-4-methylphenol (BHT) (3.7 × 103) and 2,4,6-trimethylphenol (TMP) (0.56 × 103) M−1 s−1. The results show an overall leveling and depression of antioxidant activities in DLPC membranes in the series (a), (b), (c) compared to those reported in solution in chlorobenzene, where large differences were attributed to steroelectronic effects of the para ether oxygen stabilizing the derived phenoxyl radicals in (a) and (b) types. The results in aqueous micellar and membrane systems are interpreted in terms of polar solvation effects. Hydrogen bonding by water at both the ether and phenolic groups decreases the activity of the (a) series. Hydrogen bonding at the phenolic hydroxyl appears to be the more significant factor since steric hindrance to H-bonding at hydroxyl allows 4a and 5a to be the most active antioxidants of the α-tocopherol series (a) and DBHA to be the most active antioxidant of the (b) series. Keywords: antioxidant activities, phenols, membranes, peroxidation, kinetics.
Catalysis by acetylcholinesterase in two-hydronic-reactive states. Integrity of deuterium oxide effects and hydron inventories