Chem. 63, 2633 (1985).The kinetics of autoxidation of linoleic acid in dimyristoylphosphatidylcholine (DMPC) bilayers were studied at 30°C and pH 7 under 760 Torr 02. Reactions were initiated using either the lipid-soluble di-tert-butylhyponitrite (DBHN) or watersoluble azobis(2-amidinopropane) . HCI (ABAP). Rates of chain initiation, R i , were measured with a lipid-soluble antioxidant, a-tocopherol, or a water-soluble one, 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxyate (Trolox). The slightly higher oxidizability pbtained (kp/2k$ = 2.76 x lo-' M-i s-4 compared to methyl linoleate in chlombenzene (kp/2k$ = 2.18 x ]0-2 M-i -2 s 3 is attributed to a moderate polar solvent effect on ionized linoleate near the bilayer surface. A low initiator efficiency, e = 0.0895 for DBHN in DMPC, is attributed to the cage effect in the bilayer of high microviscosity. Similar autoxidation experiments on methyl linoleate in DMPC bilayers gave a lower oxidizability (kp/2k) = 1.79 x lo-' M-i s-i), indicating that the ester is sequestered deeper in the hydrophobic region of DMPC than is ionized linoleate. Some absolute rate constants are determined using the rotating sector technique for linoleic acid in 0.50 M SDS micelles, and egg lecithin and dilinoleoylphosphatidylcholine (DLPC) bilayers. A hundredfold decrease in the termination rate constant, 2k,, for DLPC bilayer compared to homogeneous solution is attributed to chain termination in a bilayer region of high polarity. A concomitant reduction (up to tenfold) in the propagation rate constant, k,, is attributed to diffusion of polar peroxyl radicals away from the oxidizable region of the bilayer.LAWRENCE ROSS COATES BARCLAY, STEVEN JEFFREY LOCKE, JOSEPH MARK MACNEIL et JOANN VANKESSEL. Can. J. Chem.
63, 2633 (1985).Opt5rant h 30°C, i un pH de 7 et sous une pression de 760 Torr d'02, on a ttudiC la cinktique de I'auto-oxydation de I'acide IinolCique dans des couches doubles de dimyristoylphosphatidylcholine (DMPC). On a initie les reactions i I'aide soit de I'hyponitrite du di-tert-butyle (HNDB) qui est soluble dans les lipides soit le chlorhydrate de I'azo bis(amidin0-2 propane) (ABAP) qui est soluble dans I'eau. On a mesure les vitesses d'initiation de chaines, Ri, en presence d'un antioxydant soluble dans I'eau, I'a-tocophCrol, ainsi que d'un antioxydant soluble days I'eau, I'hydroxy-q tt5pamethyl-2,5,7,8 chromanecarboxylate-2 (Trolox). L'oxyd,abifite est 1Cgkrement supt5rieure (k,/2k? = 2,76 x lo-' M-7 s-3 h celle du linoleate de mCthyle (kp/2k,3 = 2,18 x lo-' M-i s-3; on attribue ce resultat h une influence modCree du solvant polaire sur le linoltate ionis6 prks de la surface i couche double. On attribue la faible efficacitk comme initiateur, e = 0,0895, du HNDB dans le DMPC i un effet de cage dans la double couche qui aurait une microviscositC ClevCe. Des experiences semblables d'a~to~oxydation sur le linolkate de mCthyle dans des doubles couches de DMPC donnent lieu i des oxydabilites plus faibles (kp/2k,5 = 1,79 x M-f s-$; ce rksultat indiquerait que I'ester est plus sequ...