Photo-initiated peroxidation of lipids in micelles by azaaromatics.

Abstract

The monoazaaromatics, pyridine (1), hexyl nicotinate (2), and quinoline (3) and diazaaromatics, pyrimidine (4) and purine (5), readily act as photo-initiators for the peroxidation of methyl linoleate in 0.50 M SDS at 37 degrees C giving free radical chain oxidations of linoleate. Quantitative kinetic runs on the order in substate, RH, and in the rate of chain initiation, Ri, showed that the classical rate law for autoxidation, -d[O2]/dt = (kp/(2 kt 1/2))[RH] x Ri 1/2, is applicable to these photo-initiated oxidations. The oxidizability of methyl linoleate under these conditions is 2.92 x 10(-2) M-1/2 s-1/2. These peroxidations were inhibited by chromanol phenolic antioxidants of the vitamin E class, such as lipid-soluble 2,2,5,7,8-pentamethyl-6-hydroxychroman (PMHC) and water-soluble 2-carboxy- 2,5,7,8-tetramethyl-6-hydroxychroman (Trolox) and derived rate constants for inhibition of peroxidation were kinh (PMHC) = 4.35 x 10(4) M-1 s-1 and k(inh) (Trolox) = 2.81 x 10(4) M-1 s-1 during inhibited oxidation of methyl linoleate photo-initiated by 4. The products from photo-initiated peroxidation of methyl linoleate by 1 through 5 were determined by reduction and high-performance liquid chromatography analyses to be the 9- and 13-positional hydroperoxides of the four geometrical isomers: cis-9, trans-11 (6), trans-10, cis-12 (7), trans-9, trans-11 (8), and trans-10, trans-12 (9)-octadecadienoates typical of the free radical chain mechanism of lipid peroxidation. Products from dye-sensitized oxidation by Methylene Blue or Rose Bengal of methyl linoleate gave a product distribution of six hydroperoxides typical of oxidation by singlet oxygen. Thermal or photo-initiated peroxidation of methyl linoleate in SDS gave some selectivity of oxidation at the 13-position of the linoleate chain. The ratio of 13- to 9-oxidation varied in the range 1.23 to 1.14 as the cis/trans to trans/trans ratio of geometrical isomers varied from 0.44 to 1.25 during photooxidation of increased amounts of linoleate in SDS. This selectivity is attributed to loss of the pseudo symmetry around the pentadienyl system in the lipid chain in the SDS system during the peroxidation.