Diffusion of zinc through oxidized lipid bilayers
Egg phosphatidylcholine was oxidized by atmospheric oxygen under UV light for 16 hours, and the oxidized products formed were fractionated with high-pressure liquid chromatography in reverse phase. Three fractions that appeared at retention times of 19 minutes, 21 minutes and 24 minutes respectively (fraction 19, fraction 21 and fraction 24) were isolated and stabilized by reduction with triphenylphosphine. Zinc diffusion across 1-palmitoyl-2 oleoyl-sn-glycero-3-phosphocholine (POPC) liposome bilayers mixed with the isolated oxidized fractions was measured. The rate constant for zinc diffusion through the POPC liposome was highest in fraction 19 followed by fraction 21 and fraction 24.NMR data suggests that all oxidized fractions were derived from the major egg polyunsaturated PC, 1-palmitoyl-2-linoleoyl-sn-glycero-3-phosphocholine. The primary oxidized product, fraction 24 contains a mixture of isomers in which the linoleoyl group has formed the 9-hydroxy-10,12-trans-cis diene and trans-trans diene or the 13-hydroxy12,10-trans-cis diene and trans-trans diene. The primary oxidized products on further oxidation, result in secondary oxidized products, contained in fraction 21 and fraction 19.Experimental data indicates that the major components of fraction 21 are the 9-hydroxy12,13-epoxy-l0-trans-monoene (and 13-hydroxy-9,10-epoxy-11-trans-monoene) and the major components of fraction 19 are the 9,12,13-trihydroxy-l0-trans-monoene (and 9,10,13-trihydroxy-1 l-trans-monoene).