Autoxidation of fatty acid monolayers adsorbed on silica gel: III. Effects of saturated fatty acids and cholesterol.

Autoxidation of fatty acid monolayers on silica consisting of multiple components to simulate biomembranes has been studied by the rate of fatty acid disappearance and the products formed. When palmitic acid was incorporated into linoleic acid monolayers, the decrease in rate was proportional to the amounts of plamitic acid present. The protective effect of the saturated fatty acid diminished rapidly as the chain length of the saturated fatty acid decreased below C12. With acids of medium chain length, C12 was more effective than C16. In pure linoleic acid monolayers, when the surface coverage was reduced to only 5% of the available adsorption sites, and in the case of palmitic acid-linoleic acid monolayers, the rate dropped drastically and the major identified product formed was hydroxyepoxyoctadecenoic acid. On the contrary, the major product formed in the case of saturated monolayers of pure linoleic acid was a mixture of unsubstituted epoxy acids. The inclusion of cholesterol in linoleic acid monolayers increased the rate of disappearance of linoleic acid slightly, whereas cholesteryl acetate decreased the rate. The protective effect exerted by cholesteryl acetate appeared to be similar to that of palmitic acid.