Cholesterol versus alpha-tocopherol: effects on properties of bilayers made from heteroacid phosphatidylcholines.

The techniques of differential scanning calorimetry, fluorescence of merocyanine 540, fluorescence polarization of 1,6-diphenyl-1,3,5-hexatriene, proton permeability, and lipid peroxidation are used to compare the perturbations of cholesterol and alpha-tocopherol on lipid bilayer membranes composed of different phosphatidylcholines containing stearic acid in the sn-1 position and an unsaturated fatty acid (either oleic, alpha-linolenic, gamma-linolenic, or docosahexaenoic acid) in the sn-2 position. It is concluded that the structural roles of cholesterol and alpha-tocopherol may be similar with membranes composed of some phosphatidylcholines but are clearly different with membranes composed of other related phosphatidylcholines. alpha-Tocopherol exerts a much larger effect than cholesterol on membranes rich in polyunsaturated fatty acids that have their initial double bond before the delta 9 position. Cholesterol interacts more favorably with fatty acids that do not have an double bond before the delta 9 position. The membrane structural effects are explained in terms of the larger size of the sterol ring structure of cholesterol compared to the smaller chromanol ring of the alpha-tocopherol.