Correlation of side chain mobility with cholesterol retention by phospholipid vesicles

Multilamellar vesicles were prepared from choline phospholipids with various fatty acyl chains, singly and in mixtures, with and without cholesterol. Mobility of acyl side chains for each type of vesicle was measured by fluorescence polarization with diphenylhexatriene, and the amounts of cholesterol and phospholipid retained by them after extraction with a nonpolar solvent were determined. The data suggest that structures of acyl chains determine the extractability of cholesterol. Phosphatidylcholines with unsaturated or short saturated side chains above transition temperature retain less cholesterol upon extraction with petroleum ether than phosphatidylcholines with saturated side chains below transition temperature. Correlation of cholesterol retention with side chain mobility showed that cholesterol is more easily removed from vesicles with mobile acyl side chains than from vesicles with rigid side chains. The presence of cholesterol also alters extractability of phospholipids from vesicles and suggests that sterol affects the polarity rather than spacing of headgroups on vesicle surfaces.