Spontaneous interbilayer transfer of hexosylceramides between phospholipid bilayers

The kinetics of spontaneous transfer of various glucosyl- and galactosylceramides between 1-palmitoyl-2-oleoylphosphatidylcholine vesicles have been examined at 45 degrees C. Bovine brain galactosylceramides, kerasin and phrenosin, were found to transfer with biexponential kinetics. The kerasin fast pool is approximately 17% with a half-time of 29 h and the slow pool approximately 83% with a half-time of 2700 h. In contrast, semisynthetic N-palmitoylgalactosylceramide at the same temperature transfers with single-exponential kinetics with a half-time of 32 h. The half-time for N-lignoceroylgalactosylceramide under the same conditions proved to be greater than 3500 h. No concentration dependence for these half-times was found in the concentration range studied (0-10 mol%). Similar results were obtained for semisynthetic glucosylceramides. The biexponential kinetics observed for the two bovine brain ceramides, both of which are mixtures of short and long acyl chain molecules, are most probably a reflection of the strong dependence of transfer rate on acyl chain length. The very slow transfer rates of the long acyl chain hexosylceramides ensure that these molecules are lost very slowly, if at all, by spontaneous transfer from the external surface of plasma membranes; a result that is consistent with the putative biological role of glycosphingolipids.