Thermotropic behavior of stratum corneum lipids containing a pseudo-ceramide

The mechanism of the self-assembly of the lamellar structure of natural stratum corneum lipids (SCL) has been a subject of considerable interest. We have examined this question by using a synthetic pseudo-ceramide (sphingolipid E, SLE) which was analogous to the naturally occurring ceramide type 2. The thermotropic properties and the structural characteristics of SLE, together with other main components of SCL, fatty acids, and cholesterol, were investigated by differential scanning calorimetry and X-ray analysis. A mixture of SLE and stearic acid was in a stable alpha-form having a lamellar structure, which is very similar to that of natural SCL. However, lipid mixtures in which stearic acid were replaced by oleic acid did not form lamellar structures, and existed in the crystalline states. This indicates that the stable bilayer formation of the natural SCL is strongly dependent on the molecular fatty acid structure. Moreover, incorporation of cholesterol (0-50%) into equimolar mixtures of SLE/stearic acid and of SLE/oleic acid caused a marked decrease of melting entropies, while the aggregation states of both systems were not changed. This effect of cholesterol can be attributed to the disorder of the molecular packing. These results suggest that the hydrophobic interactions between the SCL are important for bilayer formation as are the hydrophilic interactions between the polar groups.