Mammalian Stratum Corneum Contains Physiologic Lipid Thermal Transitions

Using a new high-sensitivity differential scanning calorimeter, capable of very slow scanning rates and large sample volumes, we examined the thermal transitions in neonatal mouse stratum corneum. Both physiological and supraphysiological transitions were found in intact tissue that were displaced on cooling and obliterated by solvent treatment establishing them as lipids. Physiologic peaks were encountered in lipid extracts from the same tissues. With heating and cooling recycling we found a novel effect of thermal “fractionation” of the peaks into discrete subfractions that appeared to correspond roughly the number of bands found on thin-layer chromatography of the lipid extracts

Calorimetric and Electron Spin Resonance Examination of Lipid Phase Transitions in Human Stratum Corneum: Molecular Basis for Normal Cohesion and Abnormal Desquamation in Recessive X-Linke Ichthyosis

Lipids appear to play a critical role as regulators of stratum corneum desquamation. In this study, we observed discrete lipid phase transitions at physiologic temperatures in both normal human scale (NHS) and in lipid extracts of NHS by differential scanning calorimetry. In contrast, such thermal transitions were not observed in recessive x-linked ichthyosis scale (RXLIS). To gain further insight into the molecular basis of the lipid phase transitions in NHS vs. RXLIS, comparable samples were evaluated by electron spin resonance, utilizing the perdeuterated probe, di-t-butyl nitroxide. Upon electron spin resonance analysis, both NHS and RXLIS demonstrated thermal phase transitions in the physiologic range; however, the nature of the lipid environments in each type varied. Whereas the environment of the spin probe was more polar in NHS than in RXLIS, the spin probe partitioned into a more “fluid” environment in RXLIS; i.e., the spin probe was more mobile in RXLIS titan in NHS lipid matrices. Because an alteration in the cholesteryl sulfate : cholesterol ratio is the primary lipid abnormality in RXLIS, model cholesterol-fatty acid-cholesteryl sulfate mixtures were prepared in proportion to the lipid composition of NHS and RXLIS. Differences were observed in both thermal transitions and in lipid microenvironments in these mixtures that paralleled those observed in scale samples. Based on these results, a model is proposed that invokes abnormal hydrogen bonding, due to increased cholesteryl sulfate, as the mechanism for the abnormal desquamation in recessive X-linked ichthyosis