Structure of stratum corneum lipids characterized by FT-Raman spectroscopy and DSC. II. Mixtures of ceramides and saturated fatty acids.

Fourier transform (FT) Raman spectroscopy and differential scanning calorimetry (DSC) were used to study the thermotropic phase behaviour of mixtures of ceramides type IV (CER) and stearic acid (SA). For comparison the melting behaviour of SA was re-examined. The Raman spectra of all mixtures in the solid state show sharp bands associated with trans sequencies of the alkyl chain residues of both lipids. These features demonstrate that the hydrocarbon chains are highly ordered in the mixtures, too. The temperature dependence of the conformationally sensitive bands is used to estimate the degree of order in terms of the relative population of trans and gauche conformations. The DSC heating curves for the mixtures show two endothermic transitions which are typical for eutectic melting. The factor group splitting of the CH2 scissoring mode, arising from the orthorhombic subcell packing of SA, disappears in the course of the eutectic melting of samples with a SA content lower than 90 mol%. Both DSC and Raman spectroscopic studies reveal that CER and SA are immiscible in the solid state. The phase diagram of the system is a simple eutectic type one. The addition of SA to CER shifts the melting temperature of ceramides to lower values. However, though SA is a major component of stratum corneum (SC) it is not efficient enough to increase the fluidity of ceramides.