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Properties of Ceramides and Their Impact on the Stratum Corneum Structure: A Review

The lipid matrix of the stratum corneum (SC) is the major diffusion-rate-limiting pathway by which most drugs intracellularly pass the SC. The major lipid classes extracted from the SC are ceramides, cholesterol and free fatty acids. Ceramides that comprise nine subclasses play a crucial role in maintaining the barrier function of the skin. A profound knowledge of the physical properties of ceramides is essential for a deeper understanding of the impact of each ceramide species on the barrier function. The review summarizes the thermotropic and/or lyotropic behaviour of sphingosine-type ceramides (CER AS, CER NS) and phytosphingosine-type ceramides (CER AP, CER NP) revealed by differential scanning calorimetry, X-ray diffraction, Fourier transform infrared spectroscopy and Fourier transform Raman spectroscopy in past decades. Polymorphism is a characteristic feature of ceramides. At physiological temperatures, all crystalline phases of ceramides exhibit lamellar structures with highly ordered hydrocarbon chains. The differential behaviour of the head groups of ceramides may be an important determinant for the skin barrier function.