Structural and barrier properties of the skin ceramide lipid bilayer: a molecular dynamics simulation study.

Skin provides excellent protection against the harsh external environment and foreign substances. The lipid matrix of the stratum corneum, which contains various kinds of ceramides, plays a major role in the barrier function of the skin. Here we report a study of the effects of ceramide type on the structural and transport properties of ceramide bilayers using molecular dynamics (MD) simulations. Specifically, the effects of headgroup chemistry (number and positions of hydroxyl groups) and tail structure (unsaturation of the sphingoid moiety) on the structural and transport properties of various ceramide bilayers at 310 K were analyzed. Theoretical results for structural properties such as area per lipid, bilayer thickness, lateral arrangement, order parameter, and hydrogen bonding are reported here and compared with corresponding experimental data. Our study revealed that the presence of a double bond disrupts the bilayer packing, which leads to a low area compressibility modulus, a large area per lipid, and low bilayer thickness. Furthermore, the effect of structural changes on water permeation was studied using steered MD simulations. Water permeation was found to be influenced by headgroup polarity, chain packing, and the ability of the water to hydrogen bond with the ceramides. The molecular-level information obtained from the current study should aid the design of mixed bilayer systems with desired properties and provide the basis for the development of higher order coarse-grained models.