Microphase transitions of Langmuir-Blodgett lipid-assembled monolayers with new types of ceramides, ultra-long-chain ceramide and 1-O-acylceramide.

ABSTRACT

HYPOTHESIS: Intercellular lipid lamellae, consisting of ceramide, cholesterol, and free fatty acids, are the primary pathways for substances in the stratum corneum (SC). The microphase transition of lipid-assembled monolayers (LAMs), mimicking an initial layer of the SC, would be affected by new types of ceramides ceramide with ultra-long chain (CULC) and 1-O-acylceramide (CENP) with three chains in different direction. EXPERIMENTS The LAMs were fabricated with varying the mixing ratio of CULC (or CENP) against base ceramide via Langmuir-Blodgett assembly. Surface pressure-area isotherms and elastic modulus-surface pressure plots were obtained to characterize π-dependent microphase transitions. The surface morphology of LAMs was observed by atomic force microscopy. FINDINGS: The CULCs favored lateral lipid packing, and the CENPs hindered the lateral lipid packing by lying alignment, which was due to their different molecular structures and conformations. The sporadic clusters and empty spaces in the LAMs with CULC were presumably due to the short-range interactions and self-entanglements of ultra-long alkyl chains following the freely jointed chain model, respectively, which was not noticeably observed in the neat LAM films and the LAM films with CENP. The addition of surfactants disrupted the lateral packing of lipids, thus weakening the LAM elasticity. These findings allowed us to understand the role of CULC and CENP in the lipid assemblies and microphase transition behaviors in an initial layer of SC.