The structure of D-erythro-C18 ceramide at the air-water interface

X-ray reflectivity (XR) and diffraction at grazing angles of incidence (GID) were conducted to determine the structure of synthetic D-erythro C18-ceramide films at the air-water interface at various surface pressures (pi). Analysis of the GID reveals that the monomolecular film, at the crystalline phase (pi > 0 mN/m), is predominantly hexagonal. In this crystalline phase, the analysis of the reflectivity yields an electron density profile that consists of three distinct homogeneous slabs, one associated with the headgroup region and the other two with the hydrocarbon chains. At large molecular areas (pi approximately 0), isolated crystalline domains coexist with two-dimensional gas phase. Within the crystalline domains, we find an orthorhombic arrangement of the chains that coexists with the hexagonal symmetry. It is argued that the two-dimensional orthorhombic crystals are induced by hydrogen bonding between headgroups even at very low surface pressures. Although their structure is incommensurate with the simple hexagonal arrangement, they act as nucleation centers for the conventional hexagonal phase which dominates at high pi.