Molecular parameters of semisynthetic derivatives of gangliosides and sphingosine in monolayers at the air-water interface

Abstract

The molecular parameters (molecular area, surface potential, collapse pressure, dipole moment contributions) of semisynthetic derivatives of ganglioside GM1 and of sphingosine were studied in lipid monolayers at the air-NaCl (145 mM, pH 5.6) interface at 22 ± 0.3°C. The chemical modifications included alterations of the fatty acyl chain moiety linked to the 2-amino position of the sphingosine (Sph) base. The compounds studied were PKS-1 ( N-acetyl Sph), PKS-2 ( N-chloroacetyl Sph), PKS-3 ( N-dichloroacetyl Sph), PKS-4 ( N-trichloroacetyl Sph), Lyso-GM1 (ganglioside GM1 lacking the N-linked fatty acyl chain and the N-acetyl group on the sialic acid), Liga-4 ( N-acetyl, lyso[NeuAc]GM1) and Liga-20 ( N-dichloroacetyl, lyso[NeuAc]GM1). Relatively small modifications of the chemical structure of sphingolipids introduce dramatic consequences on their surface molecular properties. The absence of the long chain fatty acyl moiety and of the N-acetyl group on the neuraminic acid in Lyso-GM1 leads to a more condensed behavior and to an increase of the collapse pressure compared with GM1. The acetylation or chloroacetylation at the 2-amino position in Liga-4 and Liga-20 induce an expansion of the surface pressure-area isotherm and a decrease of the collapse pressure. The limiting molecular areas of GM1 derivatives, taken at the collapse pressure point, are consistent with the oligosaccharide chain being oriented approximately perpendicularly to the interface. Sphingosine shows a liquid expanded isotherm. The acetylation and successive chlorination of the acetyl residue at the 2-amino position of Sph cause a progressive increase in the limiting molecular area. The variation of the resultant dipole moment under compression, calculated from the surface potential values, suggests the reorientation of selective groups within these molecules that depend on the degree of intermolecular packing. Thermodynamic-geometric correlations on the basis of the molecular parameters of these derivatives suggest that small alterations of the substituent group at the 2-amino position of Sph could have large and amplified consequences on the type, curvature and stability of the possible self-aggregated structure that these lipids may form in aqueous medium.