Evidence that trans-bilayer interdigitation of glycosphingolipid long chain fatty acids may be a general phenomenon.
'Interdigitation' is a term coined to describe the phenomenon whereby pure phosphatidylcholines with intramolecular fatty acid chain length heterogeneity when hydrated to form bilayers may insert the methyl ends of long fatty acids from one side across more than half of the membrane thickness to protrude amongst the acyl chains of the opposite side of the bilayer (Keough, K.M.W. and Davis, P.J. (1979) Biochemistry 18, 1453-1459; Huang, C. and Mason, J.T. (1986) Biochim. Biophys. Acta 864, 423-470). In this article we address the fate of long fatty acid chains of glycosphingolipids present as minor components in membranes of non-interdigitating phosphatidylcholines. In this pursuit, derivatives of galactosyl ceramide, lactosyl ceramide, globoside and GM1 were synthesized having either 18-carbon or 24-carbon fatty acid with a spin label covalently attached at C-16. Labelled glycolipids were incorporated at 1-2 mol% into bilayers of synthetic phosphatidylcholines, their mixtures with cholesterol, or natural egg phosphatidylcholine. In each case the C-16 carbon of the glycolipid long chain fatty acid showed considerably greater 'order' and immobility than did C-16 of the fatty acid which was similar in length to the host matrix phospholipids. We interpret this as strong evidence that the long chain fatty acid interdigitates across the mid point of the bilayer in the systems studied. Clearly this phenomenon did not require that the phospholipid host matrix have mixed chain lengths. Furthermore it was totally independent of glycolipid family: for a given host matrix and (glycolipid) fatty acid chain length the order parameter values found were the same amongst all four glycolipid families tested.
Mehlhorn
I E
IE
Department of Biochemistry, University of Western Ontario, London, Canada.
Florio
E
E
Barber
K R
KR
Lordo
C
C
Grant
C W
CW
D005227:Fatty Acids; D006028:Glycosphingolipids; D008051:Lipid Bilayers; D008560:Membrane Fluidity; D008563:Membrane Lipids; D008968:Molecular Conformation; D013113:Spin Labels
D005227:Fatty Acids; D006028:Glycosphingolipids; D008051:Lipid Bilayers; D008563:Membrane Lipids; D013113:Spin Labels