alpha-methylene ordering of acyl chains differs in glucolipids and phosphatidylglycerol from Acholeplasma laidlawii membranes: (2)H-NMR quadrupole splittings from individual lipids in mixed bilayers.
A Acholeplasma laidlawii strain A-EF22 was grown in a medium supplemented with alpha-deuterated oleic acid. Phosphatidylglycerol (PG), the glucolipids monoglucosyldiacylglycerol (MGlcDAG), diglucosyldiacylglycerol (DGlcDAG) and monoacyldiglucosyldiacylglycerol, and the phosphoglucolipid glycerophosphoryldiglucosyldiacylglycerol (GPDGlcDAG) were purified, and the phase behaviour and molecular ordering for the individual lipids, as well as for mixtures of the lipids, were studied by (2)H-, (31)P-NMR and X-ray scattering methods. The chemical structure of all the A. laidlawii lipids, except PG, has been determined and verified previously; here also the chemical structure of PG was verified, utilising mass spectrometry and (1)H and (13)C high resolution NMR spectroscopy. For the first time, lipid dimers were found in the mass spectrometry measurements. The major findings in this work are: (1) addition of 50 mol% of PG to the non-lamellar-forming lipid MGlcDAG does not significantly alter the transition temperature between lamellar and non-lamellar phases; (2) the (2)H-NMR quadrupole splitting patterns obtained from the lamellar liquid crystalline phase are markedly different for PG on one hand, and DGlcDAG and GPDGlcDAG on the other hand; and (3) mixtures of PG and DGlcDAG or MGlcDAG give rise to (2)H-NMR spectra consisting of a superposition of splitting patterns of the individual lipids. These remarkable features show that the local ordering of the alpha-carbon of the acyl chains is different for PG than for MGlcDAG and DGlcDAG, and that this difference is preserved when PG is mixed with the glucolipids. The results obtained are interpreted in terms of differences in molecular shape and hydrophilicity of the different polar headgroups.
Orädd
G
G
Department of Chemistry, Umeå University, SE-901 87 Umeå, Sweden. gregor.oradd@chem.umu.se
Andersson
A
A
Rilfors
L
L
Lindblom
G
G
Strandberg
E
E
Andrén
P E
PE
D000127:Acholeplasma / Q000737:chemistry*; D003903:Deuterium; D006017:Glycolipids / Q000737:chemistry*; D006838:Hydrocarbons; D008051:Lipid Bilayers / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy / Q000379:methods; D013058:Mass Spectrometry; D008563:Membrane Lipids / Q000737:chemistry* / Q000302:isolation & purification; D008697:Methane / Q000031:analogs & derivatives* / Q000737:chemistry*; D015394:Molecular Structure; D010715:Phosphatidylglycerols / Q000737:chemistry*; D014961:X-Ray Diffraction
D006017:Glycolipids; D006838:Hydrocarbons; D008051:Lipid Bilayers; D008563:Membrane Lipids; D010715:Phosphatidylglycerols; C030011:carbene; D003903:Deuterium; D008697:Methane