Structure and dynamics of a glyceroglycolipid: a deuterium NMR study of head group orientation, ordering, and effect on lipid aggregate structure

The head group orientation and the motional characteristics of 1,2-di-O-tetradecyl-3-O-..beta..-D-glucopyranosylglycerol selectively /sup 2/H-labeled on the glucose moiety have been investigated by differential scanning calorimetry and /sup 2/H NMR. The glycolipid undergoes a major endothermic transition at 52/sup 0/C, which is attributed to the gel to liquid-crystal phase transition. The nature of a less energetic endothermic transition at 58/sup 0/C, determined to be a lamellar to hexagonal mesophase transition by /sup 2/H NMR, is confirmed by x-ray diffraction. In the Lamellar phase, the glycolipid head group undergoes axially symmetric motion and has an orientational order parameter S/sub mol/ of 0.45. The head group is extended away from the bilayer surface. On entering the hexagonal mesophase, the orientational order parameter for the sugar ring is reduced slightly to 0.38, but the local rotation axis undergoes a large reorientation with respect to the carbohydrate ring. In a phospholipid matrix, the orientation of the carbohydrate head group of the glycolipid is affected by the greater extension of the surface residues of the host lipid.

[1]  H. Jarrell,et al.  Effects of replacement of a double bond by a cyclopropane ring in phosphatidylethanolamines: a 2H NMR study of phase transitions and molecular organization. , 1985, Biochemistry.

[2]  H. Hinz,et al.  Head-group contributions to bilayer stability: monolayer and calorimetric studies on synthetic, stereochemically uniform glucolipids. , 1985, Biochemistry.

[3]  I. Smith.  Conformational and Motional Properties of Lipids in Biological Membranes as Determined by Deuterium Magnetic Resonance , 1984 .

[4]  J. Seelig,et al.  Structure of Escherichia coli membranes. Deuterium magnetic resonance studies of the phosphoglycerol head group in intact cells and model membranes , 1983 .

[5]  H. Jarrell,et al.  A 2H-NMR analysis of dihydrosterculoyl-containing lipids in model membranes: structural effects of a cyclopropane ring. , 1983, Chemistry and physics of lipids.

[6]  James H. Davis,et al.  The description of membrane lipid conformation, order and dynamics by 2H-NMR. , 1983, Biochimica et biophysica acta.

[7]  D. Marsh,et al.  Calorimetric studies of the gel-fluid (L beta-L alpha) and lamellar-inverted hexagonal (L alpha-HII) phase transitions in dialkyl- and diacylphosphatidylethanolamines. , 1983, Biochemistry.

[8]  S. Pizzo,et al.  Characterization of functional human alpha 2-macroglobulin half-molecules isolated by limited reduction with dithiothreitol. , 1983, Biochemistry.

[9]  E. Oldfield,et al.  Physical studies of cell surface and cell membrane structure. Deuterium nuclear magnetic resonance studies of N-palmitoylglucosylceramide (cerebroside) head group structure. , 1982, Biochemistry.

[10]  E. Arnett,et al.  Chiral aggregation phenomena. 4. A search for stereospecific interactions between highly purified enantiomeric and racemic dipalmitoyl phosphatidylcholines and other chiral surfactants in monolayers, vesicles, and gels , 1982 .

[11]  P. Cullis,et al.  31P-NMR studies of oriented phospholipid multilayers , 1982 .

[12]  W. Pangborn,et al.  Ether linkages in glycerolipids. Their effect on long chain packing , 1982 .

[13]  M. Bloom,et al.  Direct determination of the oriented sample nmr spectrum from the powder spectrum for systems with local axial symmetry , 1981 .

[14]  J. Seelig,et al.  Structure of Escherichia coli membranes. Glycerol auxotrophs as a tool for the analysis of the phospholipid head-group region by deuterium magentic resonance. , 1981, Biochemistry.

[15]  J. Seelig,et al.  Bilayers of phosphatidylglycerol. A deuterium and phosphorus nuclear magnetic resonance study of the head-group region. , 1980, Biochemistry.

[16]  R. Gigg.  Synthesis of glycolipids. , 1980, Chemistry and physics of lipids.

[17]  S. Rottem.  Membrane lipids of mycoplasmas. , 1980, Biochimica et biophysica acta.

[18]  J. Silvius,et al.  Lipid and protein composition and thermotropic lipid phase transitions in fatty acid-homogeneous membranes of Acholeplasma laidlawii B. , 1980, Biochimica et biophysica acta.

[19]  K. Harlos,et al.  Influence of calcium on phosphatidylglycerol. Two separate lamellar structures. , 1980, Biochemistry.

[20]  H. Rogers,et al.  Microbial cell walls and membranes , 1980 .

[21]  E. Oldfield,et al.  Physical studies of cell surface and cell membrane structure. Deuterium nuclear magnetic resonance investigation of deuterium-labelled N-hexadeconoylgalactosylceramides (cerebrosides). , 1979, Biochimica et biophysica acta.

[22]  A. Blume,et al.  The influence of charge on phosphatidic acid bilayer membranes. , 1979, Biochimica et biophysica acta.

[23]  G. Lindblom,et al.  Water binding and phase structures for different Acholeplasma laidlawii membrane lipids studied by deuteron nuclear magnetic resonance and x-ray diffraction. , 1978, Biochimica et biophysica acta.

[24]  M. Kates,et al.  The phytanyl ether-linked polar lipids and isoprenoid neutral lipids of extremely halophilic bacteria. , 1978, Progress in the chemistry of fats and other lipids.

[25]  H. Koch,et al.  A novel method for specific labelling of carbohydrates with deuterium by catalytic exchange , 1977 .

[26]  J. Seelig.  Deuterium magnetic resonance: theory and application to lipid membranes , 1977, Quarterly Reviews of Biophysics.

[27]  S. Chan,et al.  More on the motional state of lipid bilayer membranes: interpretation of order parameters obtained from nuclear magnetic resonance experiments. , 1977, Biochemistry.

[28]  G. A. Jeffrey,et al.  The crystal and molecular structure of methyl -D-glucopyranoside hemihydrate , 1977 .

[29]  J. Seelig,et al.  Investigation of phosphatidylethanolamine bilayers by deuterium and phosphorus-31 nuclear magnetic resonance. , 1976, Biochemistry.

[30]  M. Bloom,et al.  Quadrupolar echo deuteron magnetic resonance spectroscopy in ordered hydrocarbon chains , 1976 .

[31]  M. Anteunis,et al.  Conformation of the C-5/C-6 fragment of aldohexopyranoses , 1976 .

[32]  C. Polnaszek,et al.  A study of mobility and order in model membranes using 2H NMR relaxation rates and quadrupole splittings of specifically deuterated lipids. , 1974, Biochemical and biophysical research communications.

[33]  J. Seelig,et al.  Deuterium magnetic resonance studies of phospholipid bilayers. , 1974, Biochemical and biophysical research communications.

[34]  J. Green,et al.  The phase behavior of monogalactosyl, digalactosyl, and sulphoquinovosyl diglycerides. , 1973, Biochimica et biophysica acta.