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

Jarrell, Harold C.; Giziewicz, Jerzy; Smith, Ian C. P.

doi:10.1021/bi00361a032

Cited by 69 publications

(80 citation statements)

References 37 publications

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“…The sugar ring was described as rotating rapidly about a segmental axis which was fluctuating or wobbling about a preferred direction. The time-averaged amplitude of the wobbling, given by the order parameter S,,,,,, was found to be 0.45 (Jarrell et al, 1986). The orientation of the rigid glucopyranose ring relative to the segmental rotation axis is that shown in Figure 1 and is similar to that reported for a glycosphingolipid (Skarjune & Oldfield, 1982) as discussed in detail elsewhere (Jarrell et al, 1986).…”

supporting

confidence: 79%

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Determination of conformational properties of glycolipid head groups by deuterium NMR of oriented multibilayers

Jarrell¹,

Jovall²,

Giziewicz³

et al. 1987

Biochemistry

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110

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The conformations and orientations of the glucose and glycerol moieties of a monoglucosyl lipid in hydrated bilayers have been determined in detail by deuterium nuclear magnetic resonance (2H NMR). Multibilayer membranes of 1,2-di-O-tetradecyl-3-O-(beta-D-glucopyranosyl)glycerol (DTGL), of dimyristoylphosphatidylcholine (DMPC), and of a mixture of DTGL and DMPC were oriented between glass plates. The glucolipid was selectively labeled with deuterium on the pyranose ring and at C3 of glycerol, whereas DMPC was labeled at the C4 position of the sn-2 chain. Quadrupolar splittings were measured as a function of the angle between the bilayer normal and the magnetic field direction. The results establish that the director of motional averaging, the direction about which motion and order are axially symmetric, is the bilayer normal for all the head group, the glycerol backbone, and the hydrophobic core. Segmental order parameters were determined to be 0.45, 0.65, and 0.40, respectively, for the various regions of DTGL in the membranes. The latter results indicate that there is some motion on the time scale of 10(5) s-1 about the C1'(glucose)-O-C3(glycerol) glycosidic bond but that its amplitude is very restricted. Comparison of 1H-decoupled and 1H-coupled 2H NMR spectra of the C3-labeled glycolipid gave estimates of the 2H-2H dipolar coupling between the deuterons at this position. The orientation of the glycerol C3 hydroxymethylene subunit was calculated relative to the bilayer normal, and the C2-C3 bond was found to be tilted away from the bilayer normal by 3 +/- 1 degree.(ABSTRACT TRUNCATED AT 250 WORDS)

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supporting

confidence: 79%

“…was undergoing axially symmetric motion in the liquid-crystalline phase (Jarrell et al, 1986). The sugar ring was described as rotating rapidly about a segmental axis which was fluctuating or wobbling about a preferred direction.…”

mentioning

confidence: 99%

Determination of conformational properties of glycolipid head groups by deuterium NMR of oriented multibilayers

Jarrell¹,

Jovall²,

Giziewicz³

et al. 1987

Biochemistry

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110

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“…The conformation of Glca1Gro suggests that the orientation of the glucosyl residue is almost parallel to the membrane surface. This is consistent with the 2 H-NMR data reported by Jarrell et al [18] in which the deuterons at the C4 position in the glucosyl residue of Glca3glycerol diether was shown to be diverted away from the lipid axis, suggesting the parallel orientation to the membrane surface, in contrast with the Glcb residue, which is perpendicular to the lipid bilayer [21,39]. This orientation could produce the relatively short saccharide chain of S 2 -DGD-1 with a widely expanded structure on the membrane surface, whereas in glycosphingolipids containing the longer carbohydrate chains, it has been shown that their`L' shape conformation results in the saccharide chain lying on the membranes [40,41].…”

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confidence: 90%

Conformational studies on a unique bis-sulfated glycolipid using NMR spectroscopy and molecular dynamics simulations

Iida-Tanaka¹,

Fukase²,

Utsumi³

et al. 2000

Eur J Biochem

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The time-averaged solution conformation of a unique bis-sulfated glycolipid (HSO 3 ) 2 -2,6Mana-2Glca-1-sn-2,3-O-alkylglycerol, was studied in terms of the torsional angles of two glycosidic linkages, f (H1-C1-O-Cx) and c (C1-O-Cx-Hx), derived from heteronuclear three-bond coupling constants ( 3 J C,H ), and inter-residual proton± proton distances from J-HMBC 2D and ROESY experiments, respectively. The dihedral angles of Glca1Gro in glycolipids were determined for the first time. The C1-C4 diagonal line of the a-glucose ring makes an angle of < 120 8 with the glycerol backbone, suggesting that the a-glucose ring is almost parallel to the membrane surface in contrast with the perpendicular orientation of the b-isomer. Furthermore, minimum-energy states around the conformation were estimated by Monte Carlo/stochastic dynamics (MCSD) mixed-mode simulations and the energy minimization with assisted model building and energy refinement (AMBER) force field. The Glca1Gro linkage has a single minimum-energy structure. On the other hand, three conformers were observed for the Mana2Glc linkage. The flexibility of Mana2Glc was further confirmed by the absence of inter-residual hydrogen bonds which were judged from the temperature coefficients of the chemical shifts, dd/dT (210 23 p.p.m.´8C 21), of hydroxy protons. The conformational flexibility may facilitate interaction of extracellular substances with both sulfate groups.

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“…While this value is somewhat larger than the value generally assumed for carbohydrates (164 kHz (14)), it is within the range measured very recently by Serianni and co-workers using 2 H spin-lattice relaxation times (15). Interestingly, in the present study we find that v Q for the anomeric deuteron is significantly larger than that for all other endocyclic deuterons in methyl-β-D-glucopyranoside, whereas in the study of Serianni et al the reverse was found.…”

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confidence: 59%

Residual 2H Quadrupolar Couplings in Weakly Aligned Carbohydrates

Kjellberg¹,

Homans²

2001

Journal of Magnetic Resonance

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

Cited by 69 publications

References 37 publications

Determination of conformational properties of glycolipid head groups by deuterium NMR of oriented multibilayers

Determination of conformational properties of glycolipid head groups by deuterium NMR of oriented multibilayers

Conformational studies on a unique bis-sulfated glycolipid using NMR spectroscopy and molecular dynamics simulations

Residual 2H Quadrupolar Couplings in Weakly Aligned Carbohydrates

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