Thermotropic phase properties of 1,2-di-O-tetradecyl-3-O-(3-O-methyl-β- D-glucopyranosyl)-sn-glycerol

Theodore "Ted" Trouard, D. A. Mannock, G. Lindblom, L. Rilfors, M. Akiyama, R. N. McElhaney

Research output: Contribution to journalArticle

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Abstract

The hydration properties and the phase structure of 1,2-di-O-tetradecyl- 3-O-(3-O-methyl-β-D-glucopyranosyl)-sn-glycerol (3-O-Me-β-D-GlcDAlG) in water have been studied via differential scanning calorimetry, 1H-NMR and 2H-NMR spectroscopy, and x-ray diffraction. Results indicate that this lipid forms a crystalline (L(c)) phase up to temperatures of 60-70°C, where a transition through a metastable reversed hexagonal (H(II)) phase to a reversed micellar solution (L2) phase occurs. Experiments were carried out at water concentrations in a range from 0 to 35 wt %, which indicate that all phases are poorly hydrated, taking up <5 mol water/mol lipid. The absence of a lamellar liquid crystalline (L(α)) phase and the low levels of hydration measured in the discernible phases suggest that the methylation of the saccharide moiety alters the hydrogen bonding properties of the headgroup in such a way that the 3-O-Me-β-D-GlcDAlG headgroup cannot achieve the same level of hydration as the unmethylated form. Thus, in spite of the small increase in steric bulk resulting from methylation, there is an increase in the tendency of 3-O-Me-β-D-GlcDAlG to form nonlamellar structures. A similar phase behavior has previously been observed for the Acholeplasma laidlawii A membrane lipid 1,2-diacyl-3-O-(6-O-acyl-α-D-glucopyranosyl)-sn-glycerol in water (Lindblom et al. 1993. J. Biol. Chem. 268:16198-16207). The phase behavior of the two lipids suggests that hydrophobic substitution of a hydroxyl group in the sugar ring of the glucopyranosylglycerols has a very strong effect on their physicochemical properties, i.e., headgroup hydration and the formation of different lipid aggregate structures.

Original languageEnglish (US)
Pages (from-to)1090-1100
Number of pages11
JournalBiophysical Journal
Volume67
Issue number3
StatePublished - 1994
Externally publishedYes

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Glycerol
Lipids
Water
Methylation
Acholeplasma laidlawii
Differential Scanning Calorimetry
Hydrogen Bonding
Membrane Lipids
Hydroxyl Radical
Magnetic Resonance Spectroscopy
X-Rays
Temperature

ASJC Scopus subject areas

  • Biophysics

Cite this

Trouard, T. T., Mannock, D. A., Lindblom, G., Rilfors, L., Akiyama, M., & McElhaney, R. N. (1994). Thermotropic phase properties of 1,2-di-O-tetradecyl-3-O-(3-O-methyl-β- D-glucopyranosyl)-sn-glycerol. Biophysical Journal, 67(3), 1090-1100.

Thermotropic phase properties of 1,2-di-O-tetradecyl-3-O-(3-O-methyl-β- D-glucopyranosyl)-sn-glycerol. / Trouard, Theodore "Ted"; Mannock, D. A.; Lindblom, G.; Rilfors, L.; Akiyama, M.; McElhaney, R. N.

In: Biophysical Journal, Vol. 67, No. 3, 1994, p. 1090-1100.

Research output: Contribution to journalArticle

Trouard, TT, Mannock, DA, Lindblom, G, Rilfors, L, Akiyama, M & McElhaney, RN 1994, 'Thermotropic phase properties of 1,2-di-O-tetradecyl-3-O-(3-O-methyl-β- D-glucopyranosyl)-sn-glycerol', Biophysical Journal, vol. 67, no. 3, pp. 1090-1100.
Trouard, Theodore "Ted" ; Mannock, D. A. ; Lindblom, G. ; Rilfors, L. ; Akiyama, M. ; McElhaney, R. N. / Thermotropic phase properties of 1,2-di-O-tetradecyl-3-O-(3-O-methyl-β- D-glucopyranosyl)-sn-glycerol. In: Biophysical Journal. 1994 ; Vol. 67, No. 3. pp. 1090-1100.
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abstract = "The hydration properties and the phase structure of 1,2-di-O-tetradecyl- 3-O-(3-O-methyl-β-D-glucopyranosyl)-sn-glycerol (3-O-Me-β-D-GlcDAlG) in water have been studied via differential scanning calorimetry, 1H-NMR and 2H-NMR spectroscopy, and x-ray diffraction. Results indicate that this lipid forms a crystalline (L(c)) phase up to temperatures of 60-70°C, where a transition through a metastable reversed hexagonal (H(II)) phase to a reversed micellar solution (L2) phase occurs. Experiments were carried out at water concentrations in a range from 0 to 35 wt {\%}, which indicate that all phases are poorly hydrated, taking up <5 mol water/mol lipid. The absence of a lamellar liquid crystalline (L(α)) phase and the low levels of hydration measured in the discernible phases suggest that the methylation of the saccharide moiety alters the hydrogen bonding properties of the headgroup in such a way that the 3-O-Me-β-D-GlcDAlG headgroup cannot achieve the same level of hydration as the unmethylated form. Thus, in spite of the small increase in steric bulk resulting from methylation, there is an increase in the tendency of 3-O-Me-β-D-GlcDAlG to form nonlamellar structures. A similar phase behavior has previously been observed for the Acholeplasma laidlawii A membrane lipid 1,2-diacyl-3-O-(6-O-acyl-α-D-glucopyranosyl)-sn-glycerol in water (Lindblom et al. 1993. J. Biol. Chem. 268:16198-16207). The phase behavior of the two lipids suggests that hydrophobic substitution of a hydroxyl group in the sugar ring of the glucopyranosylglycerols has a very strong effect on their physicochemical properties, i.e., headgroup hydration and the formation of different lipid aggregate structures.",
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AU - Mannock, D. A.

AU - Lindblom, G.

AU - Rilfors, L.

AU - Akiyama, M.

AU - McElhaney, R. N.

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AB - The hydration properties and the phase structure of 1,2-di-O-tetradecyl- 3-O-(3-O-methyl-β-D-glucopyranosyl)-sn-glycerol (3-O-Me-β-D-GlcDAlG) in water have been studied via differential scanning calorimetry, 1H-NMR and 2H-NMR spectroscopy, and x-ray diffraction. Results indicate that this lipid forms a crystalline (L(c)) phase up to temperatures of 60-70°C, where a transition through a metastable reversed hexagonal (H(II)) phase to a reversed micellar solution (L2) phase occurs. Experiments were carried out at water concentrations in a range from 0 to 35 wt %, which indicate that all phases are poorly hydrated, taking up <5 mol water/mol lipid. The absence of a lamellar liquid crystalline (L(α)) phase and the low levels of hydration measured in the discernible phases suggest that the methylation of the saccharide moiety alters the hydrogen bonding properties of the headgroup in such a way that the 3-O-Me-β-D-GlcDAlG headgroup cannot achieve the same level of hydration as the unmethylated form. Thus, in spite of the small increase in steric bulk resulting from methylation, there is an increase in the tendency of 3-O-Me-β-D-GlcDAlG to form nonlamellar structures. A similar phase behavior has previously been observed for the Acholeplasma laidlawii A membrane lipid 1,2-diacyl-3-O-(6-O-acyl-α-D-glucopyranosyl)-sn-glycerol in water (Lindblom et al. 1993. J. Biol. Chem. 268:16198-16207). The phase behavior of the two lipids suggests that hydrophobic substitution of a hydroxyl group in the sugar ring of the glucopyranosylglycerols has a very strong effect on their physicochemical properties, i.e., headgroup hydration and the formation of different lipid aggregate structures.

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