Skip to main content
Biophysical Journal logoLink to Biophysical Journal
. 1995 Apr;68(4):1383–1395. doi: 10.1016/S0006-3495(95)80311-5

Molecular organization and motions of crystalline monoacylglycerols and diacylglycerols: a C-13 MASNMR study.

W Guo 1, J A Hamilton 1
PMCID: PMC1282033  PMID: 7787024

Abstract

Six saturated acylglycerols (1-myristoyl-sn-glycerol, 1-palmitoyl-sn-glycerol, 1,2-dimyristoyl-sn-glycerol, 1,2-dipalmitoyl-sn-glycerol, 1,2-dipalmitoyl-rac-glycerol, and 1,3-dimyristoylglycerol) were studied in their various polymorphic forms (sub-alpha, alpha, beta') by natural abundance C-13 nuclear magnetic resonance (NMR) with magic angle spinning (MASNMR). C-13 MASNMR does not require single crystals and can observe relatively disordered crystals, distinct advantages over crystallographic diffraction methods. Well resolved spectra were obtained for each acylglycerol, and the chemical shifts of corresponding carbons were different for each crystalline phase and the isotropic liquid phase; moreover, in the case of monoacylglycerols, the symmetrically nonequivalent molecules in the same crystalline structure gave distinct C-13 resonances for the same carbon. The C-13 chemical shifts corresponding to each polymorphic phase were interpreted in terms of differences in intramolecular bond distances, intermolecular interactions (such as H bonding), and molecular motions. Mobilities of the glycerol backbone and acyl chains were assessed by the C-13 linewidths and the C-H dipolar relaxation rates. The chemical shift anisotropy(ies) (delta sigma) of the carbonyl group(s) of each acylglycerol was determined from slow-spinning MAS spectra, and was discussed in terms of the conformational and/or motional changes for the carbonyl carbon(s).

Full text

PDF
1383

Selected References

These references are in PubMed. This may not be the complete list of references from this article.

  1. Adebodun F., Chung J., Montez B., Oldfield E., Shan X. Spectroscopic studies of lipids and biological membranes: carbon-13 and proton magic-angle sample-spinning nuclear magnetic resonance study of glycolipid-water systems. Biochemistry. 1992 May 12;31(18):4502–4509. doi: 10.1021/bi00133a017. [DOI] [PubMed] [Google Scholar]
  2. Bruzik K. S., Salamonczyk G. M., Sobon B. 13C CP-MAS study of the gel phases of 1,2-dipalmitoylphosphatidylcholine. Biochim Biophys Acta. 1990 Mar 30;1023(1):143–146. doi: 10.1016/0005-2736(90)90020-o. [DOI] [PubMed] [Google Scholar]
  3. De Boeck H., Zidovetzki R. Interactions of saturated diacylglycerols with phosphatidylcholine bilayers: A 2H NMR study. Biochemistry. 1992 Jan 21;31(2):623–630. doi: 10.1021/bi00117a046. [DOI] [PubMed] [Google Scholar]
  4. Di L., Small D. M. Physical behavior of the mixed chain diacylglycerol, 1-stearoyl-2-oleoyl-sn-glycerol: difficulties in chain packing produced marked polymorphism. J Lipid Res. 1993 Sep;34(9):1611–1623. [PubMed] [Google Scholar]
  5. Dorset D. L., Pangborn W. A. Polymorphic forms of 1,2-dipalmitoyl-sn-glycerol: a combined X-ray and electron diffraction study. Chem Phys Lipids. 1988 Sep;48(1-2):19–28. doi: 10.1016/0009-3084(88)90130-2. [DOI] [PubMed] [Google Scholar]
  6. Epand R. M., Epand R. F., Lancaster C. R. Modulation of the bilayer to hexagonal phase transition of phosphatidylethanolamines by acylglycerols. Biochim Biophys Acta. 1988 Nov 22;945(2):161–166. doi: 10.1016/0005-2736(88)90478-6. [DOI] [PubMed] [Google Scholar]
  7. Ganong B. R., Loomis C. R., Hannun Y. A., Bell R. M. Specificity and mechanism of protein kinase C activation by sn-1,2-diacylglycerols. Proc Natl Acad Sci U S A. 1986 Mar;83(5):1184–1188. doi: 10.1073/pnas.83.5.1184. [DOI] [PMC free article] [PubMed] [Google Scholar]
  8. Griffin R. G. Solid state nuclear magnetic resonance of lipid bilayers. Methods Enzymol. 1981;72:108–174. doi: 10.1016/s0076-6879(81)72010-x. [DOI] [PubMed] [Google Scholar]
  9. Guo W., Hamilton J. A. Molecular organization and motions of cholesteryl esters in crystalline and liquid crystalline phases: a 13C and 1H magic angle spinning NMR study. Biochemistry. 1993 Sep 7;32(35):9038–9052. doi: 10.1021/bi00086a009. [DOI] [PubMed] [Google Scholar]
  10. Hamilton J. A., Bhamidipati S. P., Kodali D. R., Small D. M. The interfacial conformation and transbilayer movement of diacylglycerols in phospholipid bilayers. J Biol Chem. 1991 Jan 15;266(2):1177–1186. [PubMed] [Google Scholar]
  11. Hamilton J. A., Fujito D. T., Hammer C. F. Solubilization and localization of weakly polar lipids in unsonicated egg phosphatidylcholine: A 13C MAS NMR study. Biochemistry. 1991 Mar 19;30(11):2894–2902. doi: 10.1021/bi00225a024. [DOI] [PubMed] [Google Scholar]
  12. Kodali D. R., Fahey D. A., Small D. M. Structure and polymorphism of saturated monoacid 1,2-diacyl-sn-glycerols. Biochemistry. 1990 Dec 4;29(48):10771–10779. doi: 10.1021/bi00500a008. [DOI] [PubMed] [Google Scholar]
  13. Kodali D. R., Redgrave T. G., Small D. M., Atkinson D. Synthesis and polymorphism of 3-acyl-sn-glycerols. Biochemistry. 1985 Jan 15;24(2):519–525. doi: 10.1021/bi00323a041. [DOI] [PubMed] [Google Scholar]
  14. Larsson K. Classification of glyceride crystal forms. Acta Chem Scand. 1966;20(8):2255–2260. doi: 10.3891/acta.chem.scand.20-2255. [DOI] [PubMed] [Google Scholar]
  15. Meulendijks G. H., De Haan J. W., Van Genderen M. H., Buck H. M. Conformational transmission in condensed lipid model compounds. Chain packing modification by head-group-induced conformational changes in the glyceryl backbone. Eur J Biochem. 1989 Jul 1;182(3):531–538. doi: 10.1111/j.1432-1033.1989.tb14860.x. [DOI] [PubMed] [Google Scholar]
  16. Pascher I., Sundell S., Hauser H. Glycerol conformation and molecular packing of membrane lipids. The crystal structure of 2,3-dilauroyl-D-glycerol. J Mol Biol. 1981 Dec 15;153(3):791–806. doi: 10.1016/0022-2836(81)90419-8. [DOI] [PubMed] [Google Scholar]
  17. Pearson R. H., Pascher I. The molecular structure of lecithin dihydrate. Nature. 1979 Oct 11;281(5731):499–501. doi: 10.1038/281499a0. [DOI] [PubMed] [Google Scholar]
  18. Smith S. O., Kustanovich I., Bhamidipati S., Salmon A., Hamilton J. A. Interfacial conformation of dipalmitoylglycerol and dipalmitoylphosphatidylcholine in phospholipid bilayers. Biochemistry. 1992 Nov 24;31(46):11660–11664. doi: 10.1021/bi00161a054. [DOI] [PubMed] [Google Scholar]
  19. Soulages J. L., Rivera M., Walker F. A., Wells M. A. Hydration and localization of diacylglycerol in the insect lipoprotein lipophorin. A 13C-NMR study. Biochemistry. 1994 Mar 22;33(11):3245–3251. doi: 10.1021/bi00177a015. [DOI] [PubMed] [Google Scholar]
  20. Wittebort R. J., Schmidt C. F., Griffin R. G. Solid-state carbon-13 nuclear magnetic resonance of the lecithin gel to liquid-crystalline phase transition. Biochemistry. 1981 Jul 7;20(14):4223–4228. doi: 10.1021/bi00517a042. [DOI] [PubMed] [Google Scholar]

Articles from Biophysical Journal are provided here courtesy of The Biophysical Society

RESOURCES