Skip to main content
NCBI home page
Biophysical Journal logoLink to Biophysical Journal
. 1985 Nov;48(5):765–773. doi: 10.1016/S0006-3495(85)83834-0

A model of orientational ordering in phosphatidylcholine bilayers based on conformational analysis of the glycerol backbone region.

L M Strenk, P W Westerman, J W Doane
PMCID: PMC1329401  PMID: 4074836

Abstract

Molecular and conformational ordering in aqueous multilamellar suspensions of 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) have been examined by deuterium nuclear magnetic resonance (2H NMR) in the liquid crystalline (L alpha) phase. Motionally averaged quadrupolar splittings vQ from six sites in the vicinity of the glycerol backbone have been analyzed by a molecular frame and order matrix approach in which the usual assumption of a freely-rotating molecule is not invoked. By assuming a relatively rigid glycerol backbone region, the six vQ values are found to be consistent with a conformation of the glycerol backbone that is almost identical to that of one of the two structures in crystalline DMPC dihydrate (Pearson, R. H., and I. Pascher, 1979, Nature (Lond.) 281: 499-501). The orientation of the most-ordered axis of the DMPC molecule is found to be tilted at an angle of 27 +/- 2 degrees with respect to the long axis of the sn-1 chain in its extended all trans conformation. The ordering of the most ordered molecular axis with respect to the bilayer normal is expressed by an order parameter of Szz approximately equal to 0.6 +/- 0.1, consistent with values in analogous thermotropic liquid crystals.

Full text

PDF
765

Selected References

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

  1. Aasen A. J., Lauer W. M., Holman R. T. Mass spectrometry of triglycerides. II. Specifically deuterated triglycerides and elucidation of fragmentation mechanisms. Lipids. 1970 Nov;5(11):869–877. doi: 10.1007/BF02531118. [DOI] [PubMed] [Google Scholar]
  2. Browning J. L., Seelig J. Bilayers of phosphatidylserine: a deuterium and phosphorus nuclear magnetic resonance study. Biochemistry. 1980 Mar 18;19(6):1262–1270. doi: 10.1021/bi00547a034. [DOI] [PubMed] [Google Scholar]
  3. Davis J. H. The description of membrane lipid conformation, order and dynamics by 2H-NMR. Biochim Biophys Acta. 1983 Mar 21;737(1):117–171. doi: 10.1016/0304-4157(83)90015-1. [DOI] [PubMed] [Google Scholar]
  4. Engel A. K., Cowburn D. The origin of multiple quadrupole couplings in the deuterium NMR spectra of the 2 chain of 1,2 dipalmitoyl-sn-glycero-3-phosphorylcholine. FEBS Lett. 1981 Apr 20;126(2):169–171. doi: 10.1016/0014-5793(81)80233-5. [DOI] [PubMed] [Google Scholar]
  5. Finer E. G., Flook A. G., Hauser H. The nature and origin of the NMR spectrum of unsonicated and sonicated aqueous egg yolk lecithin dispersions. Biochim Biophys Acta. 1972 Jan 27;260(1):59–69. doi: 10.1016/0005-2760(72)90074-4. [DOI] [PubMed] [Google Scholar]
  6. Gally H. U., Niederberger W., Seelig J. Conformation and motion of the choline head group in bilayers of dipalmitoyl-3-sn-phosphatidylcholine. Biochemistry. 1975 Aug 12;14(16):3647–3652. doi: 10.1021/bi00687a021. [DOI] [PubMed] [Google Scholar]
  7. Gally H. U., Pluschke G., Overath P., Seelig J. Structure of Escherichia coli membranes. Fatty acyl chain order parameters of inner and outer membranes and derived liposomes. Biochemistry. 1980 Apr 15;19(8):1638–1643. doi: 10.1021/bi00549a018. [DOI] [PubMed] [Google Scholar]
  8. Gally H. U., Pluschke G., Overath P., Seelig J. Structure of Escherichia coli membranes. Glycerol auxotrophs as a tool for the analysis of the phospholipid head-group region by deuterium magentic resonance. Biochemistry. 1981 Mar 31;20(7):1826–1831. doi: 10.1021/bi00510a017. [DOI] [PubMed] [Google Scholar]
  9. 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]
  10. Haberkorn R. A., Griffin R. G., Meadows M. D., Oldfield E. Deuterium nuclear magnetic resonance investigation of the dipalmitoyl lecithin-cholesterol-water system. J Am Chem Soc. 1977 Oct 26;99(22):7353–7355. doi: 10.1021/ja00464a043. [DOI] [PubMed] [Google Scholar]
  11. Hauser H., Guyer W., Pascher I., Skrabal P., Sundell S. Polar group conformation of phosphatidylcholine. Effect of solvent and aggregation. Biochemistry. 1980 Jan 22;19(2):366–373. doi: 10.1021/bi00543a018. [DOI] [PubMed] [Google Scholar]
  12. Hauser H., Pascher I., Pearson R. H., Sundell S. Preferred conformation and molecular packing of phosphatidylethanolamine and phosphatidylcholine. Biochim Biophys Acta. 1981 Jun 16;650(1):21–51. doi: 10.1016/0304-4157(81)90007-1. [DOI] [PubMed] [Google Scholar]
  13. Hauser H., Pascher I., Sundell S. Conformation of phospholipids. Crystal structure of a lysophosphatidylcholine analogue. J Mol Biol. 1980 Mar 5;137(3):249–264. doi: 10.1016/0022-2836(80)90315-0. [DOI] [PubMed] [Google Scholar]
  14. Hauser H., Phillips M. C., Levine B. A., Williams R. J. Ion-binding to phospholipids. Interaction of calcium and lanthanide ions with phosphatidylcholine (lecithin). Eur J Biochem. 1975 Oct 1;58(1):133–144. doi: 10.1111/j.1432-1033.1975.tb02357.x. [DOI] [PubMed] [Google Scholar]
  15. Hershberg R. D., Reed G. H., Slotboom A. J., De Haas G. H. Nuclear magnetic resonance studies of the aggregation of dihexanoyllecithin and of diheptanolyllecithin in aqueous solutions. Biochim Biophys Acta. 1976 Jan 22;424(1):73–81. doi: 10.1016/0005-2760(76)90051-5. [DOI] [PubMed] [Google Scholar]
  16. Hitchcock P. B., Mason R., Thomas K. M., Shipley G. G. Structural chemistry of 1,2 dilauroyl-DL-phosphatidylethanolamine: molecular conformation and intermolecular packing of phospholipids. Proc Natl Acad Sci U S A. 1974 Aug;71(8):3036–3040. doi: 10.1073/pnas.71.8.3036. [DOI] [PMC free article] [PubMed] [Google Scholar]
  17. Kohler S. J., Klein M. P. Orientation and dynamics of phospholipid head groups in bilayers and membranes determined from 31P nuclear magnetic resonance chemical shielding tensors. Biochemistry. 1977 Feb 8;16(3):519–526. doi: 10.1021/bi00622a028. [DOI] [PubMed] [Google Scholar]
  18. Marsh D. Molecular motion in phospholipid bilayers in the gel phase: long axis rotation. Biochemistry. 1980 Apr 15;19(8):1632–1637. doi: 10.1021/bi00549a017. [DOI] [PubMed] [Google Scholar]
  19. McLaughlin A. C., Cullis P. R., Hemminga M. A., Hoult D. I., Radda G. K., Ritchie G. A., Seeley P. J., Richards R. E. Application of 31P NMR to model and biological membrane systems. FEBS Lett. 1975 Sep 15;57(2):213–218. doi: 10.1016/0014-5793(75)80719-8. [DOI] [PubMed] [Google Scholar]
  20. Oldfield E., Meadows M., Rice D., Jacobs R. Spectroscopic studies of specifically deuterium labeled membrane systems. Nuclear magnetic resonance investigation of the effects of cholesterol in model systems. Biochemistry. 1978 Jul 11;17(14):2727–2740. doi: 10.1021/bi00607a006. [DOI] [PubMed] [Google Scholar]
  21. 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]
  22. Petersen N. O., Chan S. I. More on the motional state of lipid bilayer membranes: interpretation of order parameters obtained from nuclear magnetic resonance experiments. Biochemistry. 1977 Jun 14;16(12):2657–2667. doi: 10.1021/bi00631a012. [DOI] [PubMed] [Google Scholar]
  23. Rance M., Jeffrey K. R., Tulloch A. P., Butler K. W., Smith I. C. Orientational order of unsaturated lipids in the membranes of Acholeplasma laidlawii as observed by 2H-NMR. Biochim Biophys Acta. 1980 Aug 4;600(2):245–262. doi: 10.1016/0005-2736(80)90430-7. [DOI] [PubMed] [Google Scholar]
  24. Roberts M. F., Bothner-By A. A., Dennis E. A. Magnetic nonequivalence within fatty acyl chains of phospholipids in membrane models: 1H nuclear magnetic resonance studies of the alpha-methylene groups. Biochemistry. 1978 Mar 7;17(5):935–942. doi: 10.1021/bi00598a030. [DOI] [PubMed] [Google Scholar]
  25. Salsbury N. J., Darke A., Chapman D. Deuteron magnetic resonance studies of water associated with phospholipids. Chem Phys Lipids. 1972 Mar;8(2):142–151. doi: 10.1016/0009-3084(72)90026-6. [DOI] [PubMed] [Google Scholar]
  26. Seelig A., Seelig J. Bilayers of dipalmitoyl-3-sn-phosphatidylcholine. Conformational differences between the fatty acyl chains. Biochim Biophys Acta. 1975 Sep 16;406(1):1–5. doi: 10.1016/0005-2736(75)90037-1. [DOI] [PubMed] [Google Scholar]
  27. Seelig A., Seelig J. The dynamic structure of fatty acyl chains in a phospholipid bilayer measured by deuterium magnetic resonance. Biochemistry. 1974 Nov 5;13(23):4839–4845. doi: 10.1021/bi00720a024. [DOI] [PubMed] [Google Scholar]
  28. Seelig J. Deuterium magnetic resonance: theory and application to lipid membranes. Q Rev Biophys. 1977 Aug;10(3):353–418. doi: 10.1017/s0033583500002948. [DOI] [PubMed] [Google Scholar]
  29. Seelig J., Gally G. U., Wohlgemuth R. Orientation and flexibility of the choline head group in phosphatidylcholine bilayers. Biochim Biophys Acta. 1977 Jun 2;467(2):109–119. doi: 10.1016/0005-2736(77)90188-2. [DOI] [PubMed] [Google Scholar]
  30. Seelig J., Seelig A. Lipid conformation in model membranes and biological membranes. Q Rev Biophys. 1980 Feb;13(1):19–61. doi: 10.1017/s0033583500000305. [DOI] [PubMed] [Google Scholar]
  31. Stockton G. W., Polnaszek C. F., Leitch L. C., Tulloch A. P., Smith I. C. A study of mobility and order in model membranes using 2H NMR relaxation rates and quadrupole splittings of specifically deuterated lipids. Biochem Biophys Res Commun. 1974 Sep 23;60(2):844–850. doi: 10.1016/0006-291x(74)90318-0. [DOI] [PubMed] [Google Scholar]
  32. Sundaralingam M. Discussion paper: molecular structures and conformations of the phospholipids and sphingomyelins. Ann N Y Acad Sci. 1972 Jun 20;195:324–355. [PubMed] [Google Scholar]
  33. Sundaralingam M., Jensen L. H. Crystal and molecular structure of a phospholipid component: L-alpha-glycerophosphorylcholine cadmium chloride trihydrate. Science. 1965 Nov 19;150(3699):1035–1036. doi: 10.1126/science.150.3699.1035. [DOI] [PubMed] [Google Scholar]
  34. Vaz M. J., Vaz N. A., Doane J. W., Westerman P. W. Orientational order and rotational diffusion of the head group in the bilayer membrane. A nuclear magnetic resonance study. Biophys J. 1979 Nov;28(2):327–338. doi: 10.1016/S0006-3495(79)85180-2. [DOI] [PMC free article] [PubMed] [Google Scholar]
  35. Westerman P. W., Vaz M. J., Strenk L. M., Doane J. W. Phase transitions in phosphatidylcholine multibilayers. Proc Natl Acad Sci U S A. 1982 May;79(9):2890–2894. doi: 10.1073/pnas.79.9.2890. [DOI] [PMC free article] [PubMed] [Google Scholar]
  36. 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]
  37. Wohlgemuth R., Waespe-Sarcevic N., Seelig J. Bilayers of phosphatidylglycerol. A deuterium and phosphorus nuclear magnetic resonance study of the head-group region. Biochemistry. 1980 Jul 8;19(14):3315–3321. doi: 10.1021/bi00555a033. [DOI] [PubMed] [Google Scholar]

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

RESOURCES