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. 2002 Aug;83(2):977–984. doi: 10.1016/s0006-3495(02)75223-5

The effects of acyl chain length and saturation of diacylglycerols and phosphatidylcholines on membrane monolayer curvature.

Joseph A Szule 1, Nola L Fuller 1, R Peter Rand 1
PMCID: PMC1302201  PMID: 12124279

Abstract

The second messenger, diacylglycerol (DAG), introduces negative curvature in phospholipid monolayers and strongly induces the lamellar (L(alpha)) to reverse hexagonal (H(II)) phase transition. The chain lengths and degree of unsaturation of symmetric DAGs influence this effect. Within dioleoylphosphatidylcholine (DOPC) monolayers, the apparent spontaneous radius of curvature (R(0)) of the short, saturated dicaprylglycerol (C10-DCG) itself was determined to be -13.3 A, compared with an R(0) value of -10.1 A for the long, di-monounsaturated dioleoylglycerol (C18-DOG). Such increased length and unsaturation of the DAG acyl chains produces this small change. Di-saturated phosphatidylcholines (PCs) with equal length chains (from C10-C18) with 25 mol % DOG do not form the H(II) phase, even under the unstressed conditions of excess water and alkane. Di-unsaturated PCs with equal chain length (from C14-C18) with 25 mol % DOG do form the H(II) phase. Asymmetric chained PCs (position 1 saturated with varying lengths, position 2 differentially unsaturated with varying lengths) all form the H(II) phase in the presence of 25 mol % DOG. As a general rule for PCs, their unsaturation is critical for the induction of the H(II) phase by DOG. The degree of curvature stress induced by the second messenger DOG in membranes, and any protein that might be affected by it, would appear to depend on chain unsaturation of neighboring PCs.

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Selected References

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

  1. Bolen E. J., Sando J. J. Effect of phospholipid unsaturation on protein kinase C activation. Biochemistry. 1992 Jun 30;31(25):5945–5951. doi: 10.1021/bi00140a034. [DOI] [PubMed] [Google Scholar]
  2. Chen Z., Rand R. P. Comparative study of the effects of several n-alkanes on phospholipid hexagonal phases. Biophys J. 1998 Feb;74(2 Pt 1):944–952. doi: 10.1016/S0006-3495(98)74017-2. [DOI] [PMC free article] [PubMed] [Google Scholar]
  3. Chen Z., Rand R. P. The influence of cholesterol on phospholipid membrane curvature and bending elasticity. Biophys J. 1997 Jul;73(1):267–276. doi: 10.1016/S0006-3495(97)78067-6. [DOI] [PMC free article] [PubMed] [Google Scholar]
  4. Chernomordik L., Kozlov M. M., Zimmerberg J. Lipids in biological membrane fusion. J Membr Biol. 1995 Jul;146(1):1–14. doi: 10.1007/BF00232676. [DOI] [PubMed] [Google Scholar]
  5. Cullis P. R., de Kruijff B. Lipid polymorphism and the functional roles of lipids in biological membranes. Biochim Biophys Acta. 1979 Dec 20;559(4):399–420. doi: 10.1016/0304-4157(79)90012-1. [DOI] [PubMed] [Google Scholar]
  6. Das S., Rand R. P. Modification by diacylglycerol of the structure and interaction of various phospholipid bilayer membranes. Biochemistry. 1986 May 20;25(10):2882–2889. doi: 10.1021/bi00358a022. [DOI] [PubMed] [Google Scholar]
  7. Go M., Sekiguchi K., Nomura H., Kikkawa U., Nishizuka Y. Further studies on the specificity of diacylglycerol for protein kinase C activation. Biochem Biophys Res Commun. 1987 Apr 29;144(2):598–605. doi: 10.1016/s0006-291x(87)80008-6. [DOI] [PubMed] [Google Scholar]
  8. Goldberg E. M., Zidovetzki R. Effects of dipalmitoylglycerol and fatty acids on membrane structure and protein kinase C activity. Biophys J. 1997 Nov;73(5):2603–2614. doi: 10.1016/S0006-3495(97)78290-0. [DOI] [PMC free article] [PubMed] [Google Scholar]
  9. Gruner S. M. Intrinsic curvature hypothesis for biomembrane lipid composition: a role for nonbilayer lipids. Proc Natl Acad Sci U S A. 1985 Jun;82(11):3665–3669. doi: 10.1073/pnas.82.11.3665. [DOI] [PMC free article] [PubMed] [Google Scholar]
  10. Heimburg T., Würz U., Marsh D. Binary phase diagram of hydrated dimyristoylglycerol-dimyristoylphosphatidylcholine mixtures. Biophys J. 1992 Nov;63(5):1369–1378. doi: 10.1016/S0006-3495(92)81714-9. [DOI] [PMC free article] [PubMed] [Google Scholar]
  11. Helfrich P., Jakobsson E. Calculation of deformation energies and conformations in lipid membranes containing gramicidin channels. Biophys J. 1990 May;57(5):1075–1084. doi: 10.1016/S0006-3495(90)82625-4. [DOI] [PMC free article] [PubMed] [Google Scholar]
  12. Helfrich W. Elastic properties of lipid bilayers: theory and possible experiments. Z Naturforsch C. 1973 Nov-Dec;28(11):693–703. doi: 10.1515/znc-1973-11-1209. [DOI] [PubMed] [Google Scholar]
  13. Holub B. J., Kuksis A., Thompson W. Molecular species of mono-, di-, and triphosphoinositides of bovine brain. J Lipid Res. 1970 Nov;11(6):558–564. [PubMed] [Google Scholar]
  14. Huang H. W. Deformation free energy of bilayer membrane and its effect on gramicidin channel lifetime. Biophys J. 1986 Dec;50(6):1061–1070. doi: 10.1016/S0006-3495(86)83550-0. [DOI] [PMC free article] [PubMed] [Google Scholar]
  15. Jiménez-Monreal A. M., Villalaín J., Aranda F. J., Gómez-Fernández J. C. The phase behavior of aqueous dispersions of unsaturated mixtures of diacylglycerols and phospholipids. Biochim Biophys Acta. 1998 Aug 14;1373(1):209–219. doi: 10.1016/s0005-2736(98)00106-0. [DOI] [PubMed] [Google Scholar]
  16. LUZZATI V., HUSSON F. The structure of the liquid-crystalline phasis of lipid-water systems. J Cell Biol. 1962 Feb;12:207–219. doi: 10.1083/jcb.12.2.207. [DOI] [PMC free article] [PubMed] [Google Scholar]
  17. Leikin S., Kozlov M. M., Fuller N. L., Rand R. P. Measured effects of diacylglycerol on structural and elastic properties of phospholipid membranes. Biophys J. 1996 Nov;71(5):2623–2632. doi: 10.1016/S0006-3495(96)79454-7. [DOI] [PMC free article] [PubMed] [Google Scholar]
  18. Lewis R. N., Mannock D. A., McElhaney R. N., Turner D. C., Gruner S. M. Effect of fatty acyl chain length and structure on the lamellar gel to liquid-crystalline and lamellar to reversed hexagonal phase transitions of aqueous phosphatidylethanolamine dispersions. Biochemistry. 1989 Jan 24;28(2):541–548. doi: 10.1021/bi00428a020. [DOI] [PubMed] [Google Scholar]
  19. López-García F., Villalaín J., Gómez-Fernández J. C., Quinn P. J. The phase behavior of mixed aqueous dispersions of dipalmitoyl derivatives of phosphatidylcholine and diacylglycerol. Biophys J. 1994 Jun;66(6):1991–2004. doi: 10.1016/S0006-3495(94)80992-0. [DOI] [PMC free article] [PubMed] [Google Scholar]
  20. Marignani P. A., Epand R. M., Sebaldt R. J. Acyl chain dependence of diacylglycerol activation of protein kinase C activity in vitro. Biochem Biophys Res Commun. 1996 Aug 14;225(2):469–473. doi: 10.1006/bbrc.1996.1196. [DOI] [PubMed] [Google Scholar]
  21. Mori T., Takai Y., Yu B., Takahashi J., Nishizuka Y., Fujikura T. Specificity of the fatty acyl moieties of diacylglycerol for the activation of calcium-activated, phospholipid-dependent protein kinase. J Biochem. 1982 Feb;91(2):427–431. doi: 10.1093/oxfordjournals.jbchem.a133714. [DOI] [PubMed] [Google Scholar]
  22. Nielsen C., Goulian M., Andersen O. S. Energetics of inclusion-induced bilayer deformations. Biophys J. 1998 Apr;74(4):1966–1983. doi: 10.1016/S0006-3495(98)77904-4. [DOI] [PMC free article] [PubMed] [Google Scholar]
  23. Nishizuka Y. The role of protein kinase C in cell surface signal transduction and tumour promotion. Nature. 1984 Apr 19;308(5961):693–698. doi: 10.1038/308693a0. [DOI] [PubMed] [Google Scholar]
  24. Nozawa Y., Fukushima H., Iida H. Studies on tetrahymena membranes. Modification of surface membrane lipids by replacement of tetrahymanol by exogenous ergosterol in Tetrahymena pyriformis. Biochim Biophys Acta. 1975 Oct 6;406(2):248–263. doi: 10.1016/0005-2736(75)90008-5. [DOI] [PubMed] [Google Scholar]
  25. Ortiz A., Aranda F. J., Villalaín J., San Martín C., Micol V., Gómez-Fernandez J. C. 1,2-Dioleoylglycerol promotes calcium-induced fusion in phospholipid vesicles. Chem Phys Lipids. 1992 Oct;62(3):215–224. doi: 10.1016/0009-3084(92)90058-w. [DOI] [PubMed] [Google Scholar]
  26. Rand R. P., Fuller N. L., Gruner S. M., Parsegian V. A. Membrane curvature, lipid segregation, and structural transitions for phospholipids under dual-solvent stress. Biochemistry. 1990 Jan 9;29(1):76–87. doi: 10.1021/bi00453a010. [DOI] [PubMed] [Google Scholar]
  27. Rand R. P., Fuller N. L. Structural dimensions and their changes in a reentrant hexagonal-lamellar transition of phospholipids. Biophys J. 1994 Jun;66(6):2127–2138. doi: 10.1016/S0006-3495(94)81008-2. [DOI] [PMC free article] [PubMed] [Google Scholar]
  28. Ray T. K., Skipski V. P., Barclay M., Essner E., Archibald F. M. Lipid composition of rat liver plasma membranes. J Biol Chem. 1969 Oct 25;244(20):5528–5536. [PubMed] [Google Scholar]
  29. Roos D. S., Choppin P. W. Biochemical studies on cell fusion. I. Lipid composition of fusion-resistant cells. J Cell Biol. 1985 Oct;101(4):1578–1590. doi: 10.1083/jcb.101.4.1578. [DOI] [PMC free article] [PubMed] [Google Scholar]
  30. Roos D. S., Choppin P. W. Biochemical studies on cell fusion. II. Control of fusion response by lipid alteration. J Cell Biol. 1985 Oct;101(4):1591–1598. doi: 10.1083/jcb.101.4.1591. [DOI] [PMC free article] [PubMed] [Google Scholar]
  31. Rothman J. E., Lenard J. Membrane asymmetry. Science. 1977 Feb 25;195(4280):743–753. doi: 10.1126/science.402030. [DOI] [PubMed] [Google Scholar]
  32. Siegel D. P., Banschbach J., Alford D., Ellens H., Lis L. J., Quinn P. J., Yeagle P. L., Bentz J. Physiological levels of diacylglycerols in phospholipid membranes induce membrane fusion and stabilize inverted phases. Biochemistry. 1989 May 2;28(9):3703–3709. doi: 10.1021/bi00435a012. [DOI] [PubMed] [Google Scholar]
  33. Verkleij A. J., Zwaal R. F., Roelofsen B., Comfurius P., Kastelijn D., van Deenen L. L. The asymmetric distribution of phospholipids in the human red cell membrane. A combined study using phospholipases and freeze-etch electron microscopy. Biochim Biophys Acta. 1973 Oct 11;323(2):178–193. doi: 10.1016/0005-2736(73)90143-0. [DOI] [PubMed] [Google Scholar]
  34. Wieslander A., Rilfors L., Lindblom G. Metabolic changes of membrane lipid composition in Acholeplasma laidlawii by hydrocarbons, alcohols, and detergents: arguments for effects on lipid packing. Biochemistry. 1986 Nov 18;25(23):7511–7517. doi: 10.1021/bi00371a038. [DOI] [PubMed] [Google Scholar]

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