Skip to main content
Biophysical Journal logoLink to Biophysical Journal
. 1995 Aug;69(2):460–469. doi: 10.1016/S0006-3495(95)79919-2

Effects of chain unsaturation on the equation of state for lipid monolayers at the air-water interface.

S S Feng 1, R C MacDonald 1
PMCID: PMC1236271  PMID: 8527660

Abstract

An equation of state for lipid monolayers at the air-water interface is presented, which takes into account the effects of the conformation and the number and position of double bonds of the hydrocarbon chains. The total Hamiltonian of the monolayer is assumed to consist of three terms. Two of them are calculated exactly within the limitations of the formulation. These are the two-dimensional entropy of mixing of the lipid and water molecules at the surface and the conformational entropy of the chains using a model available from the literature. These two terms give rise to positive surface pressure. The third term, which includes all energies that are not amenable to calculation, was obtained as the difference between the sum of the two calculated terms and experimental data and is found to represent an approximately area-independent tension. The effects of chain unsaturation on the equation of state were modeled in the present theory in two ways; the chain bend caused by cis double bonds increases the minimal molecular area, and the double bond linkage on a chain decreases the degrees of freedom of the chain. Calculations revealed that the former is highly significant whereas the latter is negligible. The deduced equation of state reproduces experimental data with appropriate values for three parameters, which represent the collapse area, the overlap of adjacent chains, and the combined effects of the intra- and intermolecular interactions other than the surface mixing entropy and the chain conformational energy.

Full text

PDF
460

Selected References

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

  1. Berde C. B., Andersen H. C., Hudson B. S. A theory of the effects of head-group structure and chain unsaturation on the chain melting transition of phospholipid dispersions. Biochemistry. 1980 Sep 2;19(18):4279–4293. doi: 10.1021/bi00559a021. [DOI] [PubMed] [Google Scholar]
  2. Coolbear K. P., Berde C. B., Keough K. M. Gel to liquid-crystalline phase transitions of aqueous dispersions of polyunsaturated mixed-acid phosphatidylcholines. Biochemistry. 1983 Mar 15;22(6):1466–1473. doi: 10.1021/bi00275a022. [DOI] [PubMed] [Google Scholar]
  3. Dill K. A., Stigter D. Lateral interactions among phosphatidylcholine and phosphatidylethanolamine head groups in phospholipid monolayers and bilayers. Biochemistry. 1988 May 3;27(9):3446–3453. doi: 10.1021/bi00409a048. [DOI] [PubMed] [Google Scholar]
  4. Evans R. W., Tinoco J. Monolayers of sterols and phosphatidylcholines containing a 20-carbon chain. Chem Phys Lipids. 1978 Oct;22(3):207–220. doi: 10.1016/0009-3084(78)90027-0. [DOI] [PubMed] [Google Scholar]
  5. Evans R. W., Williams M. A., Tinoco J. Surface areas of 1-palmitoyl phosphatidylcholines and their interactions with cholesterol. Biochem J. 1987 Jul 15;245(2):455–462. doi: 10.1042/bj2450455. [DOI] [PMC free article] [PubMed] [Google Scholar]
  6. Fattal D. R., Ben-Shaul A. Mean-field calculations of chain packing and conformational statistics in lipid bilayers: comparison with experiments and molecular dynamics studies. Biophys J. 1994 Sep;67(3):985–995. [PMC free article] [PubMed] [Google Scholar]
  7. Jacobs R. E., Hudson B., Andersen H. C. A theory of the chain melting phase transition of aqueous phospholipid dispersions. Proc Natl Acad Sci U S A. 1975 Oct;72(10):3993–3997. doi: 10.1073/pnas.72.10.3993. [DOI] [PMC free article] [PubMed] [Google Scholar]
  8. Janiak M. J., Small D. M., Shipley G. G. Nature of the Thermal pretransition of synthetic phospholipids: dimyristolyl- and dipalmitoyllecithin. Biochemistry. 1976 Oct 19;15(21):4575–4580. doi: 10.1021/bi00666a005. [DOI] [PubMed] [Google Scholar]
  9. MacDonald R. C., Simon S. A. Lipid monolayer states and their relationships to bilayers. Proc Natl Acad Sci U S A. 1987 Jun;84(12):4089–4093. doi: 10.1073/pnas.84.12.4089. [DOI] [PMC free article] [PubMed] [Google Scholar]
  10. Mingins J., Stigter D., Dill K. A. Phospholipid interactions in model membrane systems. I. Experiments on monolayers. Biophys J. 1992 Jun;61(6):1603–1615. doi: 10.1016/S0006-3495(92)81964-1. [DOI] [PMC free article] [PubMed] [Google Scholar]
  11. Möhwald H. Phospholipid and phospholipid-protein monolayers at the air/water interface. Annu Rev Phys Chem. 1990;41:441–476. doi: 10.1146/annurev.pc.41.100190.002301. [DOI] [PubMed] [Google Scholar]
  12. Pearce L. L., Harvey S. C. Langevin dynamics studies of unsaturated phospholipids in a membrane environment. Biophys J. 1993 Sep;65(3):1084–1092. doi: 10.1016/S0006-3495(93)81143-3. [DOI] [PMC free article] [PubMed] [Google Scholar]
  13. Schindler H. Exchange and interactions between lipid layers at the surface of a liposome solution. Biochim Biophys Acta. 1979 Aug 7;555(2):316–336. doi: 10.1016/0005-2736(79)90171-8. [DOI] [PubMed] [Google Scholar]
  14. Schindler H. Formation of planar bilayers from artificial or native membrane vesicles. FEBS Lett. 1980 Dec 15;122(1):77–79. doi: 10.1016/0014-5793(80)80405-4. [DOI] [PubMed] [Google Scholar]
  15. Stigter D., Mingins J., Dill K. A. Phospholipid interactions in model membrane systems. II. Theory. Biophys J. 1992 Jun;61(6):1616–1629. doi: 10.1016/S0006-3495(92)81965-3. [DOI] [PMC free article] [PubMed] [Google Scholar]
  16. Szleifer I, I, Kramer D, Ben-Shaul A, Roux D, Gelbart WM. Curvature elasticity of pure and mixed surfactant films. Phys Rev Lett. 1988 May 9;60(19):1966–1969. doi: 10.1103/PhysRevLett.60.1966. [DOI] [PubMed] [Google Scholar]
  17. Tardieu A., Luzzati V., Reman F. C. Structure and polymorphism of the hydrocarbon chains of lipids: a study of lecithin-water phases. J Mol Biol. 1973 Apr 25;75(4):711–733. doi: 10.1016/0022-2836(73)90303-3. [DOI] [PubMed] [Google Scholar]
  18. Wolfe D. H., Brockman H. L. Regulation of the surface pressure of lipid monolayers and bilayers by the activity of water: derivation and application of an equation of state. Proc Natl Acad Sci U S A. 1988 Jun;85(12):4285–4289. doi: 10.1073/pnas.85.12.4285. [DOI] [PMC free article] [PubMed] [Google Scholar]

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

RESOURCES