Stereoselective Recognition in Phospholipid Monolayers

  • Edward M. Arnett
  • Jeffrey M. Gold
  • Noel Harvey
  • Eric A. Johnson
  • L. Graham Whitesell
Part of the Advances in Experimental Medicine and Biology book series (AEMB, volume 238)


During the past ten years we have investigated the stereochemistry of intermolecular interactions in monolayers at the air-water interface,1–3 a field which has never been developed explicitly before to our knowledge. Although we demonstrated clear enantiomeric and diastereomeric interactions for a number of chiral surfactants, we found no evidence whatsoever for stereoselective interaction in dipalmitoylphosphatidylcholine (DPPC) monolayers or vesicles by standard monolayer techniques, differential scanning calorimetry or ultra-highfield NMR.4 The present article extends these observations to dimyristoyl- and dilauroylphosphatidylcholine. Results from dynamic surface tension studies are also reported. In no case could chiral recognition be demonstrated using the 95% confidence limit as the criterion.

In our previous study of DPPC mixtures with another chiral surfactant the question arose as to whether chiral interactions could be transmitted through intervening phospholipid molecules.4 This question is addressed by examining the force-area curves for a variety of mixed monolayers composed of chiral surfactants and phospholipids. We conclude that the chiral discrimination observed in some of these mixed monolayers is due to the direct interaction of chiral centers, and not due to the transmission of chirality from one stereocenter to the next through intermediate achiral molecules.

Finally, we will consider the question of why phospholipids, the most ubiquitous of natural chiral surfactants, should show so little chiral discrimination in view of the wide occurrence of high stereoselectivity in many natural processes.


Racemic Mixture Chiral Recognition Film Composition Molecular Area Dynamic Surface Tension 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


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  1. 1.
    E.M. Arnett, J. Chao, B. Kinzig, M. Stewart, and O. Thompson, Chiral Aggregation Phenomena. 1. Acid Dependent Chiral Recognition in a Monolayer, J. Am. Chem. Soc. 100:5575 (1978).CrossRefGoogle Scholar
  2. 2.
    E.M. Arnett, O. Thompson, Chiral Aggregation Phenomena. 2. Evidence for Partial “Two-Dimensional Resolution” in a Chiral Monolayer, J. Am. Chem. Soc. 103:908 (1981).Google Scholar
  3. 3.
    E.M. Arnett, J. Chao, B. Kinzig, M. Stewart, O. Thompson, and R. Verbiar, Chiral Aggregation Phenomena. 3. Chiral Discrimination in Monolayer Packing of N-(α-Methylbenzyl) steramides on Aqueous Acid Subphases: Thermodynamic Behavior, J. Am. Chem. Soc. 104:389 (1982).CrossRefGoogle Scholar
  4. 4.
    E.M. Arnett, J. Gold, Chiral Aggregation Phenomena. 4. A Search for Stereospecific Interactions between Highly Purified Enantiomeric and Racemic Dipalmitoyl Phosphatidyl-cholines and Other Chiral Surfactants in Monolayers, Vesicles, and Gels, J. Am. Chem. Soc. 104:636 (1982).CrossRefGoogle Scholar
  5. 5.
    M.C. Phillips, D. Chapman, Monolayer Characteristics of Saturated 1,2-Diacyl Phosphatidylcholines (Lecithins) and Phosphatidylethanolamines at the Air-Water Interface, Biochim. Biophys. Acta 163:301 (1968).CrossRefGoogle Scholar
  6. 6.
    J. Minones, M.I. Sandez Macho, E. Iribarnegaray Jado, P. Sanz Pedro, Effect of Silicic Acid on Phospholipid Monolayers. Part I. Interaction with Synthetic Lecithins, Med. Segur. Trab. 27:40 (1979).Google Scholar
  7. 7.
    L.L.M. Van Deenen, V.M.T. Hautsmuller, G. H. deHaas, and F. Muldler, Monomolecular Layers of Synthetic Phosphatides, J. Pharm. Pharmacol. 14:429 (1962).CrossRefGoogle Scholar
  8. 8.
    D.A. Cadenhead, R.J. Remchak, and M.C. Phillips, Monolayer Characteristics of 1,2-Dimyristin, l,2-Dimyristoyl-3-Cephalin and 1,2-Dimristoyl-3-Lecithin at the Air-Water Interface, Kolloid Z. Z. Polym. 220:59 (1967).CrossRefGoogle Scholar
  9. 9.
    R.M. Weis, H.M. McConnell, Two-Dimensional Chiral Crystals of Phospholipid, Nature 310:47 (1984).CrossRefGoogle Scholar
  10. 10.
    N.L. Gershfeld, Film Balance and the Evaluation of Intermolecular Energies in Monolayers, in: “Techniques of Surface and Colloid Chemistry and Physics”, R.J. Good, R.R. Stromberg, and R.L. Patrick, eds., Marcel Dekker, Inc., New York, (1972).Google Scholar
  11. 11.
    O. Thompson, Doctoral Dissertation, University of Pittsburgh, 1982.Google Scholar
  12. 12.
    J.T. Mason, A.V. Broccoli, and C.H. Huang, A Method for the Synthesis of Isomerically Pure Saturated Mixed-Chain Phosphatidylcholines, Anal. Biochem. 113:96 (1981).CrossRefGoogle Scholar
  13. 13.
    R. Aneja, J.S. Chada, A Total Synthesis of Phosphatidylcholines, Biochem. Biophys. Acta 248:455 (1971).CrossRefGoogle Scholar
  14. 14.
    E. Johnson, Doctoral Dissertation, Duke University, 1985.Google Scholar
  15. 15.
    Z. Selinger, Y. Lapidot, Synthesis of Fatty Acid Anhydrides by Reaction with Dicyclohexylcarbodiimide, J. Lipid Res. 7:174 (1966).PubMedGoogle Scholar
  16. 16.
    G.L. Gaines, “Insoluble Monolayers at the Liquid-Gas Interface”, Interscience, New York (1966).Google Scholar
  17. 17.
    E.M. Arnett, E.A. Johnson, D. Mirajovsky and R. Verbiar, in preparation.Google Scholar
  18. 18.
    D.A. Cadenhead, Monomolecular Films at the Air-Water Interface: Some Practical Applications, Industr. Eng. Chem. 61:22 (1969).CrossRefGoogle Scholar
  19. 19.
    J.M. Gold, Doctoral Dissertation, Duke University (1982).Google Scholar
  20. 20.
    G.L. Jendrasiak, The Interaction of Iodine with Lecithin Micelles, Chem. Phys. Lipids 4:85 (1970).CrossRefGoogle Scholar
  21. 21.
    E.M. Arnett and P. Zingg, Chiral Discrimination in the Energetics of Ion Aggregation, J. Am. Chem. Soc. 103:1221 (1981).CrossRefGoogle Scholar
  22. 22.
    R. Defay, I. Pregogine, A. Bellemans and D. Everette, “Surface Tension and Adsorption”, Wiley, New York (1966) pp. 74–78.Google Scholar
  23. 23.
    D.J. Crisp, “Surface Chemistry,” Suppl. Research, London (1949) pp. 17, 23.Google Scholar
  24. 24.
    E.M. Arnett, N. Harvey and L.G. Whitesell, unpublished data.Google Scholar

Copyright information

© Plenum Press, New York 1988

Authors and Affiliations

  • Edward M. Arnett
    • 1
  • Jeffrey M. Gold
    • 1
  • Noel Harvey
    • 1
  • Eric A. Johnson
    • 1
  • L. Graham Whitesell
    • 1
  1. 1.Department of ChemistryDuke UniversityDurhamUSA

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