Abstract
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.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
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).
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).
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).
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).
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).
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).
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).
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).
R.M. Weis, H.M. McConnell, Two-Dimensional Chiral Crystals of Phospholipid, Nature 310:47 (1984).
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).
O. Thompson, Doctoral Dissertation, University of Pittsburgh, 1982.
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).
R. Aneja, J.S. Chada, A Total Synthesis of Phosphatidylcholines, Biochem. Biophys. Acta 248:455 (1971).
E. Johnson, Doctoral Dissertation, Duke University, 1985.
Z. Selinger, Y. Lapidot, Synthesis of Fatty Acid Anhydrides by Reaction with Dicyclohexylcarbodiimide, J. Lipid Res. 7:174 (1966).
G.L. Gaines, “Insoluble Monolayers at the Liquid-Gas Interface”, Interscience, New York (1966).
E.M. Arnett, E.A. Johnson, D. Mirajovsky and R. Verbiar, in preparation.
D.A. Cadenhead, Monomolecular Films at the Air-Water Interface: Some Practical Applications, Industr. Eng. Chem. 61:22 (1969).
J.M. Gold, Doctoral Dissertation, Duke University (1982).
G.L. Jendrasiak, The Interaction of Iodine with Lecithin Micelles, Chem. Phys. Lipids 4:85 (1970).
E.M. Arnett and P. Zingg, Chiral Discrimination in the Energetics of Ion Aggregation, J. Am. Chem. Soc. 103:1221 (1981).
R. Defay, I. Pregogine, A. Bellemans and D. Everette, “Surface Tension and Adsorption”, Wiley, New York (1966) pp. 74–78.
D.J. Crisp, “Surface Chemistry,” Suppl. Research, London (1949) pp. 17, 23.
E.M. Arnett, N. Harvey and L.G. Whitesell, unpublished data.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1988 Plenum Press, New York
About this chapter
Cite this chapter
Arnett, E.M., Gold, J.M., Harvey, N., Johnson, E.A., Whitesell, L.G. (1988). Stereoselective Recognition in Phospholipid Monolayers. In: Gaber, B.P., Schnur, J.M., Chapman, D. (eds) Biotechnological Applications of Lipid Microstructures. Advances in Experimental Medicine and Biology, vol 238. Springer, New York, NY. https://doi.org/10.1007/978-1-4684-7908-9_3
Download citation
DOI: https://doi.org/10.1007/978-1-4684-7908-9_3
Published:
Publisher Name: Springer, New York, NY
Print ISBN: 978-1-4684-7910-2
Online ISBN: 978-1-4684-7908-9
eBook Packages: Springer Book Archive