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Molecular Origin of the Intrinsic Bending Force for Helical Morphology Observed in Chiral Amphiphilic Assemblies: Concentration and Size Dependence

Nandi, Nilashis and Bagchi, Biman (1996) Molecular Origin of the Intrinsic Bending Force for Helical Morphology Observed in Chiral Amphiphilic Assemblies: Concentration and Size Dependence. In: Journal of American Chemical Society, 118 (45). pp. 11208-11216.

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Official URL: http://pubs.acs.org/doi/abs/10.1021/ja9533757

Abstract

The formation of the helical morphology in monolayers and bilayers of chiral amphiphilic assemblies is believed to be driven at least partly by the interactions at the chiral centers of the amphiphiles. However, a detailed microscopic understanding of these interactions and their relation with the helix formation is still not clear. In this article a study of the molecular origin of the chirality-driven helix formation is presented by calculating, for the first time, the effective pair potential between a pair of chiral molecules. This effective potential depends on the relative sizes of the groups attached to the two chiral centers, on the orientation of the amphiphile molecules, and also on the distance between them. We find that for the mirror-image isomers (in the racemic modification) the minimum energy conformation is a nearly parallel alignment of the molecules. On the other hand, the same for a pair of molecules of one kind of enantiomer favors a tilt angle between them, thus leading to the formation of a helical morphology of the aggregate. The tilt angle is determined by the size of the groups attached to the chiral centers of the pair of molecules considered and in many cases predicted it to be close to 45 degrees. The present study, therefore, provides a molecular origin of the intrinsic bending force, suggested by Helfrich (J. Chem. Phys. 1986, 85, 1085-1087), to be responsible for the formation of helical structure. This effective potential may explain many of the existing experimental results, such as the size and the concentration dependence of the formation of helical morphology. It is further found that the elastic forces can significantly modify the pitch predicted by the chiral interactions alone and that the modified real pitch is close to the experimentally observed value. The present study is expected to provide a starting point for future microscopic studies.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to American Chemical Society.
Department/Centre: Division of Chemical Sciences > Solid State & Structural Chemistry Unit
Date Deposited: 20 Nov 2009 08:47
Last Modified: 13 Apr 2011 08:02
URI: http://eprints.iisc.ernet.in/id/eprint/19214

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