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Electrolyte effects on the chiral induction and on its temperature dependence in a chiral nematic lyotropic liquid crystal

Dawin, Ute C. and Osipov, Mikhail A. and Giesselmann, F. (2010) Electrolyte effects on the chiral induction and on its temperature dependence in a chiral nematic lyotropic liquid crystal. Journal of Physical Chemistry B, 114 (32). pp. 10327-10336. ISSN 1520-6106

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Abstract

Abstract We present a study on the effect of added CsCl and of temperature variation on the chiral induction in a chiral nematic lyotropic liquid crystal (LC) composed of the surfactant cesium perfluorooctanoate (CsPFO), water, and the chiral dopant d-Leucine (d-Leu). The chiral induction was measured as the helical pitch P. The role of the additives CsCl and d-Leu on the phase behavior is investigated and discussed. The thermal stabilization effect of CsCl is shown to lead to an apparent salt effect on the pitch when the pitch is compared at a constant temperature. This apparent effect is removed by comparing the pitch measured for different salt concentrations at a temperature relative to the phase-transition temperatures; thus, the real salt effect on the pitch is described. High salt concentrations are shown to increase the pitch, that is, hinder the chiral induction. The effect is discussed in terms of a decreased solubilization of the amphiphilic chiral solute d-Leu in the micelles due to the salt-induced screening of the surfactant head groups and the consequential denser packing of the surfactants. The temperature variation of the pitch is investigated for all CsCl concentrations and is found to be essentially independent of the salt concentration. The temperature variation is analyzed and discussed in the context of a theoretical model taking into account specific properties of lyotropic liquid crystals. A hyperbolic decrease of the pitch is found with increasing temperature, which is known, from thermotropic liquid crystals, to stem from pretransitional critical fluctuations close to the lamellar phase. However, the experimental data confirmed the theoretical prediction that, at high temperature, that is, far away from the transition into the lamellar phase, the pitch is characterized by a linear temperature dependence which is determined by a combination of steric and dispersion chiral interactions. The parameters of the theoretical expression for the pitch have been determined by fitting the experimental data. The analysis of the salt concentration dependence of these parameters indicates that the chiral induction mechanism of d-Leu is dominated by chiral steric interactions.