Influence of Specific Anions on the Orientational Ordering of Thermotropic Liquid Crystals at Aqueous Interfaces
Department of Chemical and Biological Engineering, University of Wisconsin-Madison , Madison, Wisconsin 53706, United States.Langmuir (Impact Factor: 4.46). 08/2012; 28(35):12796-805. DOI: 10.1021/la3024293
We report that specific anions (of sodium salts) added to aqueous phases at molar concentrations can trigger rapid, orientational ordering transitions in water-immiscible, thermotropic liquid crystals (LCs; e.g., nematic phase of 4'-pentyl-4-cyanobiphenyl, 5CB) contacting the aqueous phases. Anions classified as chaotropic, specifically iodide, perchlorate, and thiocyanate, cause 5CB to undergo continuous, concentration-dependent transitions from planar to homeotropic (perpendicular) orientations at LC-aqueous interfaces within 20 s of addition of the anions. In contrast, anions classified as relatively more kosmotropic in nature (fluoride, sulfate, phosphate, acetate, chloride, nitrate, bromide, and chlorate) do not perturb the LC orientation from that observed without added salts (i.e., planar orientation). Surface pressure-area isotherms of Langmuir films of 5CB supported on aqueous salt solutions reveal ion-specific effects ranking in a manner similar to the LC ordering transitions. Specifically, chaotropic salts stabilized monolayers of 5CB to higher surface pressures and areal densities (12.6 mN/m at 27 Å(2)/molecule for NaClO(4)) and thus smaller molecular tilt angles (30° from the surface normal for NaClO(4)) than kosmotropic salts (5.0 mN/m at 38 Å(2)/molecule with a corresponding tilt angle of 53° for NaCl). These results and others reported herein suggest that anion-specific interactions with 5CB monolayers lead to bulk LC ordering transitions. Support for the proposition that these ion-specific interactions involve the nitrile group was obtained by using a second LC with nitrile groups (E7; ion-specific effects similar to 5CB were observed) and a third LC with fluorine-substituted aromatic groups (TL205; weak dipole and no ion-specific effects were measured). Finally, we also establish that anion-induced orientational transitions in micrometer-thick LC films involve a change in the easy axis of the LC. Overall, these results provide new insights into ionic phenomena occurring at LC-aqueous interfaces, and reveal that the long-range ordering of LC oils can amplify ion-specific interactions at these interfaces into macroscopic ordering transitions.
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ABSTRACT: This Instructional Review describes methods and underlying principles that can be used to characterize both the orientations assumed spontaneously by liquid crystals (LCs) at interfaces and the strength with which the LCs are held in those orientations (so-called anchoring energies). The application of these methods to several different classes of LC interfaces is described, including solid and aqueous interfaces as well as planar and non-planar interfaces (such as those that define a LC-in-water emulsion droplet). These methods, which enable fundamental studies of the ordering of LCs at polymeric, chemically-functionalized and biomolecular interfaces, are described in this article at a level that can be easily understood by a non-expert reader such as an undergraduate or graduate student. We focus on optical methods because they are based on instrumentation that is found widely in research and teaching laboratories.
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ABSTRACT: Aptamer-ligand binding events, involving small molecule targets, at a surfactant-laden aqueous/liquid crystal (LC) interface were found to trigger a LC reorientation that can be observed in real-time using polarized light. The response was both sensitive and selective: reorientation was observed at target concentrations on the order of the aptamer dissociation constant, but no response was observed in control experiments with target analogues. Circular dichroism and resonance energy transfer experiments suggested that the LC reorientation was due to a conformational change of the aptamer upon target binding. Specifically, under conditions where aptamer-ligand binding induced a conformational change from a relaxed random coil to more intricate secondary structures (e.g., double helix, G-quadruplex), a transition from planar to homeotropic LC orientation was observed. These observations suggest the potential for a label-free LC-based detection system that can simultaneously respond to the presence of both small molecules and nucleic acids.
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ABSTRACT: We report the interactions of a mesogenic molecule, 4'-octyl-4-biphenyl-carbonitrile (8CB), with some cations (Na(+), Cu(2+), Ni(2+), La(3+) and Al(3+)) dissolved in the aqueous subphase. Surface manometry studies show that the di- (Ni(2+) and Cu(2+)) and trivalent (La(3+)) ions promote condensation in the area per molecule and enhance the stability of the monolayer. This is inferred from the increase in the values of collapse pressure and the compression elastic modulus. The specific ion effect is seen between perchlorate and chloride anions with respect to the Al(3+) cation. The presence of monovalent ions (Na(+)) in the subphase does not influence the isotherm of 8CB. However, in this case, with pH (>6), the isotherm shifts to a higher area per molecule. The excess Gibbs free energy calculated for the 8CB monolayer indicates repulsive interaction for monovalent ions and attractive interaction for multivalent ions in the subphase. Kinetic studies of the monolayer in an ion-enriched subphase have yielded an additional characteristic time constant indicative of reorganization of the monolayer. Ellipsometric adsorption isotherm measurements carried out for representative ions show a reduction in the value of the ellipsometric angle with increasing valency. Our studies indicate that the interaction of ions with the 8CB monolayer at the air-electrolyte interface can be promoted by choosing cations of higher valency and anions of larger size, higher polarizability and chaotropic nature. These factors play an important role and can potentially affect the anchoring transition.
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