Chromonic liquid crystals are formed by the addition of aromatic molecules such as disodium chromoglycate (cromolyn) to water. In this study, we investigate the addition of salts to the lyotropic nematic phase of cromolyn aqueous solutions. The addition of sodium and potassium salts shifts the isotropic-nematic phase boundary upward by more than 10°C, so that samples that were isotropic at room temperature are transformed into nematic phases. Salt effects are predominantly dictated by the cation, not the anion, and appear to differ based on cation size. In contrast to small, hydrated cations like sodium, large, weakly hydrated cations such as tetraethylammonium and tetrabutylammonium shift the phase boundary downward, thus stabilizing the isotropic phase at the expense of the nematic one. The phase behavior results are highly correlated with viscosity measurements, with an upward shift in the phase boundary correlating with an increase in solution viscosity and vice versa. We also probe the microstructure in cromolyn-salt solutions, both indirectly by small-angle neutron scattering (SANS) and directly by cryo-transmission electron microscopy (cryo-TEM). The cryo-TEM images show the presence of rodlike aggregates that possibly undergo a higher order aggregation into bundles in the presence of salt.

We address a controversial issue regarding the nature of critical behavior in ternary electrolyte solutions of water, 3-methylpyridine, and sodium bromide. Earlier light-scattering studies showed an anomalous critical behavior in this system that was attributed to the formation of a microheterogeneous phase associated with ion-molecule clustering [M.A. Anisimov, J. Jacob, A. Kumar, V.A. Agayan, and J. V. Sengers, Phys. Rev. Lett. 85, 2336 (2000)]], while some other investigators subsequently found this system to exhibit ordinary Ising-like critical behavior. This contradiction forced us to revisit the problem and perform an accurate and comprehensive study of light scattering in this system paying attention to the achievement of thermodynamic equilibrium, hysteresis effects, aging, and prehistory of the samples, and a possible role of impurities. We show that properly aged, equilibrium samples of aqueous solutions of 3-methylpyridine with NaBr exhibit universal Ising-like critical behavior, typical for other aqueous solutions. No evidence for an equilibrium microheterogeneous phase was found. We have been able to reproduce anomalous behavior (similar to that reported initially) in a fast run on a freshly prepared sample. We attribute the observed anomalies to mesoscopic nonequilibrium aggregates, possibly associated with supramolecular restructuring in aqueous solutions. To support this conclusion we performed a study of aqueous solutions of 3-methylpyridine without NaBr and have found long-living nonequilibrium states in aqueous solutions of 3-methylpyridine.

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We have studied isotropic-to-nematic pretransitional fluctuations in an aqueous solution of disodium cromoglycate (cromolyn) by static and dynamic light scattering. Cromolyn is a representative of lyotropic chromonic liquid crystals with building units being elongated rods formed by aggregates of disk-like molecules. By combining light-scattering and viscosity measurements we have determined the correlation length and relaxation time of the orientational order-parameter fluctuations and estimated the size of the cromolyn aggregates. The pretransitional behavior of light scattering does not completely follow the classic Landau-de Gennes model. This feature is most probably associated with the variable length of cromolyn aggregates. We have observed a dramatic increase of the shear viscosity near the transition to the nematic phase, the fact which correlates with the idea of growing supramolecular aggregates. The steep temperature dependence of the viscosity is accompanied by a practically temperature-independent translational diffusion coefficient.