Nematic and columnar phases of lyotropic chromonic liquid crystals (LCLCs) have been long studied for their fundamental and applied prospects in material science and medical diagnostics. LCLC phases represent different self-assembled states of disc-shaped molecules, held together by noncovalent interactions that lead to highly sensitive concentration and temperature dependent properties. Yet, microscale insights into confined LCLCs, specifically in the context of confinement geometry and surface properties, are lacking. Here, we report the emergence of time dependent textures in static disodium chromoglycate (DSCG) solutions, confined in PDMS-based microfluidic devices. We use a combination of soft lithography, surface characterization and polarized optical imaging to generate and analyze the confinement-induced LCLC textures, and demonstrate that over time, herringbone and spherulite textures emerge due to spontaneous nematic (N) to columnar M-phase transition, propagating from the LCLC-PDMS interface into the LCLC bulk. By varying the confinement geometry, anchoring conditions and the initial DSCG concentration, we can systematically tune the temporal dynamics of the N to M-phase transition and textural behaviour of the confined LCLC. Since static molecular states register the initial conditions for LC flows, the time dependent boundary and bulk conditions reported here suggest that the local surface-mediated dynamics could be central in understanding LCLC flows, and in turn, the associated transport properties of this versatile material.
We propose lyotropic chromonic liquid crystals (LCLCs) as a distinct class of materials for organic electronics. In water, the chromonic molecules stack on top of each other into elongated aggregates that form orientationally ordered phases. The aligned aggregated structure is preserved when the material is deposited onto a substrate and dried. The dried LCLC films show a strongly anisotropic electric conductivity of semiconductor type. The field-effect carrier mobility measured along the molecular aggregates in unoptimized films of LCLC V20 is 0.03 cm^2 V^(-1) s^(-1). Easy processibility, low…
An experimental and theoretical study of lyotropic chromonic liquid crystals (LCLCs) confined in cylinders with degenerate planar boundary conditions elucidates LCLC director configurations. When the Frank saddle-splay modulus is more than twice the twist modulus, the ground state adopts an inhomogeneous escaped-twisted configuration. Analysis of the configuration yields a large saddle-splay modulus, which violates Ericksen inequalities but not thermodynamic stability. Lastly, we observe point defects between opposite-handed domains and explain a preference for point defects over domain walls.
The surface alignment of lyotropic chromonic liquid crystals (LCLCs) can be not only planar (tangential) but also homeotropic, with self-assembled aggregates perpendicular to the substrate, as demonstrated by mapping optical retardation and by three-dimensional imaging of the director field. With time, the homeotropic nematic undergoes a transition into a tangential state. The anchoring transition is discontinuous and can be described by a double-well anchoring potential with two minima corresponding to tangential and homeotropic orientation.
Using dynamic light scattering, we measure for the first time the temperature-dependent elastic moduli and associated orientational viscosity coefficients of the nematic phase in a self-assembled lyotropic chromonic liquid crystal. The bend K3 and splay K1 moduli are an order of magnitude higher than the twist K2 constant. The ratio K3/K1 shows an anomalous increase with temperature; we attribute this to the shortening of the aggregates as temperature increases. The viscosity coefficients also show a significant anisotropy, as well as a strong temperature dependence; in particular, the bend vi…
We have developed a class of idealized models of chromonic molecules which are miscible in water, but which can form aggregates which in turn organize into lyotropic liquid crystal (LC) phases. By carrying out Monte Carlo simulation in a binary mixture of model chromonic and water molecules, we have studied the effect of concentration and molecular shape on the nature of resulting mesophases. We have also computed the free energy associated with the formation of chromonic columnar aggregates by umbrella sampling. Our free energy computation helps us to verify the isodesmic behavior which is ch…
Nuclei of ordered materials emerging from the isotropic state usually show a shape topologically equivalent to a sphere; the well-known examples are crystals and nematic liquid crystal droplets. In this work, we explore experimentally and theoretically the nuclei of columnar lyotropic chromonic liquid crystal coexisting with the isotropic phase that are toroidal in shape. The geometry of toroids depends strongly on the molecular concentrations and presence of a crowding agent, polyethylene glycol. High concentrations result in thick toroids with small central holes, while low concentrations yi…
A lyotropic chromonic liquid crystal (LCLC) is an orientationally ordered system made by self-assembled aggregates of charged organic molecules in water, bound by weak non-covalent attractive forces and stabilized by electrostatic repulsions. We determine how the ionic content of the LCLC, namely the presence of mono- and divalent salts and pH enhancing agent, alter the viscoelastic properties of the LCLC. Aqueous solutions of the dye Sunset Yellow with a uniaxial nematic order are used as an example. By applying a magnetic field to impose orientational deformations, we measure the splay $K_1$…
Magnetically controlled double-twist director configuration of lyotropic chromonic liquid crystals in cylinders: Energetics, topological defects, and instability
Detection of chiral molecules requires amplification of chirality to measurable levels. Typically, amplification mechanisms are considered at the microscopic scales of individual molecules and their aggregates. Here we demonstrate chirality amplification and visualization of structural handedness in water solutions of organic molecules that extends over the scale of many micrometers. The mechanism is rooted in the long-range elastic nature of orientational order in lyotropic chromonic liquid crystals (LCLCs) formed in water solutions of achiral disc-like molecules. The nematic LCLC coexists wi…
We study the aggregation phenomenon in lyotropic chromonic liquid crystals as the molecular concentration changes and condensing agents are added into the system. Using properties of the critical points of the Oseen-Frank energy of a nematic liquid crystal, combined with the geometric constraints of the hexagonal columnar chromonic phases, we show that the minimizers of the total energy are topologically equivalent to tori, in agreement with available experimental evidence on chromonic liquid crystals and DNA condensates, in viral capsids as well as in free solution. We model the system as bi-…
Lyotropic chromonic liquid crystals (LCLCs) represent aqueous dispersions of organic disk-like molecules that form cylindrical aggregates. Despite the growing interest in these materials, their flow behavior is poorly understood. Here, we explore the effect of shear on dynamic structures of the nematic LCLC, formed by 14wt ${\%}$ water dispersion of disodium cromoglycate (DSCG). We employ in-situ polarizing optical microscopy (POM) and small-angle and wide-angle X-ray scattering (SAXS/WAXS) to obtain independent and complementary information on the director structures over a wide range of shea…
We explore micropatterned director structures of aqueous lyotropic chromonic liquid crystal (LCLC) films created on square lattice cylindrical-micropost substrates. The structures are manipulated by modulating the LCLC mesophases and their elastic properties via concentration through drying. Nematic LCLC films exhibit preferred bistable alignment along the diagonals of the micropost lattice. Columnar LCLC films, dried from nematics, form two distinct director and defect configurations: a diagonally aligned director pattern with local squares of defects, and an off-diagonal configuration with z…
We explore the structure of nuclei and topological defects in the first-order phase transition between the nematic (N) and isotropic (I) phases in lyotropic chromonic liquid crystals (LCLCs). The LCLCs are formed by self-assembled molecular aggregates of various lengths and show a broad biphasic region. The defects emerge as a result of two mechanisms. 1) Surface anisotropy mechanism that endows each N nucleus (tactoid) with topological defects thanks to preferential (tangential) orientation of the director at the closed I-N interface, and 2) Kibble mechanism with defects forming when differen…
We use optical and fluorescence microscopy, densitometry, cryo-transmission electron microscopy (cryo-TEM), spectroscopy, and synchrotron X-ray scattering, to study the phase behavior of the reversible self-assembled chromonic aggregates of an anionic dye Sunset Yellow (SSY) in aqueous solutions crowded with an electrically neutral polymer polyethylene glycol (PEG) and doped with the salt NaCl. PEG causes the isotropic SSY solutions to condense into a liquid-crystalline region with a high concentration of SSY aggregates, coexisting with a PEG-rich isotropic (I) region. PEG added to the homogen…
Chromonic liquid crystals constitute a novel lyotropic phase, whose elastic properties have so far been modeled within the classical Oseen-Frank theory, provided that the twist constant is assumed to be considerably smaller than the saddle-splay constant, in violation of one Ericksen inequality. This paper shows that paradoxical consequences follow from such a violation for droplets of these materials surrounded by an isotropic fluid. For example, tactoids with a degenerate planar anchoring simply disintegrate indefinitely in myriads of smaller ones.
