Cover Feature: Chirality Transfer from an Innately Chiral Nanocrystal Core to a Nematic Liquid Crystal 2: Lyotropic Chromonic Liquid Crystals (ChemPhysChem 3/2023)

The importance of and the difference between molecular versus structural core chirality of substances that form nanomaterials, and their ability to transmit and amplify their chirality to and within a surrounding condensed medium is yet to be exactly understood. Here we demonstrate that neat as well as disodium cromoglycate (DSCG) surface-modified cellulose nanocrystals (CNCs) with both molecular and morphological core chirality can induce homochirality in racemic nematic lyotropic chromonic liquid crystal (rac-N-LCLC) tactoids. In comparison to the parent chiral organic building blocks, D-glucose, endowed only with molecular chirality, both CNCs showed a superior chirality transfer ability. Here, particularly the structurally compatible DSCG-modified CNCs prove to be highly effective since the surface DSCG moieties can insert into the DSCG stacks that constitute the racemic tactoids. Overall, this presents a highly efficient pathway for chiral induction in an aqueous medium and thus for understanding the origins of biological homochirality in a suitable experimental system.     

Self-alignment of dye molecules in micelles and lamellae for three-dimensional imaging of lyotropic liquid crystals

We report alignment of anisotropic amphiphilic dye molecules within oblate and prolate anisotropic micelles and lamellae, the basic building blocks of surfactant-based lyotropic liquid crystals. Absorption and fluorescence transition dipole moments of these dye molecules orient either parallel or orthogonal to the liquid crystal director. This alignment enables three-dimensional visualization of director structures and defects in different lyotropic mesophases by means of fluorescence confocal polarizing microscopy and two-photon excitation fluorescence polarizing microscopy. The studied structures include nematic tactoids, Schlieren texture with disclinations in the calamitic nematic phase, oily streaks in the lamellar phase, developable domains in the columnar hexagonal phase, and various types of line defects in the discotic cholesteric phase. Orientational three-dimensional imaging of structures in the lyotropic cholesterics reveals large Burgers vector dislocations in cholesteric layering with singular disclinations in the dislocation cores that are not common for their thermotropic counterparts.     

Condensation of self-assembled lyotropic chromonic liquid crystal sunset yellow in aqueous solutions crowded with polyethylene glycol and doped with salt

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 homogeneous nematic (N) phase causes separation into the coexisting N and I domains; the SSY concentration in the N domains is higher than the original concentration of PEG-free N phase. Finally, addition of PEG to the highly concentrated homogeneous N phase causes separation into the coexisting columnar hexagonal (C) phase and I phase. This behavior can be qualitatively explained by the depletion (excluded volume) effects that act at two different levels: at the level of aggregate assembly from monomers and short aggregates and at the level of interaggregate packing. We also show a strong effect of a monovalent salt NaCl on phase diagrams that is different for high and low concentrations of SSY. Upon the addition of salt, dilute I solutions of SSY show appearance of the condensed N domains, but the highly concentrated C phase transforms into a coexisting I and N domains. We suggest that the salt-induced screening of electric charges at the surface of chromonic aggregates leads to two different effects: (a) increase of the scission energy and the contour length of aggregates and (b) decrease of the persistence length of SSY aggregates.     

Twist viscosities and flow alignment of biaxial nematic liquid crystal phases of a soft ellipsoid-string fluid studied by molecular dynamics simulation

We have calculated the twist viscosity and the alignment angle between the director and the stream lines in shear flow of a liquid crystal model system, which forms biaxial nematic liquid crystals, as functions of the density, from the Green-Kubo relations by equilibrium molecular dynamics simulation and by a nonequilibrium molecular dynamics algorithm, where a torque conjugate to the director angular velocity is applied to rotate the director. The model system consists of a soft ellipsoid-string fluid where the ellipsoids interact according a repulsive version of the Gay-Berne potential. Four different length-to-width-to-breadth ratios have been studied. On compression, this system forms discotic or calamitic uniaxial nematic phases depending on the dimensions of the molecules, and on further compression a biaxial nematic phase is formed. In the uniaxial nematic phase there is one twist viscosity and one alignment angle. In the biaxial nematic phase there are three twist viscosities and three alignment angles corresponding to the rotation around the various directors and the different alignments of the directors relative to the stream lines, respectively. It is found that the smallest twist viscosity arises by rotation around the director formed by the long axes, the second smallest one arises by rotation around the director formed by the normals of the broadsides, and the largest one by rotation around the remaining director. The first twist viscosity is rather independent of the density whereas the last two ones increase strongly with density. One finds that there is one stable director alignment relative to the streamlines, namely where the director formed by the long axes is almost parallel to the stream lines and where the director formed by the normals of the broadsides is almost parallel to the shear plane. The relative magnitudes of the components of the twist viscosities span a fairly wide interval so this model should be useful for parameterisation experimental data.     

NMR and X-ray studies of the chromonic lyomesophases formed by some xanthone derivatives

Optical microscopy, NMR and X-ray measurements are presented for four chromonic lyomesogens derived from 9-xanthone. The measurements provide details about the mesogen-water binary phase diagrams of the four compounds as well as quantitative information about the ordering and structural parameters of the mesophases. All four systems exhibit peritectic phase diagrams with a nematic (N) phase at low mesogen concentration and a hexagonal (H) phase at high concentration. The results are consistent with previously suggested models for chromonic lyomesophases in which columnar aggregates are formed by stacked mesogenic molecules. In the N phase these columns are parallel to the director but are otherwise randomly distributed in the bulk solvent, while in the H phase they form a two dimensional hexagonal array.     

Diffusion of spheres in isotropic and nematic suspensions of rods

Diffusion of a small tracer sphere (apoferritin) in isotropic and nematic networks [of fd virus] is discussed. For a tracer sphere that is smaller than the mesh size of the network, screened hydrodynamic interactions between the sphere and the network determine its diffusion coefficient. A theory is developed for such interactions as well as their relation to the long-time self-diffusion coefficient. Fluorescence correlation spectroscopy measurements on mixtures of apoferritin and fd virus are presented. The long-time self-diffusion coefficient of apoferritin is measured as a function of the fd-virus concentration, both in the isotropic and nematic state, in directions parallel and perpendicular to the nematic director. The hydrodynamic screening length of the fd-virus network as a function of fd concentration is obtained by combining these experimental data with the theory. Surprisingly, the screening length increases with increasing concentration in nematic networks. This is due to the increase in the degree of alignment, which apparently leads to a strong increase of the screening length. Hydrodynamic screening is thus strongly diminished by alignment. A self-consistent calculation of the screening length does not work at higher concentrations, probably due to the strong variation of the typical incident flow fields over the contour of a rod.     

Lyotropic mesomorphism in benzopurpurin 4B-solvent system

The results of studying chromonic mesomorphism in benzopurpurin 4B (BP-4B)-water, BP-4B-water-electrolyte (NaCl or KCl), and BP-4B-water-N,N-dimethylformamide (DMF) or formamide (FA) systems are presented. Mesophases are identified using polarization-optical microscopy and the responses of samples to disturbances induced by magnetic field and mechanical deformation. It is shown that, in water and aqueous electrolyte solutions, at BP-4B concentrations of below 0.5 and 1.5 wt %, respectively, an instable nematic mesophase is formed, which is rapidly transformed into an anisotropic gel. In this case, the formation of the nematic mesophase is preceded by the appearance of tactoids. At some concentrations of organic solvents, nematic mesophases, which are stable for a time period of longer than 2 months, are formed in BP-4B-water-DMF (BP-4B concentrations of 1.0 and 1.5 wt %) and BP-4B-water-FA (BP-4B concentration of 1.0 wt %) systems.     

Tactoids of plate-like particles: size, shape, and director field

We studied, by means of polarized light microscopy, the shape and director field of nematic tactoids as a function of their size in dispersions of colloidal gibbsite platelets in polar and apolar solvents. Because of the homeotropic anchoring of the platelets to the interface, we found large tactoids to be spherical with a radial director field, whereas small tactoids turn out to have an oblate shape and a homogeneous director field, in accordance with theoretical predictions. The transition from a radial to a homogeneous director field seems to proceed via two different routes depending in our case on the solvent. In one route, the what presumably is a hedgehog point defect in the center of the tactoid transforms into a ring defect with a radius that presumably goes to infinity with decreasing drop size. In the other route, the hedgehog defect is displaced from the center to the edge of the tactoid, where it becomes virtual again going to infinity with decreasing drop size. Furthermore, quantitative analysis of the tactoid properties provides us with useful information on the ratio of the splay elastic constant and the anchoring strength and the ratio of the anchoring strength and the surface tension.     

Confinement and orientational study at liquid crystal phase transitions

Abstract

We have studied the heat capacity of the thermotropic liquid crystal, octylcyanobiphenyl (8CB), confined to the nearly cylindrical, 0·2 μm diameter pores of Anopore membranes. Orientation of the nematic director within the pores can be controlled with surface treatment. It is known from NMR measurements that the nematic director is aligned parallel to the pore axis in the untreated membrane. A perpendicular alignment is obtained when the pore surface is treated with lecithin. The second order smectic A to nematic (S_A–N) and the weakly first order nematic to isotropic (N–I) phase transitions of 8CB were studied in these pores, for both director orientations, using an AC calorimetry technique. Effects on heat capacity amplitudes, transition temperature shifts, rounding and broadening of these phase transitions will be presented and contrasted with bulk measurements.     

On the parallel-perpendicular transition for a nematic phase at a wall

We use an Onsager-level density functional theory to investigate the behaviour of the nematic phase in contact with a solid wall. The nematic consists of hard rigid rods having perfect uniform alignment and uniform spatial density. In the absence of any particle-wall interactions besides excluded-volume forces, we predict a director orientation parallel to the wall. We show that this preference for parallel alignment is due to the entropy associated with the larger volume available to the particles in their parallel orientation. An adsorption energy favouring normal alignment gives rise to a transition from a high temperature parallel orientation to a low temperature normal orientation. We derive expressions for the temperature of this transition, relating it explicitly to the wall adsorption energy, particle axial ratio, and nematic density. Effects such as layering near the wall and imperfect nematic order are argued not to be necessary for the existence of this transition.     

A push/pull surface-mode liquid-crystal shutter: Technology and applications

The construction, operating principles and electro-optics of a surface-mode liquid-crystal shutter are reviewed. The shutter is composed of two glass plates, the inner surfaces of which are coated with a transparent electrically conductive layer. The substrates are treated to induce parallel director alignment. Polarizers are placed on the front and back of the cell oriented at right angles to each other and at 45° to the director. In the surface mode of operation a sustaining voltage is applied to the cell. This causes the director in the centre of the cell always to be oriented parallel to the electric field. The amplitude of the applied voltage determines the thickness of the surface layer-the layer in which the director orientation varies from parallel to the surface to parallel to the electric field. Light travelling through the cell will encounter retardation only in the surface layers. Hence the voltage controls the retardation of the cell, and by that means the polarization state of the light travelling through the cell. By adjusting the voltage so that the retardation is changed from 0λ to ½λ the shutter can switch from open to closed. It is possible to construct a faster-switching shutter. This so-called push/pull shutter is composed of three elements in optical series. The first two are surface-mode cells oriented such that their directors are perpendicular. The third element is a quarter-wave plate with its axes parallel to the directors. The three elements are placed between orthogonal polarizers, with the directors oriented at 45° to the polarizers axes. The closed state of the shutter is obtained by placing one shutter in the high-voltage 0λ state and the other in the low-voltage ¼λ state. The open state of the shutter is obtained by switching the voltage levels applied to the two cells. The operating principles and the electro-optics of this device are discussed in detail.     

Molecular ordering in microconfined liquid crystals: An infrared linear dichroism study

Abstract

The molecular arrangement of 5CB confined within the cylindrical pores of Anopore membranes was characterized by means of the IR-order parameter obtained from linear dichroism measurements of selected IR absorption bands. The treatment of the experimental data includes a local field correction extended to the twisted nematic configuration, yielding order parameters increased by about 30% in comparison with the uncorrected data. The nematic director of 5CB aligns along the pore axes, whereas in lecithin coated Anopore channels, the local nematic director is oriented approximately radially due to the perpendicular anchoring of the 5CB molecules at the pore wall. Doping of 5CB with the chiral agent CB15 yields local nematic directors tilted with respect to the pore axes. The average tilt angle increases up to about 40° at a fraction of CB15, x _cb15 = 0.25 (w/w). These results are discussed in terms of the conical helicoidal and alternatively the radially twisted axial arrangement of the LC molecules within submicrometer cylindrical cavities.     

Computer simulation studies of anisotropic systems. XXII. An equimolar mixture of rods and discs: A biaxial nematic?

In principle, binary mixtures of rod-like and disc-like particles should exhibit a biaxial nematic phase, but in practice phase separation into two uniaxial nematic phases prevents this. Here, we report the results of a computer simulation study of an equimolar mixture of rods and discs in which phase separation is not allowed. The particles are confined to the sites of a simple cubic lattice in which each rod is surrounded by six discs and vice versa. Neighbouring particles interact such that they prefer to align with their respective symmetry axes orthogonal to each other. In contrast, the interaction between next nearest neighbours, which are either rods or discs, is such that their symmetry axes tend to be parallel. Monte Carlo simulations of this model mixture show that an orientationally ordered phase exists at low temperatures. This nematic phase has overall uniaxial symmetry and the particles have a negative second rank orientational order parameter, indicating that they tend to align at right angles to the director. The two interpenetrating sub-lattices containing either rods or discs, however, exhibit a biaxial nematic phase. The results of the simulation are found to be in reasonable agreement with the predictions of a molecular field theory for this model mixture. We have also investigated the behaviour of this mixture when the rods and discs are allowed to exchange between their lattice sites. The mixture is found to separate into two uniaxial nematic phases composed essentially of either rods or discs, as expected.     

Dispersion and orientation of single-walled carbon nanotubes in a chromonic liquid crystal

A post-synthesis alignment of individual single-walled carbon nanotubes (SWCNTs) is desirable for translating their unique anisotropic properties to a macroscopic scale. Here, we demonstrate excellent dispersion, orientation and concomitant-polarised photoluminescence of SWCNTs in a nematic chromonic liquid crystal. The methods to obtain stable suspension are described, and order parameters of the liquid crystal matrix and of the nanotubes are measured independently.     

Molecular ordering in microconfined liquid crystals: An infrared linear dichroism study

The molecular arrangement of 5CB confined within the cylindrical pores of Anopore membranes was characterized by means of the IR-order parameter obtained from linear dichroism measurements of selected IR absorption bands. The treatment of the experimental data includes a local field correction extended to the twisted nematic configuration, yielding order parameters increased by about 30% in comparison with the uncorrected data. The nematic director of 5CB aligns along the pore axes, whereas in lecithin coated Anopore channels, the local nematic director is oriented approximately radially due to the perpendicular anchoring of the 5CB molecules at the pore wall. Doping of 5CB with the chiral agent CB15 yields local nematic directors tilted with respect to the pore axes. The average tilt angle increases up to about 40° at a fraction of CB15, x_cb15 = 0.25 (w/w). These results are discussed in terms of the conical helicoidal and alternatively the radially twisted axial arrangement of the LC molecules within submicrometer cylindrical cavities.     

Optical and surface morphological properties of polarizing films fabricated from a chromonic dye by the photoalignment technique

The inherent chromonic lyotropic liquid crystalline properties of a dye have been manipulated to fabricate multi-axial micropolarizing thin films by means of the photoalignment technique. The dye aqueous solution is deposited on a photopatterned polymer film to result in the macroscopic alignment of the dye molecules, followed by drying at ambient temperature. The solid polarizing dye layers thus produced exhibit very a high contrast ratio and degree of polarization in the region of visible light. Addition of a small amount of surfactant to the dye solution is a prerequisite for the generation of a nematic chromonic phase and for the formation of homogeneous thin dye layers on the polymer film. The correlation between the optical and surface morphological properties of the dye layers is discussed.     

Tunable polarised fluorescence of quantum dot doped nematic liquid crystals

The concentration, excitation photon wavelength, and polarisation dependent fluorescence of quantum dot (QD)–liquid crystal (LC) mixtures has been studied at room temperature using high-resolution, steady-state fluorescence spectroscopy. The fluorescence of QD–LC mixture increases with increasing QD’s concentration but the spectral red shift of ~10 nm relative to the stock QD–Toluene solution remains independent of concentration. In vertical switching (VS) cells, an external electric field changes the LC alignment direction and enhances the apparent fluorescence intensity. The apparent fluorescence anisotropy compared to that at zero applied electric field monotonically increases up to ~27% at an applied electric field of 0.6 V/µm. These results are consistent with the formation of disc-like assemblages of QDs oriented on planes perpendicular to the director of the nematic liquid crystal (NLC). These findings have important utility in polarisation sensitive photonic devices.     

The effects of surface layers on third harmonic generation from solutions of a nematogenic polymer

Third harmonic generation (THG) is used to study the third-order nonlinear optical properties of nematic and isotropic solutions of poly(1,4-phenylene-2,6-benzobisthiazole) and related small-molecule model compounds. Maker fringe patterns (MFP) obtained using both plane slab and wedge-shaped cells for fundamental wavelengths of 1.542 and 1.907 μm are analyzed in terms of postulated surface layers in the isotropic preparations. The layers are postulated to comprise regions with concentration smaller than for the bulk sample, in which the rod-like chains tend to have their axes parallel to the plane of the surface, creating a negatively birefringent uniaxial nematic layer. The THG with the nematic solution exhibits intensity with polarization components unexpected for the uniaxial nematic symmetry attributed from linear optical properties, along with other unexpected features in the MFP. This behavior is attributed to the effects of surface layers, postulated to exhibit biaxial nematic symmetry, in which the uniaxial nematic symmetry is broken in regions on the scale of a wavelength. This provides for averaging that does not cause departure from the linear optical behavior expected for a uniaxial nematic, but does produce effects on nonlinear optical properties. © 1996 John Wiley & Sons, Inc.     

Self-screening of Langmuir-Blodgett films by a discotic micellar lyotropic liquid crystal

The influence of the surface treatment on the anisotropic part of the surface tension of a lyotropic discotic micellar nematic liquid crystal doped with ferrofluid is analysed. The treatment involves Langmuir-Blodgett (LB) films deposited on the glass substrates. Textural observations and phase-shift measurements of the transmitted light were carried out. A phenomenological model which allows calculation of the director average orientation in the bulk and at the surfaces is used for interpreting the experimental data. Our results show that the average director alignment depends on the concentration of the magnetic grains of ferrofluid at the glass surfaces. On the contrary, it is practically independent of the nature of the molecule deposited on the glass substrate. According to the model, the flat glass surface, independently of the treatment or the absence of any treatment, stabilizes onto itself a lamellar layer (or bilayer) formed by the amphiphilic molecules of the liquid crystal. This layer screens the effect of the LB film (or of the pure untreated substrate) on the alignment of the lyotropic nematic mesophase.