Nematoelasticity of hybrid molecular-colloidal liquid crystals.

Colloidal rods immersed in a thermotropic liquid-crystalline solvent are at the basis of so-called hybrid liquid crystals, which are characterized by tunable nematic fluidity with symmetries ranging from conventional uniaxial nematic or antinematic to orthorhombic [Mundoor et al., Science 360, 768 (2018)SCIEAS0036-807510.1126/science.aap9359]. We provide a theoretical analysis of the elastic moduli of such systems by considering interactions between the individual rods with the embedding solvent through surface-anchoring forces, as well as steric and electrostatic interactions between the rods themselves. For uniaxial systems, the presence of colloidal rods generates a marked increase of the splay elasticity, which we found to be in quantitative agreement with experimental measurements. For orthorhombic hybrid liquid crystals, we provide estimates of all 12 elastic moduli and show that only a small subset of those elastic constants play a relevant role in describing the nematoelastic properties. The complexity and possibilities related to identifying the elastic moduli in experiments are briefly discussed.

Repulsion-attraction switching of nematic colloids formed by liquid crystal dispersions of polygonal prisms.

Self-assembly of colloidal particles due to elastic interactions in nematic liquid crystals promises tunable composite materials and can be guided by exploiting surface functionalization, geometric shape and topology, though these means of controlling self-assembly remain limited. Here, we realize low-symmetry achiral and chiral elastic colloids in the nematic liquid crystals using colloidal polygonal concave and convex prisms. We show that the controlled pinning of disclinations at the prism edges alters the symmetry of director distortions around the prisms and their orientation with respect to the far-field director. The controlled localization of the disclinations at the prism's edges significantly influences the anisotropy of the diffusion properties of prisms dispersed in liquid crystals and allows one to modify their self-assembly. We show that elastic interactions between polygonal prisms can be switched between repulsive and attractive just by controlled re-pinning the disclinations at different edges using laser tweezers. Our findings demonstrate that elastic interactions between colloidal particles dispersed in nematic liquid crystals are sensitive to the topologically equivalent but geometrically rich controlled configurations of the particle-induced defects.

Topological switching and orbiting dynamics of colloidal spheres dressed with chiral nematic solitons.

Metastable configurations formed by defects, inclusions, elastic deformations and topological solitons in liquid crystals are a promising choice for building photonic crystals and metamaterials with a potential for new optical applications. Local optical modification of the director or introduction of colloidal inclusions into a moderately chiral nematic liquid crystal confined to a homeotropic cell creates localized multistable chiral solitons. Here we induce solitons that "dress" the dispersed spherical particles treated for tangential degenerate boundary conditions, and perform controlled switching of their state using focused optical beams. Two optically switchable distinct metastable states, toron and hopfion, bound to colloidal spheres into structures with different topological charges are investigated. Their structures are examined using Q-tensor based numerical simulations and compared to the profiles reconstructed from the experiments. A topological explanation of observed multistability is constructed.

Effect of plasmon-enhancement on photophysics in upconverting nanoparticles.

Surface plasmon polaritons (SPP) waves have been shown to significantly affect the near-field photophysical phenomenon. In particular, strong Coulombic interactions can enhance nearby non-linear optics and energy transfer process, while SPP waves also affect other photophysical processes like quenching observed in fluorescent and excitonic systems. Here, using different plasmonic substrates, we show the effect of plasmon-enhancement on quenching, phonon-assisted non-radiative decay, weak Purcell effect or electromagnetic field enhancement, and energy transfer rates of upconverting doped-lanthanide nanoparticles. While the resonant plasmons enhance the local electromagnetic field and the rate of energy transfer leading to enhanced upconversion photoluminescence of infrared radiation to visible light, it can also increase the quenching and non-radiative decay rates of photoexcited electron-hole pairs leading to losses and lower efficiency. These results can guide the design of optimized substrate geometry for using surface plasmons to modulate the photophysics in other applications too.

Tunable optical metamaterial based on liquid crystal-gold nanosphere composite.

Effect of the surrounding anisotropic liquid crystal medium on the surface plasmon resonance (SPR) exhibited by concentrated suspensions of gold nanospheres has been investigated experimentally and compared with the Mie scattering theory. The observed polarization-sensitive SPR and the red-shift in the SPR wavelength with increasing concentration of the gold nanospheres in the liquid crystal matrix have been explained using calculations based on the Maxwell Garnet effective medium theory. Agglomeration of the gold nanospheres that could also lead to such a red-shift has been ruled out using Atomic force microscopy study of thin nanoparticle-doped smectic films obtained on solid substrates. Our study demonstrates feasibility of obtaining tunable optical bulk metamaterials based on smectic liquid crystal - nanoparticle composites.

Three-dimensional imaging of dielectric patterns in electrohydrodynamic convection of a nematic liquid crystal.

The transition from surface to bulk normal dielectric rolls in a nematic liquid crystal is imaged by fluorescence confocal polarizing microscopy. The three-dimensional director structure and the liquid flow are scanned in both the layer plane and the transverse plane. Two systems of small-scale convective flow are formed, one at each electrode. Strong anchoring makes director oscillations difficult and charges accumulate by the Carr-Helfrich mechanism. The middle region is a structureless convection where the director oscillates with the frequency of the applied voltage. The small-scale flow eventually fills the cell from one electrode to the other as one system of thin and elongated rolls. The true dielectric mode is not a director pattern, rather a surface flow instability.

Undulations of lamellar liquid crystals in cells with finite surface anchoring near and well above the threshold.

We study the undulations instability, also known as the Helfrich-Hurault or layers buckling effect, in a cholesteric liquid crystal confined between two parallel plates and caused by an electric field applied along the normal to layers. The cholesteric pitch is much smaller than the cell thickness but sufficiently large for optical study. The three-dimensional patterns of the undulating layers in the bulk and at the surfaces of the cells are determined by fluorescence confocal polarizing microscopy. We demonstrate that the finite surface anchoring at the bounding plates plays a crucial role in the system behavior both near and well above the undulations threshold. The displacement of the layers immediately above the undulation threshold is much larger than the value expected from the theories that assume an infinitely strong surface anchoring. We describe the experimentally observed features by taking into account the finite surface anchoring at the bounding plates and using Lubensky-de Gennes coarse-grained elastic theory of cholesteric liquid crystals. Fitting the data allows us to determine the polar anchoring coefficient Wp and shows that Wp varies strongly with the type of substrates. As the applied field increases well above the threshold value Ec, the layers profile changes from sinusoidal to the sawtooth one. The periodicity of distortions increases through propagation of edge dislocations in the square lattice of the undulations pattern. At E approximately 1.9Ec a phenomenon is observed: the two-dimensional square lattice of undulations transforms into the one-dimensional periodic stripes. The stripes are formed by two sublattices of defect walls of parabolic shape. The main reason for the structure is again the finite surface anchoring, as the superposition of parabolic walls allows the layers to combine a significant tilt in the bulk of the cell with practically unperturbed orientation of layers near the bounding plates.

Electrorotation of colloidal particles in liquid crystals.

We present the first observations of dc electric-field-induced rotational motion of finite particles in liquid crystals. We show that the electrorotation is essentially identical to the well-known Quincke rotation, which in liquid crystals triggers an additional translational motion at higher fields. In the smectic phase the translational motion is confined to the two-dimensional geometry of smectic layers, in contrast to the isotropic and nematic phases, where the particles can move in all three dimensions. We demonstrate that by a proper analysis of the electrorotation, one can determine the in-plane viscosity of smectic liquid crystals. This method needs only a small amount of material, does not require uniform alignment over large areas, and enables probing rheological properties locally.

Elasticity-mediated self-organization and colloidal interactions of solid spheres with tangential anchoring in a nematic liquid crystal.

Using laser tweezers, we study colloidal interactions of solid microspheres in the nematic bulk caused by elastic distortions around the particles with tangential surface anchoring. The interactions overcome the Brownian motion when the interparticle separation r-->p is less than 3 particle diameters. The particles attract when the angle theta between r-->p and the uniform far-field director n0 is between 0 degrees and approximately 70 degrees and repel when 75 degrees

Real-time microbe detection based on director distortions around growing immune complexes in lyotropic chromonic liquid crystals.

We describe director distortions in the nematic liquid crystal (LC) caused by a spherical particle with tangential surface orientation of the director and show that light transmittance through the distorted region is a steep function of the particle's size. The effect allows us to propose a real-time microbial sensor based on a nontoxic lyotropic chromonic LC (LCLC) that detects and amplifies the presence of immune complexes. A cassette is filled with LCLC, antibody, and antigen-bearing particles. Small and isolated particles cause no macroscopic distortions of the LCLC. Upon antibody-antigen binding, the growing immune complexes distort the director and cause detectable optical transmittance between crossed polarizers.

Switchable two-dimensional gratings based on field-induced layer undulations in cholesteric liquid crystals.

We propose switchable two-dimensional (2D) diffractive gratings with periodic refractive-index modulation arising from layer undulations in cholesteric liquid crystals. The cholesteric cell can be switched between two states: (1) flat layers of a planar cholesteric texture and (2) a square lattice of periodic director modulation associated with layer undulations that produces 2D diffraction patterns. The intensities of the diffraction maxima can be tuned by changing the applied field. The diffractive properties can be optimized for different wavelengths by appropriately choosing cholesteric pitch, cell thickness, and surface treatment.

Selective imaging of 3D director fields and study of defects in biaxial smectic A liquid crystals.

We report on the selective imaging of different director fields in a biaxial smectic A (SmAb) liquid crystal using Fluorescence Confocal Polarizing Microscopy (FCPM) and Polarizing Microscopy (PM). The patterns of two directors, namely the director n(a) perpendicular to the lamellae and the director n(b) in their planes are visualized by doping the liquid crystal with two fluorescent dyes with different orientation of the transition dipoles with respect to the lamellar matrix. The properties of defects such as disclinations and focal conic domains (FCDs) are consistent with the non-polar D2h-symmetry of the SmA(b) mesophase in the studied mixture of bent-core and rod-like molecules: (1) majority of defects in the director n(b) are half-integer "+/-1/2" disclinations; (2) the integer-strength "+/-1" defects tend to split into the "+/-1/2" disclinations. We compare the vertical cross-sections of the "+/-1" disclinations in the field in SmA(b) and uniaxial nematic samples. In SmA(b), the "+/-1" disclinations do not escape into the third dimension, while in the nematic samples with Schlieren textures they do despite the surface anchoring at the plates; the experimentally determined director field around the escaped disclination capped by a pair of surface point defects--boojums matches the one predicted recently [C. Chiccoli et al., Phys. Rev. E 66, 030701 (2002)]. The FCD structure in SmA(b) is similar to that in SmA and SmC in terms of the normal to the layers but differs significantly in terms of the director n(b) field parallel to the smectic layers. The FCDs in SmA(b) can be associated with topologically non-trivial configurations of n(b) in the surrounding matrix that are equivalent to the disclination lines.

Electric-field-induced nematic-cholesteric transition and three-dimensional director structures in homeotropic cells.

We study the phase diagram of director structures in cholesteric liquid crystals of negative dielectric anisotropy in homeotropic cells of thickness d which is smaller than the cholesteric pitch p. The basic control parameters are the frustration ratio d/p and the applied voltage U. Upon increasing U, the direct transition from completely unwound homeotropic structure to the translationally invariant configuration (TIC) with uniform in-plane twist is observed at small d/p < or = 0.5. Cholesteric fingers that can be either isolated or arranged periodically occur at 0.5 < or = d/p<1 and at the intermediate U between the homeotropic unwound and TIC structures. The phase boundaries are also shifted by (1) rubbing of homeotropic substrates that produces small deviations from the vertical alignment; (2) particles that become nucleation centers for cholesteric fingers; (3) voltage driving schemes. A novel reentrant behavior of TIC is observed in the rubbed cells with frustration ratios 0.6 < or = d/p < or = 0.75, which disappears with adding nucleation sites or using modulated voltages. In addition, fluorescence confocal polarizing microscopy (FCPM) allows us to directly and unambiguously determine the three-dimensional director structures. For the cells with strictly vertical alignment, FCPM confirms the director models of the vertical cross sections of four types of fingers previously either obtained by computer simulations or proposed using symmetry considerations. For rubbed homeotropic substrates, only two types of fingers are observed, which tend to align along the rubbing direction. Finally, the new means of control are of importance for potential applications of the cholesteric structures, such as switchable gratings based on periodically arranged fingers and eyewear with tunable transparency based on TIC.

Ordered droplet structures at the liquid crystal surface and elastic-capillary colloidal interactions.

We demonstrate a variety of ordered patterns, including hexagonal structures and chains, formed by colloidal particles (droplets) at the free surface of a nematic liquid crystal (LC). The surface placement introduces a new type of particle interaction as compared to particles entirely in the LC bulk. Namely, director deformations caused by the particles lead to distortions of the interface and thus to capillary attraction. The elastic-capillary coupling is strong enough to remain relevant even at the micron-scale when its buoyancy-capillary counterpart becomes irrelevant.

Anchoring-mediated interaction of edge dislocations with bounding surfaces in confined cholesteric liquid crystals.

We employ the fluorescent confocal polarizing microscopy to image edge dislocations in cholesteric liquid crystals. Surface anchoring at the bounding plates determines the structure and behavior of defects. Two types of plates set in-plane director orientation but differ in the type of associated anchoring potentials. Plates with strong polar anchoring and nonzero azimuthal anchoring repel the dislocations, while plates with weak polar anchoring and no azimuthal anchoring allow the dislocations to escape through the boundary. To explain the results, we propose a coarse-grained model of cholesteric anchoring.

Preparation and in vitro characterization of a eutectic based semisolid self-nanoemulsified drug delivery system (SNEDDS) of ubiquinone: mechanism and progress of emulsion formation.

The objectives of the present work were, first, to develop a self-nanoemulsified drug delivery system (SNEDDS) based on the eutectic properties of ubiquinone (CoQ10); and second, to study the progress of emulsion formation and drug release mechanisms by turbidimetry and droplet size analysis. Binary phase diagrams of CoQ10 with menthol and essential oils were constructed and used to develop the self-nanoemulsified formulation. Pseudo ternary phase diagram was constructed to identify the efficient self-emulsification region. Release mechanisms of the resultant formulas were quantified using turbidimetry in combination with dissolution studies. Turbidity time profiles revealed three distinctive regions: lag phase, plateau, and the pseudolinear phase. Lag phase was attributed to the liquid crystalline properties of the formula. Plateau turbidity was correlated with droplet size. Laser diffraction analysis revealed an average droplet diameter of 100 nm. Emulsification rate was obtained from the corrected slope of the pseudolinear phase of the profile. Stability of the formula was further evaluated using Fourier transform-infrared (FT-IR) attached to an attenuated total reflectance (ATR) accessory. The present study revealed a eutectic based semisolid self-emulsified delivery system that can overcome the drawbacks of the traditional emulsified systems such as low solubility and irreversible precipitation of the active drug in the vehicle with time.

Three-dimensional director structures of defects in Grandjean-Cano wedges of cholesteric liquid crystals studied by fluorescence confocal polarizing microscopy.

We use a nondestructive technique of fluorescence confocal polarizing microscopy to visualize three-dimensional director patterns of defects in Grandjean-Cano wedges filled with a cholesteric liquid crystal of pitch p=5 microm. Strong surface anchoring of the director causes a stable lattice of dislocations in the bulk. Optical slicing in the vertical cross sections of the wedges allows us to establish the detailed structure of dislocations and their kinks. Dislocations of Burgers vector b=p/2 are located in the thin part of the sample, very close to the bisector plane. Their cores are split into a pair of tau(-1/2) and lambda(+1/2) disclinations. Pairs of lambda(-1/2) and tau(+1/2) disclinations are observed when the b=p/2 dislocation forms a kink. The kinks along the b=p/2 dislocations change the level of dislocations by +/-p/4 and +/-p/2; these kinks are confined to the glide plane and are very long, (5-10) p. Above some critical thickness h(c) of the wedge sample, the dislocations are of Burgers vector b=p. They are often found away from the bisector plane. The core of b=p dislocations is split into a pair of nonsingular lambda(-1/2) and lambda(+1/2) disclinations. The kinks along the b=p dislocation are of a typical size p and form cusps in the direction perpendicular to the glide plane. At the cusp, lambda(-1/2) and lambda(+1/2) disclinations interchange ends. Other defect structures inlude "Lehmann clusters," i.e., dislocations of zero Burgers vector formed by two lambda(-1/2) and two lambda(+1/2) disclinations and dislocations of nonzero Burgers vector with a core split into more than two disclinations. We employ the coarse-grained Lubensky-de Gennes model of the cholesteric phase to describe some of the observed features. We calculate the elastic energy of a dislocation away from the core, estimate the energy of the core split into disclinations of different types, study the effect of finite sample thickness on the dislocations energy, and calculate the Peach-Koehler elastic forces that occur when a dislocation is shifted from its equilibrium position. Balance of the dilation/compression energy in the wedge and the energy of dislocations defines the value of h(c) and allows to estimate the core energy of the dislocations. Finally, we consider the Peierls-Nabarro mechanisms hindering glide of dislocations across the cholesteric layers. Because of the split disclination character of the core, glide is difficult as compared to climb, especially for b=p dislocations.