Twofold light and magnetic responsive behavior in nanoparticle-lyotropic liquid crystal systems

We demonstrate the dual magnetic and light responsive nature of hybrid mesophases constituted by Fe(3)O(4) nanoparticles dispersed in lipid-based lyotropic liquid crystals (LC). When subjected to an external magnetic field in the mesophase isotropic state, the nanoparticles aggregate and orient along the magnetic field direction, and upon cooling the system through the disorder-order transition the aggregates drive the orientation of the mesophase via heterogeneous nucleation; furthermore, order-disorder transitions in the lipidic mesophase can be triggered by Fe(3)O(4)-induced photothermal effect under visible light exposure. Both the orientational order and the photothermal effect of the hybrid mesophase can be tuned by the nanoparticle content, offering a general route for controlled assembly of complex fluids with combined magnetic and light responsiveness.     

Thermally induced cholesteric-isotropic transition in lyotropic polypeptide liquid crystals

The thermally induced cholesteric to isotropic transition of lyotropic polybenzylglutamate liquid crystals in six solvent combinations was examined optically. The solvents chosen for study support both low and high pitch values, positive and negative pitch temperature coefficients, and polypeptide denaturation. The biphasic zone below the clearing temperature is broad and solvent dependent. Unusual large-scale phase separations and solution morphologies occur in some solvents. No evidence was found for pretransitional chiral orientational ordering near the clearing point in the high-temperature isotropic phase.     

Liquid crystal effects on bacterial viability

The primary objective of this research was to test the hypothesis that lyotropic chromonic liquid crystals (neutral grey, red 14, blue 27, cromolyn) are not toxic to bacteria as compared with surfactant-based lyotropic (CPCl and CsPFO) or thermotropic (5CB and E7) liquid crystals. Biocompatibility of most liquid crystals is currently unknown and is required for the development of systems interfacing liquid crystals and biological systems. Potential liquid crystal toxicity was evaluated by two methods. The first examined bacterial survival measured by bacterial growth over 24 hours, after exposure to various liquid crystals. The second toxicity method evaluated liquid crystal effects on bacterial membrane permeability using two fluorescent dyes. Three different types of bacteria were evaluated to assess bacterial structure differences with respect to liquid crystal toxicity. The results of this study indicate that lyotropic chromonic liquid crystals are not toxic to bacteria, whereas thermotropic and surfactant-based lyotropic liquid crystals are toxic to one or more forms of bacteria. We conclude that lyotropic chromonic liquid crystals may be the preferred material in designing liquid crystal-based systems that interact with biological systems, especially in the use of liquid crystal-based biosensors.     

Liquid crystal effects on bacterial viability

The primary objective of this research was to test the hypothesis that lyotropic chromonic liquid crystals (neutral grey, red 14, blue 27, cromolyn) are not toxic to bacteria as compared with surfactant‐based lyotropic (CPCl and CsPFO) or thermotropic (5CB and E7) liquid crystals. Biocompatibility of most liquid crystals is currently unknown and is required for the development of systems interfacing liquid crystals and biological systems. Potential liquid crystal toxicity was evaluated by two methods. The first examined bacterial survival measured by bacterial growth over 24 hours, after exposure to various liquid crystals. The second toxicity method evaluated liquid crystal effects on bacterial membrane permeability using two fluorescent dyes. Three different types of bacteria were evaluated to assess bacterial structure differences with respect to liquid crystal toxicity. The results of this study indicate that lyotropic chromonic liquid crystals are not toxic to bacteria, whereas thermotropic and surfactant‐based lyotropic liquid crystals are toxic to one or more forms of bacteria. We conclude that lyotropic chromonic liquid crystals may be the preferred material in designing liquid crystal‐based systems that interact with biological systems, especially in the use of liquid crystal‐based biosensors.     

Conformational and Orientational Order of Molecules in Nematic Liquid Crystals

The statistical properties of the conformational and orientational distribution of molecules with internal rotation in the isotropic and nematic phases of liquid crystal (LC) are investigated in terms of molecular statistical theory. The paper discusses the effect of mutual correlation between the molecular conformational and orientational degrees of freedom on the conformational, orientational, and mixed order parameters of molecules in LC and on the nematic–isotropic liquid transition temperature. For these order parameters, the recurrent relation method is suggested and used to derive the partial functions of the conformational and orientational distributions of molecules in LC.     

无机溶致液晶研究进展

目前发现的液晶多数为有机液晶,无机液晶非常少见。非球形无机胶体(棒状或盘状)体系在排斥体积熵的作用下可形成液晶相,即无机溶致液晶。由于其具有的理论意义和潜在的应用价值,无机液晶近年来引起了人们的关注。本文综述了无机溶致液晶的研究历史和最新进展。     

Glassiness of thermotropic liquid crystals across the isotropic-nematic transition

The orientational dynamics of thermotropic liquid crystals across the isotropic-nematic phase transition have traditionally been investigated at long times or low frequencies using frequency domain measurements. The situation has now changed significantly with the recent report of a series of interesting transient optical Kerr effect (OKE) experiments that probed orientational relaxation of a number of calamitic liquid crystals (which consist of rod-like molecules) directly in the time domain, over a wide time window ranging from subpicoseconds to tens of microseconds. The most intriguing revelation is that the decay of the OKE signal at short to intermediate times (from a few tens of picoseconds to several hundred nanoseconds) follows multiple temporal power laws. Another remarkable feature that has emerged from these OKE measurements is the similarity in the orientational relaxation behavior between the isotropic phase of calamitic liquid crystals near the isotropic-nematic transition and supercooled molecular liquids, notwithstanding their largely different macroscopic states. In this article, we present an overview of the understanding that has emerged from recent computational and theoretical studies of calamitic liquid crystals across the isotropic-nematic transition. Topics discussed include (a) single-particle as well as collective orientational dynamics at a short-to-intermediate time window, (b) heterogeneous dynamics in orientational degrees of freedom diagnosed by a non-Gaussian parameter, (c) fragility, and (d) temperature-dependent exploration of underlying energy landscapes as calamitic liquid crystals settle into increasingly ordered mesophases upon cooling from the high-temperature isotropic phase. A comparison of our results with those of supercooled molecular liquids reveals an array of analogous features in these two important classes of soft matter systems. We further find that the onset of growth of the orientational order in the parent nematic phase induces translational order, resulting in smectic-like layers in the potential energy minima of calamitic systems if the parent nematic phase is sandwiched between the high-temperature isotropic phase and the low-temperature smectic phase. We discuss implications of this startling observation. We also discuss recent results on the orientational dynamics of discotic liquid crystals that are found to be rather similar to those of calamitic liquid crystals.     

Phase behavior of lyotropic rigid-chain polymer liquid crystal studied by dissipative particle dynamics

The phase behavior of lyotropic rigid-chain liquid crystal polymer was studied by dissipative particle dynamics (DPD) with variations of the solution concentration and temperature. A chain of fused DPD particles was used to represent each mesogenic polymer backbone surrounded with the strongly interacted solvent molecules. The free solvent molecules were modeled as independent DPD particles, where each particle includes a lump of solvent molecules with the volume roughly equal to the solvated polymer segment. The simulation shows that smectic-B (S(B)), smectic-A (S(A)), nematic (N), and isotropic (I) phases exist within certain regions in the temperature and concentration parameter space. The temperature-dependent S(B)∕S(A), S(A)∕N, and N∕I phase transitions occur in the high concentration range. In the intermediate concentration range, the simulation shows coexistence of the anisotropic phases and isotropic phase, where the anisotropic phases can be the S(B), S(A), or N phases. Mole fraction and compositions of the coexisted phases are determined from the simulation, which indicates that concentration of rigid rods in isotropic phase increases as the temperature increases. By fitting the orientational distribution function of the systems, the biphasic coexistence is further confirmed. From the parameter α obtained for the simulation, the distribution of the rigid rods in the two coexistence phases is quantitatively evaluated. By using model and simulation methods developed in this work, the phase diagrams of the lyotropic rigid-chain polymer liquid crystal are obtained. Incorporating the solvent particles in the DPD simulation is critical to predict the phase coexistence and obtain the phase diagrams.     

Pattern formation from consistent dynamical closures of uniaxial nematic liquid crystals

Pattern formation in uniaxial polymeric liquid crystals is studied for different dynamic closure approximations. Using the principles of mesoscopic non-equilibrium thermodynamics in a mean-field approach, we derive a Fokker-Planck equation for the single-particle non-homogeneous distribution function of particle orientations and the evolution equations for the second and fourth order orientational tensor parameters. Afterwards, two dynamic closure approximations are discussed, one of them considering the relaxation of the fourth order orientational parameter and leading to a novel expression for the free-energy like function in terms of the scalar order parameter. Considering the evolution equation of the density of the system and values of the interaction parameter for which isotropic and nematic phases coexist, our analysis predicts that patterns and traveling waves can be produced in lyotropic uniaxial nematics even in the absence of external driving.     

Lyotropic liquid crystal guest–host material and anisotropic thin films for optical applications

We propose a new approach for the production of thin film optical functional materials. The method is based on molecular design whereby two different types of lyotropic liquid crystals (LC), lyotropic LC based on columnar supramolecules and water-soluble rod-like polymer molecules are mixed. The resulting lyotropic guest–host system allows production of optical retardation films with tunable optical anisotropy controlled by composition of the guest–host system. Coatable retarders can be used in modern liquid crystal displays and TVs for optical compensation and enhancement of the LCD's performance.     

Orientational ordering in discotic columnar phases. A theoretical approach

We discuss the different transitions from hexagonal to lower symmetry phases which result from a molecular tilt inside the columns. Several orientational structures are explained and others are predicted. Our model also applies to other physical phenomena, in particular the elliptical deformation of columnar aggregates in lyotropic liquid crystals     

Local high-density distributions of phospholipids induced by the nucleation and growth of smectic liquid crystals at the interface

Amphiphilic molecules adsorbed at the interface could control the orientation of liquid crystals (LCs) while LCs in turn could influence the distributions of amphiphilic molecules. The studies on the interactions between liquid crystals and amphiphilic molecules at the interface are important for the development of molecular sensors. In this paper, we demonstrate that the development of smectic LC ordering from isotropic at the LC/water interface could induce local high-density distributions of amphiphilic phospholipids. Mixtures of liquid crystals and phospholipids in chloroform are first emulsified in water. By fluorescently labeling the phospholipids adsorbed at the interface, their distributions are visualized under fluorescent confocal microscope. Interestingly, local high-density distributions of phospholipids showing a high fluorescent intensity are observed on the surface of LC droplets. Investigations on the correlation between phospholipid density, surface tension and smectic LC ordering suggest that when domains of smectic LC layers nucleate and grow from isotropic at the LC/water interface as chloroform slowly evaporates at room temperature, phospholipids transition from liquid-expanded to liquid-condensed phases in response to the smectic ordering, which induces a higher surface tension at the interface. The results will provide an important insight into the interactions between liquid crystals and amphiphilic molecules at the interface.     

Solubilization of thermotropic liquid crystal compounds in aqueous surfactant solutions

We study the micellar solubilization of three thermotropic liquid crystal compounds by immersing single drops in aqueous solutions of the ionic surfactant tetradecyltrimethylammonium bromide. For both nematic and isotropic drops, we observe a linear decrease of the drop size with time as well as convective flows and self-propelled motions. The solubilization is accompanied by the appearance of small aqueous droplets within the nematic or isotropic drop. At low temperatures, nematic drops expell small nematic droplets into the aqueous environment. Smectic drops show the spontaneous formation of filament-like structures which resemble the myelin figures observed in lyotropic lamellar systems. In all cases, the liquid crystal drops become completely solubilized, provided the weight fraction of the liquid crystal in the system is not larger than a few percent. The solubilization of the liquid crystal drops is compared with earlier studies of the solubilization of alkanes in ionic surfactant solutions.     

Macroscopic liquid crystal response to isolated DNA helices

Nematic liquid crystals (LC) were exposed to isolated DNA molecules extended on a surface that imparted a negligible influence on the LC orientation. Although single-stranded DNA aligned the LC in the extension direction, double-stranded DNA (dsDNA) caused alignment at an oblique angle, providing a characteristic response to the chiral dsDNA helix that was readily observed optically. The intrinsic amplification due to LC orientational correlations enabled a macroscopic visible response to a single molecule of extended dsDNA.     

Phase and orientational ordering of low molecular weight rod molecules in a quenched liquid crystalline polymer matrix with mobile side chains

We study the phase diagram and orientational ordering of guest liquid crystalline (LC) rods immersed in a quenched host made of a liquid crystalline polymer (LCP) matrix with mobile side chains. The LCP matrix lies below the glass transition of the polymer backbone. The side chains are mobile and can align to the guest rod molecules in a plane normal to the local LCP chain contour. A field theoretic formulation for this system is proposed and the effects of the LCP matrix on LC ordering are determined numerically. We obtain simple analytical equations for the nematic/isotropic phase diagram boundaries. Our calculation show a nematic-nematic (N/N) first order transition from a guest stabilized to a guest-host stabilized region and the possibility of a reentrant transition from a guest stabilized nematic region to a host only stabilized regime separated by an isotropic phase. A detailed study of thermodynamic variables and interactions on orientational ordering and phases is carried out and the relevance of our predictions to experiments and computer simulations is presented.     

Oriented monolayers prepared from lyotropic chromonic liquid crystal

We use a layer-by layer electrostatic self-assembly technique to obtain in-plane oriented aggregates of mesogenic dye molecules cast from lyotropic chromonic liquid crystals (LCLCs) on mica substrates. The aqueous solutions of dye used for deposition are in the nematic phase. Atomic force microscopy and X-ray photoelectron spectroscopy of the dried film reveal that the LCLC molecules adsorb at the charged substrate preserving ordered aggregates of elongated shape characteristic of the nematic phase in the aqueous solution. These elongated aggregates of LCLC molecules form films with in-plane orientational order and are compositionally distinct from the substrate.     

Properties of the discotic-nematic to isotropic transition: influence of short range orientational order

The present investigation concerns the analysis of the influence of short range orientational correlation on the thermodynamic properties of discotic-nematic liquid crystals. Two-site cluster approximation is applied to the orientational molecular coordinates to include the short range orientational correlation. The role of short range orientational order, dispersion interaction, molecular length-to-width ratio and pressure on the thermodynamic and orientational behaviour of discotic nematogens close to the discotic-nematic to isotropic transition are analysed. It is observed that the short range orientational order has a strong influence on the thermodynamic properties and that the transition properties of both the calamitic and discotic mesogens exhibit quite similar behaviour.     

Properties of the discotic-nematic to isotropic transition: influence of short range orientational order

The present investigation concerns the analysis of the influence of short range orientational correlation on the thermodynamic properties of discotic-nematic liquid crystals. Two-site cluster approximation is applied to the orientational molecular coordinates to include the short range orientational correlation. The role of short range orientational order, dispersion interaction, molecular length-to-width ratio and pressure on the thermodynamic and orientational behaviour of discotic nematogens close to the discotic-nematic to isotropic transition are analysed. It is observed that the short range orientational order has a strong influence on the thermodynamic properties and that the transition properties of both the calamitic and discotic mesogens exhibit quite similar behaviour.     

Short time dynamics in the isotropic phase of liquid crystals: the aspect ratio and the power law decay

Optical heterodyne detected optical Kerr effect (OHD-OKE) experiments are used to study the orientational dynamics of the liquid crystal 4^′-octyl-4-biphenylcarbonitrile (8CB) in the isotropic phase near the isotropic to nematic phase transition. The results are compared to those for three other liquid crystals. The 8CB data display a short time scale temperature independent power law decay and a long time scale exponential decay with a temperature dependence described by Landau–de Gennes theory. The power law exponent is −0.56. Combining this result with previous results for three other liquid crystals [J. Chem. Phys. 116 (2002) 6339; J. Chem. Phys. 116 (2002) 360], it is found that the power law exponent depends linearly on the aspect ratio of the liquid crystal.     

Cubatic liquid-crystalline behavior in a system of hard cuboids

The lyotropic phase behavior of cuboidal particles was investigated via Monte Carlo simulations. Hard cubes were approximated by suitably shaped clusters of hard spheres. Changes in concentration and structure of the system were monitored as a function of osmotic pressure P* (imposed in an isobaric ensemble). As expected, an isotropic phase prevailed at low concentrations (low P*) and a crystalline phase formed at high concentrations (high P*). A third distinct phase was also observed for an intermediate range of concentrations (approximately marked by breaks in the P* versus concentration curve). The structure of this mesophase was characterized both visually and analytically by calculating radial distribution functions and order parameters. It was found that such a mesophase exhibits orientational ordering along three axes (cubatic order) but significant translational disorder, thus having a structure clearly distinct from both isotropic and crystalline phases.