Potassium-ion-selective sensing based on selective reflection of cholesteric liquid crystal membranes

It is well-known that cholesteric liquid crystals have an optical property, selective reflection, due to changes in the pitch of their helical structure. This unique property of cholesteric liquid crystals can be used to attain a visual sensing system showing color changes as the detection signal. In this paper, we report a visual sensing membrane comprising cholesteric liquid crystals, in which a 15-crown-5 derivative was incorporated as ion recognizing sites, for K⁺ in aqueous solution. The resulting CLC membrane showed a shift of the reflection peak sensitive to K⁺ in water. We have also designed polymer-dispersed liquid crystal membranes that showed ion-selective reflection peak shifts with improved response time.     

Liquid Crystals: A Tool for Studies on Chirality

Nematic liquid crystals are extremely sensitive to optically active molecules, which, at very low concentration, convert them into cholesteric liquid crystals. The purpose of this report is to review recent applications of liquid crystals to chirality studies. A brief discussion of the structure and properties of liquid crystals is followed by a survey of the methods currently being employed for the determination of the pitch and handedness of cholesteric liquid crystals. Of special interest in the formation of induced-cholestric phases are the twisting powers of optically active compounds and the structural relationships between dopants and nematics. Liquid crystals can be used, inter alia, for the detection of small optical activities and for the determination of thermal racemization barriers and absolute configurations.     

Chiral,Thermally Irreversible and Quasi-Stealth Photochromic Dopant to Control Selective Reflection Wavelength of Cholesteric Liquid Crystal

A chiral and thermally irreversible photochromic fulgide derivative incorporating an (R)-binaphthol unit in its acid anhydride moiety was used for the photoswitching of the pitch length of cholesteric liquid crystals. Since the absorption maximum wavelengths of both thermally stable photoisomers are nearly in the UV region (quasi-stealth photochromism), it can be exposed to visible light without inducing photochromic reactions. Therefore, when the photoswitching molecule is added to a permanent cholesteric liquid crystal whose reflection light wavelength is in the visible region, the UV light-induced photochromic reaction of the photoswitching molecule changes the wavelength of the reflection light in the visible light region. We have succeeded in regulating the color of cholesteric liquid crystalline cells between red and blue upon UV light irradiation. Attempts to introduce this system in polymer dispersed cholesteric liquid crystals are also described.     

基于胆甾相液晶的可调制光子晶体

将胆甾相液晶填充进胶体晶体内部空隙, 通过胆甾相液晶与胶体晶体的耦合, 构建了一种新型可调制液晶光子晶体. 填充于胶体晶体内部的胆甾相液晶织构呈现典型的手性近晶相(S)特征. 由于胆甾相液晶具有特定的选择性反射, 当胶体晶体的带隙处于胆甾相液晶的反射波长范围之内, 则随着温度的改变, 胶体晶体的带隙与胆甾相液晶的带隙同时发生蓝移. 在一定温度条件下, 胆甾相液晶的带隙将与胶体晶体的带隙发生耦合, 实现了光子晶体带隙在单峰与双峰之间的可逆切换.     

Amphiphilic cholesteric liquid crystals prepared from the quaternary ammonium surfactant S-(-)-1-hexadecyl-1-methyl-2-pyrrolidinemethanol bromide

We describe the first successful attempt to produce amphiphilic cholesteric liquid crystals using a chiral quaternary ammonium surfactant, namely S-(-)-1-hexadecyl-1-methyl-2-pyrrolidinemethanol bromide. Only amphiphilic cholesteric liquid crystal samples were made where the micelle structure is related to disc shaped micelles in the achiral N_D phase. The surfactant concentration dependence of the twist and the temperature dependence of the twist were made using laser diffraction. The twist in the amphiphilic cholesteric liquid crystal samples was too small to produce total iridescence.     

乙基纤维素液晶的螺旋性质及影响因素的研究

以乙基纤维素／丙烯酸体系为例，对乙基纤维素液晶的胆甾相性质及其影响因素进行了研究，测定了体系胆甾相结构的螺距。结果表明，乙基纤维素／丙烯酸液晶体的螺旋方向为左旋，随溶液液浓度的增大，胆甾相结构的螺距减小。胆甾相结合的螺距还明显地受到温度，压力、溶剂组成，高分子掺杂等因素的影响。     

Amphiphilic cholesteric liquid crystals prepared from the quaternary ammonium surfactant S-(−)-1-hexadecyl-1-methyl-2-pyrrolidinemethanol bromide

Abstract

We describe the first successful attempt to produce amphiphilic cholesteric liquid crystals using a chiral quaternary ammonium surfactant, namely S-(?)-1-hexadecyl-1-methyl-2-pyrrolidinemethanol bromide. Only amphiphilic cholesteric liquid crystal samples were made where the micelle structure is related to disc shaped micelles in the achiral N_D phase. The surfactant concentration dependence of the twist and the temperature dependence of the twist were made using laser diffraction. The twist in the amphiphilic cholesteric liquid crystal samples was too small to produce total iridescence.     

AFM investigations of a glassy cholesteric liquid crystal with hydrophobic aerosil particles

AFM investigations of a glassy heterogeneous system consisting of an oligomeric cholesteric liquid crystal and the hydrophobic aerosil R812 were carried out. With increasing aerosil concentration, a suppression of the characteristic cholesteric surface pattern was observed. Typical separated aerosil aggregates appear in the samples. Their size and form change from small lumps through bigger rod-like entities to large crystallite-like aggregates of aerosil particles. This matches with observations of light scattering of systems with low molecular mass liquid crystals and of the memory effect. The pitch of the cholesteric fingerprint pattern slightly decreases with increase in the aerosil concentration.     

New micro-structure designs of a wide band reflective polarizer with a pitch gradient

New microstructure designs for fabricating a wide band reflective polarizer (WBRP) from cholesteric liquid crystals are reported. The pitch difference in the WBRP is formed by orienting a single layer consisting of different glassy siloxane cyclic side chain oligomer powders on a heater. The molecular arrangement obtained is frozen by quenching. The experimental results show that various micro-areas exhibiting different reflection wavelengths and pitch gradients are formed in the WBRP. A WBRP exhibiting the reflection properties of the original cholesteric liquid crystals is fabricated by a novel experimental process and the experimental results are in accordance with the microstructure designs of the WBRP.     

Liquid Crystals as Stationary Phases for High Performance Liquid Chromatography

Abstract

Liquid crystals have not yet been used as stationary phases in High Performance Liquid Chromatography. This is surprising since Gas Chromatography has demonstrated some remarkable separations, many of which are not possible with normal stationary phases, that have been achieved where liquid crystals have been employed as the stationary phase. The objective of the work reported here was to evaluate the chromatographic properties of several cholesteric liquid crystals as stationary phases in HPLC. Included in this study was an investigation of the feasibility of bonding a cholesteric moiety to a solid support for use in HPLC. The columns showed a dramatic increase in capacity factor for steroid molecules as the temperature of the column was increased.     

Liquid crystals and biological morphogenesis: Ancient and new questions

Superposed series of arcs were observed in extracellular matrices of diverse tissues in plants and animals, and also within certain chromosomes. These bow-shaped patterns were shown to originate from oblique sections in a three-dimensional arrangement of fibrils, which was reminiscent of a well-known structure present in a specific type of liquid crystal, called “cholesteric”, since it was first described in several cholesterol esters. These liquid crystals were also obtained with numerous chiral polymers, such as double-stranded nucleic acids, diverse polypeptides and polysaccharides. However, the fibrous matrices with arced patterns are not at all fluid in general and are considered as stabilized analogues of cholesteric liquid crystals. These geometrical similarities between fibrous tissues and liquid crystals were at the origin of numerous works defining a new type of self-assembly involving two successive steps: a phase transition from an isotropic liquid phase to a liquid crystalline one, followed by a sol–gel stabilization of the liquid crystal. One is tempted to apply to these biological materials the main concepts introduced by physicists in the field of liquid crystals, but many aspects require a new discussion, especially because living cells are present in such systems, and this opens considerable perspectives for research.     

Light-induced structural changes in chiral liquid crystals

Novel light-sensitive chiral dopants are studied as a light-sensitive component in chiral liquid crystals which may be used in tunable optical devices. Light-induced cis-trans- isomerization of chiral dopants results in changes of helical twisting power which translates into variations of helical pitch. Due to the light absorption in the liquid crystal cell the pitch variation is non-uniform across the cell, which leads, at first, to a deformation of cholesteric layers, and then to the formation of cholesteric bubbles. The sequence of structural changes has a distinct visual pattern and occurs at the surface close to the UV light source. Small deformations of cholesteric layers and bubbles are unstable and disappear after removing UV irradiation. The increasing size of the cholesteric bubbles results in better stability; large bubbles do not disappear after removing UV light. A theoretical model is suggested to describe the undulations of cholesteric layers.     

Lasing from chiral photonic band gap materials based on cholesteric glasses

Glass-forming cholesteric liquid crystals were studied as promising dye-doped lasing materials at different pumping energies and temperatures. Cholesteric samples doped with laser dye pyrromethane 597 were pumped by Nd:YAG laser. Lasing was found to depend strongly on the vitrification rate of cholesteric samples, their temperature and multidomain structure. The lasing threshold and intensity as a function of thickness of cholesteric resonator are determined by two competing factors: narrowing of the band edge modes and increasing disorder.     

Lasing from chiral photonic band gap materials based on cholesteric glasses

Glass-forming cholesteric liquid crystals were studied as promising dye-doped lasing materials at different pumping energies and temperatures. Cholesteric samples doped with laser dye pyrromethane 597 were pumped by Nd:YAG laser. Lasing was found to depend strongly on the vitrification rate of cholesteric samples, their temperature and multidomain structure. The lasing threshold and intensity as a function of thickness of cholesteric resonator are determined by two competing factors: narrowing of the band edge modes and increasing disorder.     

Polymer-dispersed liquid crystals From the nematic curvilinear aligned phase to ferroelectric films

Polymer-dispersed liquid crystals (PDLC) are widely used for electro-optic applications such as flexible displays, privacy windows or projection displays. Besides these applications, the confinement of a liquid crystal to small cavities is of fundamental interest. The present paper contains a review of the work on nematic and cholesteric PDLCs. Moreover, some very recent developments are summarized such as the use of ferroelectric liquid crystals for PDLC applications.     

Flexible free-standing films morphology characterization: PVA/silica polymer network dispersed cholesteric liquid crystals films by sol-gel method

A novel flexible free-standing films of polyvinyl alcohol (PVA)/silica polymer network dispersed cholesteric liquid crystals (CLC) have been prepared by the sol-gel process. In the hydrolysis of silicon alkoxides tetraethoxysilane (TEOS) processes, the silica having -OH with the -OH groups on PVA formed polymer networks with Si-O-C bonds by dehydration. The cholesteric liquid crystals were incorporated into the networks. The free-standing films were obtained by the spin-coating method. In order to improve the compatibility and microstructure of the cholesteric liquid crystals with PVA/silica polymer networks, the amphiphilic compound of hexadecyl trimethyl ammonium bromide (HDTMA) was introduced into the forming film solutions. Effects of the different ratios of raw materials on the structure of films were investigated. The microscopic morphology of free-standing films and the uniform dispersion of CLCs in the films have been characterized by polarizing optical microscopy (POM), the field emission scanning electron microscope (FESEM), Fourier transform infrared (FT-IR) spectrometer and atomic force microscope (AFM). The free-standing films exhibiting excellent CLC droplets dispersion, mechanical stability, and good flexibility could be useful for flexible displays, switchable optical elements and smart windows.     

Optical wave propagation in a cholesteric liquid crystal using the finite element method

Bragg reflections of cholesteric liquid crystals at normal and oblique incidences were investigated using the finite element method (FEM). Detailed FEM derivations together with the consideration of boundary conditions are given. Two methods for achieving broadband Bragg reflection are analysed: one is to use high birefringence liquid crystal in the uniform pitch structure, the other is to use the gradient pitch structure. In each case, the number of cholesteric pitches required for establishing the Bragg reflection was simulated.     

A Review of the Status of Polymerization in Thermotropic Liquid Crystal Media and Liquid Crystalline Monomers

Thermotropic liquid crystals offer uniquely ordered media for intermolecular reactions such as polymerization. Unlike the recently investigated topochemical polymerizations where molecules are rigidly constrained on lattice points [l], the liquid crystalline state permits full two-dimensional (nematic and cholesteric) and one-dimensional (smectic) movement. In addition, various degrees of translational freedom are attainable depending on the class of mesogen. Such freedom of choice, plus the ability to orient nematic and cholesteric mesogens on a molecular scale in an electric or magnetic field or on certain surfaces, makes the liquid crystal state an attractive polymerization medium.     

Optical wave propagation in a cholesteric liquid crystal using the finite element method

Bragg reflections of cholesteric liquid crystals at normal and oblique incidences were investigated using the finite element method (FEM). Detailed FEM derivations together with the consideration of boundary conditions are given. Two methods for achieving broadband Bragg reflection are analysed: one is to use high birefringence liquid crystal in the uniform pitch structure, the other is to use the gradient pitch structure. In each case, the number of cholesteric pitches required for establishing the Bragg reflection was simulated.     

Hydrostatic pressure effects on polymer cholesteric liquid-crystalline structure. I. Equilibrium structure of hydroxypropyl cellulose aqueous solution

The effect of pressure on the polymer cholesteric liquid-crystalline structure of hydroxypropyl cellulose aqueous solutions was studied using reflection spectra measurements. Pressures applied to the polymer liquid crystals ranged from 1 to 2000 bar. The equilibrium reflection spectrum of the cholesteric structure shifted to longer wavelengths, showing that the cholesteric pitch of the liquid-crystalline structure increases as the applied pressure increases. At pressures higher than 200 bar the maximum wavelength of reflection shifted linearly with the increase in applied pressure. At lower pressures, the cholesteric structure was influenced by the surface plane of the quartz window.