Synthesis and characterization of novel liquid crystalline polymers containing cholesteryl pendant groups

In order to investigate the chiral effect of cholesteryl pendant groups on the induction of the cholesteric phase, a new cholesteryl-containing liquid crystalline monomer was synthesized and copolymerized with an achiral comonomer in various molar ratios. The layer-like arrangement of the smectic mesophase with different monomeric compositions of copolymers was investigated using an X-ray diffraction analysis. The cholesteric liquid phase was induced by the chiral segments; the dependence of the reciprocal central reflection wavelength on the mole fraction of the chiral monomer for copolymers was investigated. This paper demonstrates the effect of chiral pendant groups on the induction of the cholesteric phase and layered molecular arrangement of side-chain liquid crystalline polymers.     

Synthesis and properties of novel chiral side-chain liquid crystalline polysiloxanes containing different chiral pendant groups

Two novel chiral liquid crystalline monomers, and a series of their corresponding chiral side-chain polymers (P₁–P₇) based on poly(methylhydrogeno)siloxane have been prepared. The chemical structures and liquid crystalline properties of the synthesized monomers and polymers have been investigated using various experimental techniques. Thermal analysis shows that all polymers have wide mesophase temperature ranges with a high thermal stability. With the increase of M₂ molar ratio in the polymer systems, the isotropic phase transition and glass transition temperatures of all polymers increase, and the temperature ranges of N* phase and mesophase become broad. The effect of cholesteryl mesogens on mesophase behaviors, optical properties, and molecular arrangement of LC polysiloxanes and their advanced applications have also been discussed. For homopolymer P₁, it shows a single S_A phase. With increasing the content of M₂ in the polymer systems, P₂ and P₃ reveal a S_A–N* phase transition when they are heated, and P₄–P₇ reveal a N* phase. For N* phase polymers P₄–P₇, the reflection wavelengths exhibit blue shift, suggesting that the pitch decreases with a decrease in the amount of the smectic domains induced by the M₁. The reflection wavelengths of P₄–P₇ are almost across the entire visible region when they are heated, which offer stremendous potential for various optical applications. For P₂ and P₃, the reflection wavelengths show a very steep change around the temperature of the S_A–N* phase transition, which can be used as thermally sensitive liquid crystal devices requiring fast response, such as sensors, and thermally induced tuning.     

A study of the wide ferroelectric phase in mixtures of chiral and non-chiral tilted smectic C-type liquid crystals

A new liquid crystal of a siloxane dimer with an achiral swallow-tail, C11Si2C11, D, was synthesized and mixed with a chiral material as a chiral dopant, 4′-[11-(1,1,2,2,3,3,3-heptamethyltrisiloxanyl)undecyloxy]biphenyl-4-carboxylate, C11Si3, C, to prepare binary mixtures for this study. All mixtures possess the ferroelectric chiral smectic C phase over a broad temperature range. For respect compound C11Si3, the temperature range of the SmC* phase was only 72.6 °C, and was increased upon the addition of dimer C11Si2C11. The electro-optical properties of the SmC* phase, such as tilt angle, dielectric permittivity and switching behavior were also measured. It appeared that the mixtures had a similar viscosity, but the switching time was decreased due to the larger P_s, which was caused by an increased proportion of C11Si3. Therefore, the mixtures revealed a similar tilt angle at around 37.5° at temperatures within their respective mesophase temperature ranges. As a consequence, the correlation between the electro-optical properties and mixture proportion was determined.     

手性近晶C相串型液晶共聚物的合成与性能

以对苯二甲酰氮,2,5－二[4-((S)-2-甲基丁氧基）苯甲酰氧基]对苯二酚和三缩四乙醇为单体,采用低温溶液缩聚的方法,合成了一系列新的手性近晶C相串型液晶共聚物。通过DCS,偏光显微镜,WAXD和旋光分析等方法,发现所有的手性共聚物都有光活性,当加热至熔融温度以上时形成近晶C相,共聚物的熔融温度（Tm)和各负同性温度（Ti)随共聚物分子中三缩四乙二醇用量的改变呈规律性变化。     

Liquid Crystalline Elastomers

Today, material science is directed towards the development of multifunctional and oriented structures. One example of such supramolecular systems are liquid crystalline (LC) elastomers which combine the properties of LC phases (the combination of order and mobility) with rubber elasticity, one of the most typical polymer properties. Their most outstanding characteristic is their mechanical orientability; strains as small as 20% are enough to obtain a perfectly oriented LC monodomain. This orientability, if LC elastomers with chiral phases are used, leads, for example, to elastomers with chiral smectic C* phases which are likely to show piezo-electric behavior.     

侧向邻二氟取代三联苯光活性液晶的合成与性质

利用钯催化交叉偶合反应合成了一个系列的侧向邻二氟取代三联苯光活性液晶化合物。由于在分子中引入了手性中心和侧向氟原子，使得液晶呈现出不同寻常的近晶相织构。这类化合物均具有光活性和Ｎ＊相，其清亮点随末端烷氧基链碳原子数的增加呈现出明显的变化规律。     

含二羟基二苯酮的系列热致液晶共聚酯的合成和表征（Ⅰ）

本文采用直接熔融缩聚法合成了含４，４＇－二烃基二苯酮、对苯二甲酸、对羟基苯甲酸和一缩二乙二醇的四元共聚酯。利用差动扫描量热计（ＤＳＣ）、偏光显微镜、Ｘ射线衍射等手段对该共聚酯进行了表征。结果表明，聚合物具有向列型热致液晶特性。本文还对不同温度和剪切取向下的液晶态织构以及不同条件处理的试样的结晶行为进行了初步的探讨。     

Water vapor transport in liquid crystalline and non-liquid crystalline epoxies

This paper presents a comparison of moisture permeation in liquid crystalline and non-liquid crystalline epoxy systems. The permeability is obtained using a dynamic method. It is found that diffusion in both epoxy systems is Fickian. The liquid crystalline epoxy network exhibits higher barrier properties to moisture transport than the conventional epoxy network. The efficient chain packing of the smectic mesophase of the liquid crystalline epoxy is the main factor for this difference. The stoichiometry has a large effect on the moisture permeation. The diffusion coefficient decreases monotonically with increasing amine/epoxide functional ratio. The permeability (P) and solubility coefficient (S) reach a minimum for a functional ratio of one. The results are described on the basis of hydrogen bonding of water to the epoxy network and the two phase morphology of cured epoxies.     

Chiral Reaction Field with Thermally Invertible Helical Sense that Controls the Helicities of Conjugated Polymers

A chiral reaction field with thermally invertible helical sense enables control of the helicity of the reaction product, which is a central challenge in asymmetric synthesis that has yet to be overcome. A novel chiral compound comprising two types of chiral moieties with opposite helicities and temperature dependences is synthesized; this compound is added as a chiral dopant to a mixture of nematic liquid crystals to prepare a chiral nematic liquid crystal (N*-LC). The N*-LC containing the chiral dopant exhibits thermally invertible helicity to yield left- and right-handed helical senses at low and high temperatures, respectively. Interfacial polymerization of acetylene is achieved in the N*-LC by modulating the temperature. Helical polyacetylenes (H-PAs) that are synthesized at low (−12 °C) and high (28 °C) temperature show right- and left-handedness, respectively, in terms of the fibrils, fibril bundles, and spiral morphology. In addition, the helical sense of H-PA is opposite that of the N*-LC because of the peculiar polymerization mechanism for acetylene in the N*-LC. The current N*-LC is the first chiral reaction field that has not only the thermally invertible helical sense but also the chemical functions and stability needed to serve as the medium for polymer reactions.     

Thermotropic, Thermo-morphologic, and Thermo-optical Properties of New Smectogenic Calamitic Compounds Containing Imine Linking Groups

The synthesis and investigations of the mesomorphic, thermotropic, thermo-morphologic, and thermo-optical properties of two new salicylaldimine compounds, synthesized by our group, are reported in this work. Temperature transformations of specific textures of the smectic C mesophase, taking place in these compounds, and thermo-morphologic and thermotropic properties of the biphasic regions for direct and reverse phase transitions have been investigated. Temperature hysteresis and enlargement of the biphasic regions have been found. The character of texture transformations and temperature behavior of the optical birefringence indicate to the first order a smectic C–isotropic liquid-phase transition in these salicylaldimine compounds.     

Some peculiarities of nematic-isotropic liquid phase transitions in monomorphic and polymorphic mesogens

In this study, the dynamics of the changes of the morphological properties in the nematic mesophase and in the heterophase regions of the phase transitions between the nematic mesophase and the isotropic liquid for the thermotropic mesogens have been investigated. Experimentally, we have obtained the thermal hysteresis for the investigated phase transitions. For the analysis of the phase transition temperatures and the peculiarities of the heterophase regions, the mean field theory has been used.     

A transient mesophase on drawing polymers based on polyethylene terephthalate (PET) and polyethylene naphthoate (PEN)

This paper is centred around the identification of a transient mesophase during the drawing of PET and PEN and their associated random copolymers. While the observation of the mesophase has previously been announced as a note (Macromolecules, 31, 1998, p. 7562), this paper sets out the work in appropriate detail. Samples across the full random copolymer composition range are hot drawn, and, either immediately quenched or examined in-situ using synchrotron radiation. In each case a mesophase has been observed under drawing conditions which produced little or no crystallinity. That the phase was not the product of the quench was confirmed by the high temperature dynamic measurements. The signature of the mesophase is a sharp, meridional peak in the WAXS fibre diagram which shows no other sharp peaks suggesting crystallinity; the equatorial maxima, while equiaxial and indicating a high level of chain orientation, are diffuse. The mesophase is thus classified as smectic A. SAXS measurements on quenched samples, give no indication that the mesophase is associated with a particular microstructure. The mesophase is seen across the PET/PEN composition range, its observation being more straightforward in the random copolymers where the rate of crystallisation is significantly reduced. Subsequent crystallisation of the fibres by suitable annealing, replaces the meridional mesophase peak on the first layer line with off-meridional crystal reflections characteristic of the triclinic unit cell. The layer line is at a slightly lower angle after crystallisation indicating a longer axial repeat in the crystal than in the mesophase. The development of crystallinity gives rise to a distinct SAXS pattern indicative of a two phase microstructure. The transition from smectic A mesophase to triclinic crystal provides a rationale for the occurrence of oblique lamellae in PET, and associated random copolymers with more than 70% ethylene terephthalate units, as indicated by the four point SAXS patterns, and also for the c axis tilt observed in the WAXS patterns. Similarly, for the PEN rich copolymers, the absence of obliquity and consequent c-axis tilt, coupled with the marked layer line streaking of the triclinic reflections, can be rationalised in terms of the c-shear of the transition being compensated by faulting in the crystal.     

羧酸侧基对主链液晶聚合物性能的影响

采用溶液缩聚的方法,以4,4′-对羟基联苯(MB)、2,5-二羟基苯甲酸(MC)、癸二酰氯(SD)为单体,合成了主链液晶离聚物。通过红外光谱(FT-IR)、偏光显微镜(POM)、差示扫描量热(DSC)、X射线衍射(XRD)等手段研究了离子单体对主链液晶离聚物性能的影响。结果表明,所合成的聚合物都为热致近晶型液晶聚合物。其Tg,Tm和Ti随离子含量的增加呈现不同的变化趋势,少量的2,5-二羟基苯甲酸钠(MC-Na)增宽了聚合物的液晶区间,但较大量的MC-Na破坏了液晶相。     

Ordered materials for organic electronics and photonics

We present a critical review of semiconducting/light emitting, liquid crystalline materials and their use in electronic and photonic devices such as transistors, photovoltaics, OLEDs and lasers. We report that annealing from the mesophase improves the order and packing of organic semiconductors to produce state-of-the-art transistors. We discuss theoretical models which predict how charge transport and light emission is affected by the liquid crystalline phase. Organic photovoltaics and OLEDs require optimization of both charge transport and optical properties and we identify the various trade-offs involved for ordered materials. We report the crosslinking of reactive mesogens to give pixellated full-colour OLEDs and distributed bi-layer photovoltaics. We show how the molecular organization inherent to the mesophase can control the polarization of light-emitting devices and the gain in organic, thin-film lasers and can also provide distributed feedback in chiral nematic mirrorless lasers. We update progress on the surface alignment of liquid crystalline semiconductors to obtain monodomain devices without defects or devices with spatially varying properties. Finally the significance of all of these developments is assessed.     

High Virus Removal by Self‐Organized Nanostructured 2D Liquid‐Crystalline Smectic Membranes for Water Treatment

To obtain high quality of drinking water free from biocontaminants is especially important issue. A new strategy employing smectic liquid‐crystalline ionic membranes exhibiting 2D structures of layered nanochannels for water treatment is proposed for efficient virus removal and sufficient water flux. The smectic A (SmA) liquid‐crystalline membranes obtained by in situ polymerization of an ionic mesogenic monomer are examined for removal of three distinct viruses with small size: Qβ bacteriophage, MS2 bacteriophage, and Aichi virus. The semi‐bilayer structure of the SmA significantly obstructs the virus penetration with an average log reduction value of 7.3 log₁₀ or the equivalent of reducing 18 million viruses down to 1. Furthermore, the layered nanochannels of the SmA liquid crystal allow efficient water permeation compared to other types of liquid‐crystalline membrane consisting of nanopores.     

Mechanism of thermal phase transition of a ferroelectric liquid crystal with monotropic transition temperature studied by infrared spectroscopy combined with principal component analysis and sample-sample two-dimensional correlation spectroscopy

Infrared (IR) spectra of FLC-154 (FLC: ferroelectric liquid crystal) with monotropic phase transition under a nonalignment state with a sample layer thickness of 24.5 microm were measured for heating process from 55 to 90 degrees C and a cooling process from 90 to 55 degrees C in increments of 1 degrees C. The thermal dynamics of FLC-154 were investigated by use of IR spectroscopy combined with principal component analysis (PCA) and sample-sample two-dimensional (2D) correlation spectroscopy. During the cooling, the FLC-154 molecule passes through the monotropic smectic-C* (Sm-C*) phase, which is transformed from the Sm-A phase. The results from PCA suggest that during the heating process, the thermal dynamics of the alkyl chains, core moiety, and C=O groups are similar to each other. Furthermore, PCA and sample-sample 2D correlation spectroscopy indicate that the alkyl chains and C=O groups in the chiral and core moieties are responsible for the emergence of the Sm-C* phase. This conclusion is very important because the IR data have given more evident cause for the emergence of the Sm-C* phase than the theoretical models such as the molecular-statistical theory of ferroelectric ordering and the indigenous polarization theory. Moreover, it has been found that some of the trans conformations of the alkyl chains of FLC-154 change partly to the gauche conformation when the phase transition from the crystalline phase to the Sm-A phase occurs. It has also been found that the intermolecular interactions of the C=O group in the core moiety in the Sm-A phase are weaker than those in the crystalline phase and that the conformational change occurs on the C-O-C bonds in the core moiety upon going from the crystalline to the Sm-A phase.     

New chiral liquid crystalline monomers, polymers, and elastomers derived from menthol derivatives: synthesis and mesomorphism

To investigate liquid crystalline properties and structure relationships of chiral compounds based on menthol, a series of new chiral monomers derived from menthol derivatives, a mesogenic crosslinking agent, the corresponding side chain homopolymers with siloxane backbone, and cholesteric elastomers were synthesized. The structures and purity of these chiral compounds obtained in this study were characterized using FTIR, ¹H NMR, and elemental analyses. The mesomorphism and thermal stabilities were investigated using differential scanning calorimetry, polarizing optical microscopy, thermogravimetric analysis, and X-ray diffraction. The selective reflection of light for the chiral monomers was studied with UV/visible/near IR. The effect of the crosslinking agent content on the phase transition temperatures of the elastomers was discussed. It was found that these chiral monomers seemed beneficial for the formation of the mesophases when a flexible spacer was inserted between the mesogenic core and the terminal menthyl groups. All obtained chiral monomers showed a cholesteric phase, chiral smectic C phase, and cubic blue phase. The crosslinking agent exhibited a smectic A (S_A) phase and nematic phase. However, their corresponding homopolymers with siloxane chains tended to form a lower order S_A phase. With an increase of the mesogenic rigidity, the melting temperatures, glass transition temperatures (T _g), and isotropic temperatures (T _i) of chiral monomers or homopolymers all increased. For the elastomers, general tendency was toward increased T _g and T _i with increasing the crosslinking agent content.     

Synthesis and characterization of chiral liquid crystal polymers containing donor–acceptor group

A series of new chiral side-chain liquid crystalline polymers with electron donor–acceptor action were prepared containing chiral monomer with donor group and nematic LC monomer with acceptor group. All polymers were synthesized by graft polymerization using polymethylhydrosiloxane as backbone. The mesomorphic properties were investigated by differential scanning calorimetry (DSC), polarizing optical microscopy (POM), thermogravimetric analyses (TGA), and X-ray diffraction measurements (XRD). The chemical structures of monomers and polymers were confirmed by Fourier transform infrared (FTIR), proton nuclear magnetic resonance spectra (¹H NMR and ¹³CNMR). M ₁ did not show liquid crystalline phase and M ₂ turned out nematic phase on heating and cooling cycle. Polymers P ₂ –P ₇ were cholesteric phase. Cholesteric phase and low glass temperature liquid crystalline polymers have been obtained, which offered the possibility of application. Experimental results demonstrated that the glass-transition temperatures rose and isotropization temperatures decreased and the ranges of the mesophase temperature reduced with increasing the content of chiral agent. All of the obtained polymers showed high thermal stability.     

Nematic DNA Thermotropic Liquid Crystals with Photoresponsive Mechanical Properties

Over the last decades, water‐based lyotropic liquid crystals of nucleic acids have been extensively investigated because of their important role in biology. Alongside, solvent‐free thermotropic liquid crystals (TLCs) from DNA are gaining great interest, owing to their relevance to DNA‐inspired optoelectronic applications. Up to now, however, only the smectic phase of DNA TLCs has been reported. The development of new mesophases including nematic, hexagonal, and cubic structures for DNA TLCs remains a significant challenge, which thus limits their technological applications considerably. In this work, a new type of DNA TLC that is formed by electrostatic complexation of anionic oligonucleotides and cationic surfactants containing an azobenzene (AZO) moiety is demonstrated. DNA–AZO complexes form a stable nematic mesophase over a temperature range from ?7 to 110 °C and retain double‐stranded DNA structure at ambient temperature. Photoisomerization of the AZO moieties from the E‐ to the Z‐ form alters the stiffness of the DNA–AZO hybrid materials opening a pathway toward the development of DNA TLCs as stimuli‐responsive biomaterials.     

Pattern of liquid crystalline droplets induced by two beam interference in azobenzene derivative

A pattern of liquid crystalline droplets dispersed in the isotropic liquid can be formed during illumination by two interfering laser beams in certain range of the temperature and the light intensity. Azobenzene derivative substituted by long alkyl and alkoxy chains exhibiting smectic phases has been used for the study. The pattern can be reversibly erased and rewritten by shutting down and opening of the interfering beams. Polarized microscope images have shown the formation of numerous liquid crystalline droplets at bright regions of the interference fringes. Influence of the temperature and the light intensity has been studied by measuring the diffraction efficiency dynamics. Photothermal and photoorientational mechanisms of the formation of liquid crystalline droplets pattern have been proposed and discussed.