SIDE CHAIN LIQUID CRYSTALLINE POLYSILOXANES CONTAINING CROWN ETHER AND BENZYL ETHER MOIETIES

Two kinds of side chain liquid crystalline polysiloxanes containing crownether and benzyl ether were synthesized and characterized by optical polarization mi-croscopy. Both the monomeric liquid crystals and polymeric liquid crystals show smecticphases.     

手性席夫碱型液晶化合物的合成与表征

手性席夫碱型液晶化合物的合成与表征田颜清，林凤，赵英英，汤心颐，苏峰煜，赵晓光，周恩乐（吉林大学化学系长春１３００２３）（中国科学院长春应用化学研究所长春）关键词近晶相液晶，手性液晶，席夫碱，合成，表征自从１９７５年Ｍｅｙｅｒ等［１］首次合成铁电液晶...     

Appearance of liquid crystals in acupuncture points

Liquid crystals of biomolecules occur ubiquitously in biological systems, and to study the physiological mechanism of acupuncture, methods involving the detection of liquid crystals have been introduced. It is revealed that liquid crystals appear in the acupuncture point Zusanli 15 min after the appropriate stimulus in the acupuncture point Jiexi, which is located on the same meridian with Zusanli according to the Meridian Theory of Chinese Medicine, whereas liquid crystals are rarely observed in the points beside the Zusanli in the same condition. Subsequent studies on the composition of the liquid crystals detected, using energy dispersive X-ray analysis and histochemical analysis, suggest that the liquid crystals consist of proteins and perhaps phospholipids. The results show that these biomolecules, which are accumulated in the extracellular fluid of the acupuncture point, may function in the acupuncture effects, and moreover that liquid crystal detection can serve as a simple method to start studies of such complicated physiological phenomena.     

Appearance of liquid crystals in acupuncture points

Liquid crystals of biomolecules occur ubiquitously in biological systems, and to study the physiological mechanism of acupuncture, methods involving the detection of liquid crystals have been introduced. It is revealed that liquid crystals appear in the acupuncture point Zusanli 15 min after the appropriate stimulus in the acupuncture point Jiexi, which is located on the same meridian with Zusanli according to the Meridian Theory of Chinese Medicine, whereas liquid crystals are rarely observed in the points beside the Zusanli in the same condition. Subsequent studies on the composition of the liquid crystals detected, using energy dispersive X-ray analysis and histochemical analysis, suggest that the liquid crystals consist of proteins and perhaps phospholipids. The results show that these biomolecules, which are accumulated in the extracellular fluid of the acupuncture point, may function in the acupuncture effects, and moreover that liquid crystal detection can serve as a simple method to start studies of such complicated physiological phenomena.     

γ-取代-β-二酮二羰基合铑的合成与介晶性

合成了体系中含一个苯环、二个苯环的γ-取代-β二酮二羰基合铑棒状金属有机化合物, 并对其介晶性进行了表征。探讨了分子长宽比、刚性实和结构对液晶性质的影响。同时表明了向列相有机液晶分子的模型设计同样能很好地指导金属有机液晶分子的设计、合成及介晶性行为的研究。     

The determination of molecular parameters from dielectric measurements on nematic liquid crystals

The physical properties of liquid crystal phases (mesophases) depend in a very sensitive manner on the structure of the constituent liquid crystal-forming molecules (mesogens). Thus a small change in molecular structure can result in a dramatic change in the corresponding liquid crystal properties. The dielectric responses of materials reflect the electric properties of molecules, and so analysis of dielectric measurements on liquid crystals in terms of molecular properties should lead to the development of structure/property relationships for such mesophases. This paper explores the problems of determining molecular parameters from dielectric measurements on nematic liquid crystals. Specifically, the difficulties in defining the internal electric field and knowing the value of the order parameter are addressed. Experimental results on a range of liquid crystals show that short range correlations are important in determining both the dielectric and optical response of nematic liquid crystals. It is concluded therefore that more sophisticated molecular theories, which take account of molecular shape and volume, need to be developed before reliable structure/property relationships can be established for liquid crystals.     

Functional liquid crystal films selectively recognize amine vapours and simultaneously change their colour

During recent years, cholesteric liquid crystals have found only a few applications, one of them being temperature detection; in this study, however, we intend to show that the combination of cholesteric liquid crystals and molecules with a trifluoroacetyl function can be applied to optically detect amine vapours.     

Synthesis and mesomorphic properties of rigid-core ionic liquid crystals

Ionic liquid crystals combine the unique solvent properties of ionic liquids with self-organization found for liquid crystals. We report a detailed analysis of the structure-property relationship of a series of new imidazolium-based liquid crystals with an extended aromatic core. Investigated parameters include length and nature of the tails, the length of the rigid core, the lateral substitution pattern, and the nature of the counterion. Depending on the molecular structure, two mesophases were observed: a bilayered SmA2 phase and the more common monolayered SmA phase, both strongly interdigitated. Most materials show mesophases stable to high temperatures. For some cases, crystallization could be suppressed, and room-temperature liquid crystalline phases were obtained. The mesomorphic properties of several mixtures of ionic liquid crystals were investigated. Many mixtures showed full miscibility and ideal mixing behavior; however, in some instances we observed, surprisingly, complete demixing of the component SmA phases. The ionic liquid crystals and mixtures presented have potential applications, due to their low melting temperatures, wide temperature ranges, and stability with extra ion-doping.     

Switchable columnar metallomesogens

Chiral columnar liquid crystals have recently appeared as a promising new type of ferroelectric materials. To date, all the columnar liquid crystals that have been reported to show ferroelectric switching consist of organic compounds. However, metal-containing liquid crystals open this field to a significant number of new structures and offer the possibility of adding to the ferroelectric behavior other properties inherent to the presence of metals in the structure, such as magnetism, as well as the use of new methods of characterization (EPR, synchrotron radiation, etc.). The potential of columnar metal-containing liquid crystals as ferroelectric materials has been demonstrated even though only a few organic columnar ferroelectric liquid crystals have been described. As a first approach to this type of material, this concepts article describes the results obtained with chiral metal beta-diketonates that show ferroelectric switching in the columnar mesophase. It has been shown that these materials have a helical columnar arrangement in the mesomorphic state, and a chiral superstructure has been proposed from circular dichroism studies. This type of supramolecular structure plays a fundamental role in the ferroelectric properties of these compounds. The discussion is mainly focused on the strategy employed for the molecular design, and on the interpretation of the mesophase structure and the electrooptic effect. The use of a diverse range of techniques, both those commonly used in the field of liquid crystals and those that are more specific will be highlighted, and the principles of these specific techniques are summarized together with a justification of their applicability to this study.     

Synthesis and mesomorphic properties of steroidal liquid crystals containing perfluoroalkoxycarbonylphenyl units

Two cholesteryl esters liquid crystals containing perfluoroalkoxy terminal chains, and benzoate and carbonate moieties, have been synthesized. Their mesomorphic properties were observed and measured by optical polarizing microscopy and differential scanning calorimetry. The results show that the two liquid crystals exhibit smectic A and B phases. No chiral tilted smectic phase was observed.     

Synthesis and mesomorphic properties of steroidal liquid crystals containing perfluoroalkoxycarbonylphenyl units

Two cholesteryl esters liquid crystals containing perfluoroalkoxy terminal chains, and benzoate and carbonate moieties, have been synthesized. Their mesomorphic properties were observed and measured by optical polarizing microscopy and differential scanning calorimetry. The results show that the two liquid crystals exhibit smectic A and B phases. No chiral tilted smectic phase was observed.     

Discotic liquid crystals at the air water interface

The monolayer properties of two types of discotic liquid crystals, hexasubstituted triphenylenes 1 and azo derivatives of phloroglucinol 5, were examined. First investigations show that these discotic liquid crystals form stable monolayers. It could be shown that electron acceptors insert into the monolayer of 1. Azo discs display a packing behaviour at the monolayer that is ascribed to a side-on packing of the molecules.     

Effect of molecular structure of a dichroic dye and the ordering of a liquid crystal on the dichroism of the dye-liquid crystal binary mixtures

The orientational ordering of dyes doped into liquid crystals has been investigated. The experimental results show that the ordering of the dyes can be expressed as a function of the order parameter of the liquid crystal host and the molecular structure of the dye. In addition a theory of the ordering of molecules in a binary mixture system has been derived by extending Kimura's theory. The validity of the theory has been confirmed by comparison with the experimental results using various combination of azo dyes and liquid crystals.     

Effect of molecular structure of a dichroic dye and the ordering of a liquid crystal on the dichroism of the dye-liquid crystal binary mixtures

The orientational ordering of dyes doped into liquid crystals has been investigated. The experimental results show that the ordering of the dyes can be expressed as a function of the order parameter of the liquid crystal host and the molecular structure of the dye. In addition a theory of the ordering of molecules in a binary mixture system has been derived by extending Kimura's theory. The validity of the theory has been confirmed by comparison with the experimental results using various combination of azo dyes and liquid crystals.     

Liquid crystal side chain polysiloxanes containing various proportions of non-mesogenic units

Recent studies have established that side chain polymeric liquid crystals composed of mesogenic and non-mesogenic side groups keep their liquid-crystalline properties even for a low proportion of mesogens. We show that the detailed structures of three kinds of new diluted liquid crystal polysiloxanes depend on the nature of the co-substituent as well as on the proportion of the silicon sites occupied by the mesogenic groups. Mixtures of these systems with low molar mass liquid crystals were also investigated in terms of compatibility and/or stabilization of smectic A phases.     

Synthesis and mesomorphic properties of several series of fluorinated ester liquid crystals

Eight series of fluorosubstituted three-ring ester liquid crystals have been synthesized. Polarizing microscopic textural observations and DSC measurements of their phase transitions show that most are thermotropic liquid crystals with nematic and smectic A phases; furthermore, several show monotropic high order smectic phases. The results showed that the SmA phase is enhanced with the increasing number of fluoro-substituents at the para - and meta -positions of the terminal phenyl groups. The mesomorphic properties of these compounds are also affected by the direction of the ester bonds. The effect of the triple bond is also discussed.     

含氟液晶研究进展

本文简述了含氟液晶的研究进展。根据小分子含氟液晶中氟原子或含氟基团的位置不同,将其分为3类：末端是氟原子或含氟基团的液晶、苯环上氢原子被氟原子取代的液晶、中心桥键上的氢原子被氟原子取代的液晶。根据小分子含氟液晶特点,归纳了氟原子或含氟基团对液晶分子物理性质的影响。同时对高分子含氟液晶的研究进展也做了介绍。     

Synthesis of novel (-)-menthol-based azobenzene chiral liquid crystals and effect of terminal alkyl chains on mesomorphic behaviour

ABSTRACT

A series of novel azobenzene chiral liquid crystals (Mt4AZOnB) containing (-)-menthyl were successfully synthesised. Terminal alkyl chains of the molecules varied from methyl to hexyl. The chemical structures were characterised by Fourier transform infrared and ¹H-NMR spectra. Liquid crystalline behaviour of the chiral liquid crystals was characterised by differential scanning calorimetry and polarising optical microscopy. The effect of terminal alkyl chains on mesomorphic and photoisomerisation behaviour of azobenzene-based liquid crystals is discussed. The lower members (n = 1, 2, 3, 4) are monotropic and only the higher members (n = 5, 6) show enantiotropic behaviour. These compounds show a distinct odd-even effect for the phase transition temperature when the parity of the terminal chain is varied.     

几类非常规液晶材料的研究进展

本文综述了液晶二聚体、多爪型液晶及香蕉形液晶等几类非常规液晶材料的研究进展。结合笔者近几年的研究积累,着重介绍:(1)液晶二聚体的分子结构与液晶态结构及液晶二聚体所特有的奇偶效应与近晶多形性;(2)多爪型液晶的分子结构与液晶态结构的特点及由于兼有棒状分子与盘状分子的结构特点而具备的特殊的相变性质;(3)香蕉形液晶的分子结构与液晶态结构及香蕉形液晶所特有的手性与极化序。在介绍各类液晶材料的特点及研究热点的同时,围绕分子结构与液晶态结构的关系这一主题,深入讨论了各种液晶材料形成特殊分子排列及表现出特殊物理性质的机理。