Thermotropic liquid crystalline glycolipids

Are the liquid crystalline properties of the materials of living systems important in biological structures, functions, diseases and treatments? There is a growing consciousness that the observed lyotropic, and often thermotropic liquid crystallinity, of many biological materials that possess key biological functionality might be more than curious coincidence. Rather, as the survival of living systems depends on the flexibility and reformability of structures, it seems more likely that it is the combination of softness and structure of the liquid-crystalline state that determines the functionality of biological materials. The richest sources of liquid crystals derived from living systems are found in cell membranes, of these glycolipids are a particularly important class of components. In this critical review, we will examine the relationship between chemical structure and the self-assembling and self-organising properties of glycolipids that ultimately lead to mesophase formation.     

Dimesogenic liquid crystalline organosiloxanes

Liquid crystalline (LC) organosiloxanes with two terminal cyanobiphenylyl groups attached to a linear or cyclic siloxane center through an aliphatic spacer (CH₂) _n with i = 10 were synthesized. The ability of compounds to pass into the LC state was confirmed by thermooptical, X-ray diffraction, and calorimetric measurements. The temperatures and the enthalpies of phase transitions were determined. The types of LC structures and the capability of one compound for polymesomorphism to form the chiral S_mC* phase without a chiral center in the mesogenic group were established. The temperatures and the enthalpies of the reversible phase transitions, crystal S_mC S_mA melt and crystal S_mA melt, for linear and cyclic LC organosiloxanes, respectively, were determined. Models of molecular packing in the S_mA and S_mC* phases were proposed based on X-ray diffraction data. A specific feature of the S_mA phases of new LC organosiloxanes is a negative gradient of the temperature dependence of the interlayer spacing.     

Charge-transport in crystalline organic semiconductors with liquid crystalline order

We report the design and synthesis of a liquid crystalline material exhibiting highly ordered smectic phases and high charge carrier-mobility; by a process known as "paramorphosis" highly ordered smectic phases can be transferred to the amorphous crystalline state on crystallisation without the formation of significant crystal grain boundaries and deep traps.     

Structural models for some crystalline and liquid crystalline polymers

Structural models for the crystalline and liquid crystalline smectic phase are presented for polymethylsiloxanes with mesogenic side groups and for some crystalline and lyotropic liquid crystalline cholesteric phases of cellulose derivatives. Optical and X-ray methods have been applied in these investigations.     

Comb-shaped liquid crystalline ionogenic copolymers

 A series of new ionogenic liquid crystalline (LC) copolymers (A4CB-AA) was prepared by radical copolymerization of 4-(4-cyanobiphenyl-4′-yloxy) butyl acrylate (A4CB) and acrylic acid (AA). The presence of the AA units do not prevent the development of the nematic phase, which is typical of the initial cyanobiphenyl homopolymer. At a content of AA of 42–52 mol%, the copolymers produce the S _Ad type of mesophase, and this phenomenon is explained by an increased rigidity of the main chain due to the development of intramolecular hydrogen bonds. By increasing the concentration of AA units higher than 55 mol%, the development of mesophase is prevented, and the as-received copolymers are amorphous. A crucial role of intramolecular hydrogen bonds for the development of the S _A phase in the copolymers is proved by synthesizing and studying the copolymers, in which the same type of the mesogenic group A4CB is preserved but the second component is provided by methyl ether of acrylic acid; such copolymers are able to produce only a nematic phase. Studying orientation of LC A4CB-AA copolymers in the magnetic field by the method of wide-line ¹H NMR spectroscopy allows one to calculate the temperature dependences of order parameter S and to advance a correct interpretation of experimental data. Received: 8 January 1998 Accepted: 14 April 1998     

Columnar liquid crystalline pi-conjugated oligothiophenes

Polycatenar oligothiophenes possessing three alkoxy chains at each terminal self-organise into columnar liquid crystalline phases, and one-dimensional columnar stacks can be oriented uniaxially by mechanical shearing in the mesophases.     

Columnar liquid crystalline bis-N-annulated quaterrylenes

Columnar liquid crystalline bis-N-annulated quaterrylenes have been prepared from readily available N-annulated perylenes by DDQ/Sc(OTf)(3) oxidative coupling and ring-fusion.     

Heterotrimeric liquid crystalline thiadiazole derivatives

Abstract

Various trimeric co-oligomers combining 2-phenyl-1,3,4-thiadiazole mesogenic moieties with a biphenyl mesogenic moiety were synthesized and their mesomorphic behaviour investigated by polarizing microscopy, calorimetry and X-ray scattering. Such co-oligomeric structures provide an opportunity to combine different mesogenic units. Thus readily accessible homochiral biphenyl mesogenic units were connected with thiadiazole mesogenic units leading to an oligomeric liquid crystal material with ferroelectric properties.     

Electroluminescent segmented liquid crystalline trimers

The synthesis and liquid crystal behaviour of light‐emitting trimeric liquid crystals consisting of three mesomorphic moieties connected by aliphatic spacers are reported. The combination of an aromatic light‐emitting central core and two cholestanyl (dihydrocholesteryl) groups induces a helical liquid crystalline phase with circularly polarised photoluminescence and electroluminescence. These segmented trimers are designed to possess a high glass transition temperature below which the structure of liquid crystalline phases can be fixed. The effects of odd and even spacers, spacer length and the presence of large lateral substituents on the liquid crystal behaviour and the glass transition temperature of these trimers were studied. Electroluminescence from a segmented liquid crystalline trimer is reported for the first time.     

Heterotrimeric liquid crystalline thiadiazole derivatives

Various trimeric co-oligomers combining 2-phenyl-1,3,4-thiadiazole mesogenic moieties with a biphenyl mesogenic moiety were synthesized and their mesomorphic behaviour investigated by polarizing microscopy, calorimetry and X-ray scattering. Such co-oligomeric structures provide an opportunity to combine different mesogenic units. Thus readily accessible homochiral biphenyl mesogenic units were connected with thiadiazole mesogenic units leading to an oligomeric liquid crystal material with ferroelectric properties.     

Deuterium labelled liquid crystalline compounds

Abstract

The synthesis of 4-(2′-methylbutyl)phenyl4′n-heptylbiphenyl-4-carboxylate-d ₁₈(7BEF5-d ₁₈) is presented. The compound is intended to be used as a means of studying the collective modes of liquid crystals by the coherent inelastic neutron scattering technique. The 4′-n-heptylbiphenyl-4-carboxylic acid-d ₁₂, a liquid crystalline intermediate was prepared as well; its acid chloride was coupled with 4-(2′-methylbutyl)phenol-d ₆ to obtain the final product. The intermediates and final products were investigated by spectroscopic methods.     

Fluorescent ferroelectric liquid crystalline copolyacrylates

Fluorescent liquid crystalline side chain polymers were synthesized by copolymerization of a ferroelectric monomer and 5 per cent of various blue fluorescent naphthalic imide dye comonomers. Those copolymers were characterized by DSC, X-ray, GPC and optical microscopy. In favourable cases, fast switching fluorescent ferroelectric polymers resulted, exhibiting high tilt angles (up to ∼ 34°) and spontaneous polarization values (up to ∼ 115 nC cm^-2) in the S*_c phase. One fluorescent copolymer shows orthogonal smectic phases exclusively due to the structure of the incorporated fluorescent comonomer. In this case a strong electroclinic effect and high induced tilt angles (12° 10 V μm^-1) have been observed in the S_a phase. Order parameters, S, of the dye moieties up to 0.64 were measured in the room temperature S_b phase for the copolymers     

Lyotropic liquid crystalline phases formed in an ionic liquid

Lyotropic liquid crystalline phases of an amphiphilic block copolymer are constructed and characterized in an ionic liquid with comparison of component and temperature effects.     

Broad liquid crystalline temperature range of ferroelectric liquid crystals

Novel ferroelectric liquid crystalline compounds, containing the (S)-2-methyl-l -butyl (4-hydroxybiphenyl-4'-carbonyloxy)biphenyl-4-carboxylate mesogenic group and an oligooxyethylene spacer, were synthesized. The mesomorphic properties of these materials were investigated by differential scanning calorimetry (DSC), optical polarizing microscopy (POM) and powder X-ray diffraction measurement. The results indicate that all members of this series exhibit a very broad temperature mesophase range (reaching a maximum around 210°C) including a blue phase (BP), cholesteric (Ch), twist grain boundary A (TGB_A), chiral smectic C (S*_c), and smectic X (S_x) phases. The mesomorphic properties are discussed and a comparison is made with three phenyl rings of ester core analogues.     

Effect of ionic aggregates of sulphonate groups on the liquid crystalline behaviours of liquid crystalline elastomers

A series of siloxane-based liquid crystalline elastomers containing biphenyl benzoate mesogenic units and ionic Brilliant Yellow moieties was synthesized. The chemical structures and liquid crystalline properties of the samples were characterized by FTIR, ¹H NMR, DSC, POM and XRD. The effective crosslink density of the ionic elastomers was determined by swelling experiments in organic/buffer mixtures. All the polymers displayed a smectic mesophase. It was shown that the glass transition and melting point temperatures of the polymers increased slightly with increasing content of ionic and mesogenic groups in the polymers, while the liquid crystal mesophase region decrease slightly.     

Photoluminescent nematic liquid crystalline elastomer actuators

Nematic liquid crystalline elastomer (LCE) actuators possessing both photoluminescent (PL) and stimuli-responsive functions were fabricated and studied. PL-dyes (1-pyrenemethyl acrylate and 4-bromo-2,6-bis-(1?-methyl-benzimidazolyl) pyridine loaded with Eu(III) ion) were synthesised and characterised, and then the dyes were mixed with an acrylate side-on liquid crystalline monomer, a cross-linker and a photo-initiator. Through magnetic field alignment, well-defined LCE micropillar PL actuators were fabricated from the mixed samples by a method combining soft lithography and photo-polymerisation/photo-cross-linking. Microscopic observations indicated that the LCE micropillars showed reversible thermomechanical deformation at the nematic-to-isotropic transition temperature. During the reversible contraction and extension process, the LCE actuator containing 1-pyrenemethyl moieties showed stable photoluminescence, while for the LCE actuator doped with 4-bromo-2,6-bis-(1-methyl-benzimidazolyl)pyridine/Eu(III) complex, the PL emission was quenched at about 100°C, which was before the pillars contraction occurring at a higher temperature. When cooled down to room temperature, the contracted LCE micropillars recovered their original shape and the initial PL emission state. The micron-sized LCE actuators can be used for thermomechanical devices and machines with different PL functions at the same time.     

Self-assembled bent-core side-chain liquid crystalline polymers

The synthesis of H-bonded bent-core side-chain liquid crystal polymers carried out by two alternative synthetic routes and their properties are reported.