High pressure phase studies of some liquid crystalline cyclohexane derivatives by differential thermal analysis

T(p) phase diagrams for the mesomorphic compounds trans-4-n-butylcyclohexane-1-carboxylic acid 4-cyanophenyl ester (D4N), trans4-n-pentylcyclohexane-1-carboxylic acid 4-n-pentylphenyl ester (D55), trans-4,4'-di-n-propyl-1,1-bicyclohexyl-cis-4-carbonitrile (33CCN), trans-4-methoxy-4'-propyl-1,1'-bicyclohexane (3O1CCH) and trans-4-methoxy-4'-n-butyl-1,1'-bicyclohexane (4O1CCH) are presented. The experiments were performed using high pressure microcomputer-assisted differential thermal analysis equipment in the temperature range 300 to 500 K up to a maximum pressure of 8 kbar. Some special high pressure effects for liquid crystals, such as pressure-induced or pressure-limited phases and changes from monotropic to enantiotropic polymorphism were observed. For the correlation of the experimental results, an extension of the Simon equation was used; one of the regression parameters of the clearing curve equation was found to be correlated with the molecular structure of the liquid crystal substances under test.     

Photoisomerization-induced stable liquid crystalline cubic blue phase

We have succeeded in obtaining a photoinduced liquid crystalline cubic BP in a mixture of photoinactive and photoresponsive bent-core mesogens. The UV stimulus can convert N* to cubic BP through photoisomerization of the azobenzene linkages included in the photoresponsive bent-core molecule.     

Biaxial smectic phases in non-linear optical properties and phase behaviour of an oxdiazole liquid crystal

A symmetric, low-molecular-mass liquid crystal based on the oxadiazole ring was synthesized and characterized. The symmetric position of the heterocyclic group in the centre of the liquid crystal, bis(4-hexyloxyphenyl)4,4-(1,3,4-oxadiazole-2,5-diyl)dicarboxylate, yields a very rigid and non-linear mesogenic core. Despite this non-linear structure, a broad liquid crystalline range with a smectic C and a smectic A phase was found. Conoscopic experiments on freely suspended films revealed the existence of two optical axes in the smectic A phase, indicating a phase symmetry anticipated for either a 'McMillan' biaxial smectic phase or a biaxial (achiral) ferroelectric smectic phase.     

DNA liquid crystalline blue phases. Electron microscopy evidence and biological implications

The isotropic-liquid crystalline transition of concentrated DNA solutions is investigated using freeze-fracture electron microscopy in order to understand the first steps of the DNA condensation process. Between the isotropic liquid and the cholesteric mesophase, we report the existence of double twist DNA bundles and describe their long range ordering into 3D networks. This organization corresponds to the formation of 'blue phases' already observed in thermotropic liquid crystals, but never reported in lyotropic systems. In addition, the size of the DNA molecule, about ten times that of most thermotropic materials, allows here the molecular resolution imaging of blue phase structures. Since such structures recall chromatin organization of some Procaryotes and lower Eucaryotes, we suspect that they may be widespread and of potential interest in the regulation of chromatin functions.     

Lyotropic liquid crystalline phase behaviour in amphiphile-protic ionic liquid systems

Approximate partial phase diagrams for nine amphiphile-protic ionic liquid (PIL) systems have been determined by synchrotron source small angle X-ray scattering, differential scanning calorimetry and cross polarised optical microscopy. The binary phase diagrams of some common cationic (hexadecyltrimethyl ammonium chloride, CTAC, and hexadecylpyridinium bromide, HDPB) and nonionic (polyoxyethylene (10) oleyl ether, Brij 97, and Pluronic block copolymer, P123) amphiphiles with the PILs, ethylammonium nitrate (EAN), ethanolammonium nitrate (EOAN) and diethanolammonium formate (DEOAF), have been studied. The phase diagrams were constructed for concentrations from 10 wt% to 80 wt% amphiphile, in the temperature range 25 °C to >100 °C. Lyotropic liquid crystalline phases (hexagonal, cubic and lamellar) were formed at high surfactant concentrations (typically >50 wt%), whereas at <40 wt%, only micelles or polydisperse crystals were present. With the exception of Brij 97, the thermal stability of the phases formed by these surfactants persisted to temperatures above 100 °C. The phase behaviour of amphiphile-PIL systems was interpreted by considering the PIL cohesive energy, liquid nanoscale order, polarity and ionicity. For comparison the phase behaviour of the four amphiphiles was also studied in water.     

The phase behaviour and optical properties of a nematic/chiral dopant liquid crystalline mixture system

The phase behaviour and aggregation states of a binary mixture of a nematic liquid crystal and a chiral dopant have been investigated. The nematic liquid crystal E7 was miscible with the chiral dopant S811 over their entire concentration range. Binary E7/S811 mixtures formed the N* phase for S811 contents under 20%, and the SmA* phase for S811 contents between 40% and 90%. BP and TGBA* frustrated phases were found during cooling, for S811 contents between 25% and 35%. The helical pitches of the binary mixtures decreased with increasing chiral dopant content. From XRD profiles, the orientational ordering of the binary composites was found to increase with increasing chiral dopant content.     

Synthesis and characterization of side chain liquid crystalline polymers exhibiting cholesteric and blue phases

A series of cyclosiloxane-based cholesteric liquid crystalline (LC) polymers were synthesized from a cholesteric LC monomer cholest-5-en-3-yl(3β) 4-(2-propenyloxy)benzoate and a nematic LC monomer butyl 4-[4-(2-propenyloxy)benzoxy]benzoate. All the polymers exhibit thermotropic LC properties and show cholesteric phases. Most of the polymers display four types of phase transition behaviour corresponding to glass transition, melting point, cholesteric phase-blue phase transition and clearing point. The mesophase temperature range of the blue phases are as broad as 20°C. The blue phase was confirmed by the apperance of planar textures and cubic packings. With an increase of non-chiral component in the polymers, the clearing point decreases slightly, while the glass transition and melting temperatures change little. In the reflection spectra of the polymer series the reflected wavelength broadens and shifts to longer wavelength with increase of the non-chiral component in the polymer systems, suggesting that the helical pitch P lengthens.     

Layer frustration, polar order and chirality in liquid crystalline phases of silyl-terminated achiral bent-core molecules

A novel class of bent-core molecules with oligo(siloxane) or carbosilane units at both ends was synthesized and the self-organization of these molecules was investigated by polarizing microscopy, DSC, X-ray scattering, dielectric and electrooptical methods. Depending on the size of the silicon-containing segments, smectic and columnar liquid crystalline phases are formed. Most smectic phases are low birefringent and composed of macroscopic domains of opposite handedness (dark conglomerate phases). The switching process in these smectic phases is surface stabilized ferroelectric and, depending on the conditions, two distinct slow relaxation processes to nonpolar structures were observed. It is proposed that the smectic phases are built up by chiral and polar SmCsPF layer stacks which are separated by anticlinic interfaces. If the size of these layer stacks is sufficiently large a coupling to the substrate surfaces takes place and ferroelectric switching is observed. It is also suggested that the sponge-like layer distortion, occurring in the low birefringent mesophases, is due to an escape from the local polar order within these SmCsPF layer stacks. For compounds with larger silylated units a steric frustration arises, which leads to layer modulation (columnar ribbon phases) and this is associated with a transition from ferroelectric to antiferroelectric switching. All compounds show a switching of the molecules around the long axis which reverses the layer chirality.     

Optical and mesomorphic properties characterisation of chiral liquid crystalline copolysiloxane exhibiting cholesteric and blue phases

A series of liquid crystalline polymers (LCPs) have been synthesised by two cholesteric monomers M₁, M₂ and a nematic monomer M₃. The chemical structures and liquid crystalline properties of the monomers and polymers have been characterised by FTIR, ¹H-NMR, differential scanning calorimetry, thermogravimetric analyses, X-ray diffraction measurements and polarising optical microscopy. All LCPs show a high thermal stability with wide mesophase temperature ranges. For polymer P₁ bearing only cholesteric LC monomers component, it shows a cholesteric phase, whereas others display a blue phase besides a cholesteric phase. The formation of the blue phase is based on the structures of the polymers and the produced biaxial helix. The glass transition temperature and isotropic temperature of the polymers decrease on heating cycle with increasing the content of M₃ in the polymers. The specific rotation values of the polymers are temperature-sensitive. The reflection spectra of polymers P₁–P₆ show that the maximum reflected wavelengths shift to long wavelength with increasing the content of M₃ in the polymer systems. The frequency and intensity of the bands change sharply at the temperature where cholesteric phase changes to blue phase, but they show a weak dependence on temperature in the blue phase.     

Side chain cholesteric liquid crystalline elastomers: synthesis and phase behaviour

A series of new side chain cholesteric liquid crystalline elastomers (P-2–P-6) containing the nematic crosslinking monomer 4-(10-undecen-1-yloyloxy)benzoyl-4′-allyloxybenzoyl-p-benzenediol bisate (M-1) and the cholesteric monomer 4-cholesteryl 4-(10-undecen-1-yloyloxy)benzoate (M-2) were synthesized. The chemical structures of the monomers and elastomers obtained were confirmed by FTIR and ¹H NMR spectroscopy. Their liquid crystalline properties and phase behaviour were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. The effect of the crosslinking units on phase behaviour is discussed. Elastomers containing less than 20?mol?% of the crosslinking units showed elasticity, reversible phase transitions and cholesteric Grandjean texture. The experimental results demonstrated that the glass transition and isotropization temperatures of P-2–P-6 increased with the increasing concentration of crosslinking unit M-1.     

Cyclic versus linear siloxane liquid crystalline oligomers: phase behaviour

The phase behaviour of cyclic and linear liquid crystalline polysiloxanes containing two different cholesteric mesogens is reported. The thermal properties of the synthesized monomers and oligomers were investigated by polarizing optical microscopy and differential scanning calorimetry. The influence of the structure of cyclic siloxane on the mesomorphic properties of cyclic liquid crystalline polysiloxanes is discussed. Similar trends in the thermal transitions of cyclic and linear compounds containing the same mesogenic composition were observed, though the cyclic oligomers showed poorer mesomorphic properties as compared with their linear analogues.     

Side chain cholesteric liquid crystalline elastomers: synthesis and phase behaviour

A series of new side chain cholesteric liquid crystalline elastomers (P-2-P-6) containing the nematic crosslinking monomer 4-(10-undecen-1-yloyloxy)benzoyl-4'-allyloxybenzoyl-p-benzenediol bisate (M-1) and the cholesteric monomer 4-cholesteryl 4-(10-undecen-1-yloyloxy)benzoate (M-2) were synthesized. The chemical structures of the monomers and elastomers obtained were confirmed by FTIR and ¹H NMR spectroscopy. Their liquid crystalline properties and phase behaviour were investigated by differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction. The effect of the crosslinking units on phase behaviour is discussed. Elastomers containing less than 20 mol % of the crosslinking units showed elasticity, reversible phase transitions and cholesteric Grandjean texture. The experimental results demonstrated that the glass transition and isotropization temperatures of P-2-P-6 increased with the increasing concentration of crosslinking unit M-1.     

Cyclic versus linear siloxane liquid crystalline oligomers: phase behaviour

The phase behaviour of cyclic and linear liquid crystalline polysiloxanes containing two different cholesteric mesogens is reported. The thermal properties of the synthesized monomers and oligomers were investigated by polarizing optical microscopy and differential scanning calorimetry. The influence of the structure of cyclic siloxane on the mesomorphic properties of cyclic liquid crystalline polysiloxanes is discussed. Similar trends in the thermal transitions of cyclic and linear compounds containing the same mesogenic composition were observed, though the cyclic oligomers showed poorer mesomorphic properties as compared with their linear analogues.     

The effect of an electric field on the selective reflection bands of liquid crystalline blue phases

The effect of an electric field on the Bragg reflection of the liquid-crystalline cubic blue phases BPI and II has been studied. The results can be explained by a reorientation of the cubic BP lattice in the electric field. A BP II/I phase transition cannot be induced by the field in the systems under examination.     

Mesomorphic phase transition behaviour of photopolymerisable liquid crystalline triphenylene ether compounds

This report discusses the preparation and the unusual mesomorphism of three homologues of photopolymerisable triphenylene ether compounds. These homologues showed ‘a cold crystallisation’ on heating differential scanning calorimetry curves, and this phenomenon is attenuated with increase methylene units, spacers between the triphenylene core and the terminal photopolymerisable acrylate group. Classical textures of hexagonal columnar (Col_h) mesophase were observed by polarising optical microscopy for all three photopolymerisable mesophase compounds described here. Also described is the mesomorphism of their intermediates, hydroxylalkoxytriphenylenes. In some cases, the discotic columnar hexagonal mesophases were confirmed by wide angle X-ray scattering techniques.     

Emulsified microemulsions and oil-containing liquid crystalline phases

Self-assembled nanostructures, such as inverted type mesophases of the cubic or hexagonal geometry or reverse microemulsion phases, can be dispersed using a polymeric stabilizer, such as the PEO-PPO-PEO triblock copolymer Pluronic F127. The particles, which are described in the present study, are based on monolinolein (MLO)-water mixtures. When adding tetradecane (TC) to the MLO-water-F127 system at constant temperature, the internal nanostructure of the kinetically stabilized particles transforms from a Pn3m (cubosomes) to a H2 (hexosomes) and to a water-in-oil (W/O, L2) microemulsion phase (emulsified microemulsion (EME)). To our knowledge, this is the first time that the formation of stable emulsified microemulsion (EME) systems has been described and proven to exist even at room temperature. The same structural transitions can also be induced by increasing temperature at constant tetradecane content. The internal nanostructure of the emulsified particles is probed using small-angle X-ray scattering (SAXS) and cryogenic transmission electron microscopy (cryo-TEM). At each investigated composition and temperature, the internal structure of the dispersions is observed to be identical to the corresponding structure of the nondispersed, fully hydrated bulk phase. This is clear evidence for the fact that the self-assembled inner particle nanostructure is preserved during the dispersion procedure. In addition, the internal structure of the particles is in thermodynamic equilibrium with the surrounding water phase. The internal structure of the dispersed, kinetically stabilized particles is a "real" and stable self-assembled nanostructure. To emphasize this fact, we denoted this new family of colloidal particles (cubosomes, hexosomes, and EMEs) as "ISASOMES" (internally self-assembled particles or "somes").     

Spontaneous formation of liquid crystalline phases and phase transitions in highly concentrated plasmid DNA

The liquid crystalline (LC) properties of two supercoiled plasmid DNA samples, pBSK (2958 bp) and pGEM (3000 bp), have been studied using polarised light microscopy (PLM), circular dichroism (CD) and UV–Vis spectroscopy. The influence of methods of isolation on plasmid LC behaviour is described, and using PLM we have demonstrated the spontaneous formation of cholesteric fingerprint-like textures. Preliminary studies of LC phase transitions in pGEM show the irreversibility of LC phase formation, as a consequence of changes in the tertiary structure of supercoiled plasmids. Using UV–Vis spectroscopy a hyperchromic effect was observed with increasing temperature. The CD spectra clearly showed structural changes, and probably mismatching of DNA bases, during cooling. Finally, we have observed an irreversible phase transition in plasmid DNA which is very different from that previously reported in linear DNA.     

Observation of an electric field-induced metastable blue phase in supercooled liquid crystalline systems

In this preliminary communication, the influence of an electric field on the metastable blue phase BPS is reported. Experiments involved both supercooling of the BPI at constant applied field and increasing the electric field strength applied to BPS at constant temperature, and resulted in the observation of a new field induced metastable phase BPES.