Chiral Nematic Phase Research Articles

A Liquid Crystalline Oligomer Exhibiting Nematic and Twist-Bend Nematic Mesophases.

The twist-bend nematic phase (NTB ) has been described as the structural link between the untilted uniaxial nematic phase (N) and the helical chiral nematic phase (N*). The NTB phase exhibits phenomena of fundamental importance to science, that is, 1) the spontaneous formation of a helical pitch on the nanometer scale in a fluid and 2) the spontaneous breaking of mirror symmetry, leading to the emergence of chiral domains in an achiral system. In this Communication, we present a study on T49 [bis(4-(9-(4-((4-cyanobenzoyl)oxy)phenyl)nonyl)phenyl) 4,4'-(nonane-1,9-diyl)dibenzoate], a liquid-crystalline oligomer exhibiting the twist-bend nematic phase, which has a molecular length that is of comparable dimensions to the sub-10 nm pitch determined for CB9CB, and provide new insights into the differentiation between the nano- and macro-science for self-assembling supermolecular systems.

Tailoring of cholesteric plane spacing, dielectric relaxation and optical properties of high temperature chiral nematic phase by UV irradiation

The effect of Ultra Violet (UV) irradiation on the high temperature chiral nematic (N*) mesophase has been investigated. The controlled UV exposure produced bending in rod shape molecules. The bending of molecules affects their long molecular axis; therefore, the relaxation mode associated with the rotation of molecules along the long molecular axis shifts toward the higher frequency. The UV irradiation also increases the cholesteric plane spacing of N*LC molecules. The a.c. conductivity of N*LC has been increased enormously after UV irradiation. The efficiency of opto-dielectric effect has also been evaluated with the variation of bias voltage in the present investigation.

Non-symmetric chiral liquid crystal dimers. Preparation and characterisation of the (S)-(benzylidene-4′-substitutedaniline)-2″-methylbutyl-4‴-(4″″-phenyloxy)-benzoateoxy)hexanoates

The properties of six chiral non-symmetric dimers belonging to the family of (S)-(benzylidene-4′-substitutedaniline)-2″-methylbutyl-4‴-(4″″-phenyloxy)benzoate-oxy)hexanoates are described. The terminal substituents on the 4-benzylidene-4′-substituted fragment are H, Cl, Br, I, CH3 and C2H5. All six dimers exhibit an enantiotropic chiral nematic phase. The relationship between the chiral nematic-isotropic transition temperature and the terminal substituent is discussed in terms of the size of the substituent and its effect of the molecular shape, and its ability to interact with mesogenic group to which it is attached. The C2H5-substituted dimer also shows an enantiotropic monolayer chiral smectic C phase, the formation of which is attributed to the enhanced molecular inhomogeneity arising from the longer alkyl chain. The weak smectic tendencies seen for the halogen-substituted dimers are attributed to potentially repulsive interactions between the ester links that would occur in an intercalated smectic arrangement which would be expected for dimers of this type.

Significant Enhancement of the Chiral Correlation Length in Nematic Liquid Crystals by Gold Nanoparticle Surfaces Featuring Axially Chiral Binaphthyl Ligands.

Chirality is a fundamental scientific concept best described by the absence of mirror symmetry and the inability to superimpose an object onto its mirror image by translation and rotation. Chirality is expressed at almost all molecular levels, from single molecules to supramolecular systems, and present virtually everywhere in nature. Here, to explore how chirality propagates from a chiral nanoscale surface, we study gold nanoparticles functionalized with axially chiral binaphthyl molecules. In particular, we synthesized three enantiomeric pairs of chiral ligand-capped gold nanoparticles differing in size, curvature, and ligand density to tune the chirality transfer from nanoscale solid surfaces to a bulk anisotropic liquid crystal medium. Ultimately, we are examining how far the chirality from a nanoparticle surface reaches into a bulk material. Circular dichroism spectra of the gold nanoparticles decorated with binaphthyl thiols confirmed that the binaphthyl moieties form a cisoid conformation in isotropic organic solvents. In the chiral nematic liquid crystal phase, induced by dispersing the gold nanoparticles into an achiral anisotropic nematic liquid crystal solvent, the binaphthyl moieties on the nanoparticle surface form a transoid conformation as determined by imaging the helical twist direction of the induced cholesteric phase. This suggests that the ligand density on the nanoscale metal surfaces provides a dynamic space to alter and adjust the helicity of binaphthyl derivatives in response to the ordering of the surrounding medium. The helical pitch values of the induced chiral nematic phase were determined, and the helical twisting power (HTP) of the chiral gold nanoparticles calculated to elucidate the chirality transfer efficiency of the binaphthyl ligand capped gold nanoparticles. Remarkably, the HTP increases with increasing diameter of the particles, that is, the efficiency of the chirality transfer of the binaphthyl units bound to the nanoparticle surface is diminished as the size of the particle is reduced. However, in comparison to the free ligands, per chiral molecule all tested gold nanoparticles induce helical distortions in a 10- to 50-fold larger number of liquid crystal host molecules surrounding each particle, indicating a significantly enhanced chiral correlation length. We propose that both the helicity and the chirality transfer efficiency of axially chiral binaphthyl derivatives can be controlled at metal nanoparticle surfaces by adjusting the particle size and curvature as well as the number and density of the chiral ligands to ultimately measure and tune the chiral correlation length.

Blue phase liquid crystals affected by graphene oxide modified with aminoazobenzol group

ABSTRACTLiquid-crystalline blue phases (BPs) are stable only for very narrow temperature range between the isotropic and the chiral nematic phase that severely hinders their applicability. Herein, the aminoazobenzol group was chemically grafted onto epoxy group of graphene oxide (GO) via addition reaction. Successful grafting of aminoazobenzol group was confirmed using X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectroscopy (FTIR), UV–vis absorption spectra and thermogravimetric analysis (TGA). The resultant aminoazobenzol group–modified GO sheets, which is reduced (RGO-Az), were easily redispersable in common organic solvents or liquid crystals (LCs). By doping different contents of RGO-Az, nanosheets could stabilise BP and increase the BP range. When doped with 0.5 wt% RGO-Az, the mixtures show the wider range with 5.9°C than the range with 3.6°C of BPLCs without RGO-Az. Meanwhile, the phase sequence and the range of the aforementioned phases are reproducible upon heating and cooling, which shows that the BPs doped with RGO-Az nanosheets are thermodynamically stable.

Into the polymer brush regime through the "grafting-to" method: densely polymer-grafted rodlike viruses with an unusual nematic liquid crystal behavior.

The current work reports an intriguing discovery of how the force exerted on protein complexes like filamentous viruses by the strong interchain repulsion of polymer brushes can induce subtle changes of the constituent subunits at the molecular scale. Such changes transform into the macroscopic rearrangement of the chiral ordering of the rodlike virus in three dimensions. For this, a straightforward "grafting-to" PEGylation method has been developed to densely graft a filamentous virus with poly(ethylene glycol) (PEG). The grafting density is so high that PEG is in the polymer brush regime, resulting in straight and thick rodlike particles with a thin viral backbone. Scission of the densely PEGylated viruses into fragments was observed due to the steric repulsion of the PEG brush, as facilitated by adsorption onto a mica surface. The high grafting density of PEG endows the virus with an isotropic-nematic (I-N) liquid crystal (LC) phase transition that is independent of the ionic strength and the densely PEGylated viruses enter into the nematic LC phase at much lower virus concentrations. Most importantly, while the intact virus and the one grafted with PEG of low grafting density can form a chiral nematic LC phase, the densely PEGylated viruses only form a pure nematic LC phase. This can be traced back to the secondary to tertiary structural change of the major coat protein of the virus, driven by the steric repulsion of the PEG brush. Quantitative parameters characterising the conformation of the grafted PEG derived from the grafting density or the I-N LC transition are elegantly consistent with the theoretical prediction.

Chiral all-organic nitroxide biradical liquid crystals showing remarkably large positive magneto-LC effects.

The liquid crystalline chiral nitroxide biradical (S,S,S,S)-3 synthesized has shown much larger 'positive magneto-LC effects' in the chiral nematic (N*) phase than the monoradical (S,S)-1.

Intercalated soft-crystalline mesophase exhibited by an unsymmetrical twist-bend nematogen

A number of new states of matter have been reported in recent years for liquid crystal dimers, most notably the twist-bend nematic phase which exhibits spontaneous breaking of symmetry through the emergence of chiral structures in an achiral fluid. In this communication we report on an unsymmetrical liquid crystal dimer that exhibits a transition from the spontaneously chiral twist-bend nematic phase into a novel smectic liquid crystal phase.

Supramolecular ordered photochromic cholesteric polymers as smart labels for thermal monitoring applications

New reversible temperature-sensitive polymeric materials with a broad window of trigger temperatures were developed for application as thermal monitoring smart labels for perishable commodities. In particular new liquid crystalline copolymers functionalized with azoaromatic chromophores and chiral cholesteric moieties were synthesized by Controlled Radical Polymerization (CRP) using cheap and easily available reagents and mild reaction conditions. These materials exhibit a chiral nematic phase (N*) with an intense Bragg reflection which gives an iridescent and bright appearance to their thick films. By inducing the azoaromatic trans-cis isomerization through UV irradiation, it is possible to break the native chiral supramolecular conformational order thus leading to an amorphous transparent phase which is characterized by different UV–Vis and CD spectra and which is stable whilst the temperature is kept below the Tg of the polymer. Hence, tags can be reused even though the required process is so specific that they cannot be easily tampered. Thus, owing to the high control of the polymer molecular weight and structure allowed by the ATRP technique, it is possible to finely tune the trigger temperature and the photoswitchable properties thus allowing the fabrication of tailor made labels suitable for a huge variety of products with potential applications as sensors and in photonic and display fields.

ChemInform Abstract: Olefin Cross‐Metathesis: A Versatile Synthetic Reaction for the Design of Janus Liquid Crystals.

The olefin cross-metathesis reaction using the second-generation Grubbs catalyst was employed to prepare non-symmetrical thermotropic liquid crystals from various mesomorphic or nonmesomorphic type I and type II olefinic constructs, including linear, chiral, dendritic and ferrocenyl olefins. Smectic C, smectic A and nematic phases, as well as chiral smectic A and chiral nematic phases were observed in agreement with the structure and nature of the mesogens. The olefin cross-metathesis proved to be a valuable chemical reaction in designing dimeric and Janus-like thermotropic liquid crystals built from two different molecular entities.

Chiral Nematic Structure of Cellulose Nanocrystal Suspensions and Films; Polarized Light and Atomic Force Microscopy.

Cellulosic liquid crystalline solutions and suspensions form chiral nematic phases that show a rich variety of optical textures in the liquid crystalline state. These ordered structures may be preserved in solid films prepared by evaporation of solvent or suspending medium. Film formation from aqueous suspensions of cellulose nanocrystals (CNC) was investigated by polarized light microscopy, optical profilometry and atomic force microscopy (AFM). An attempt is made to interpret qualitatively the observed textures in terms of the orientation of the cellulose nanocrystals in the suspensions and films, and the changes in orientation caused by the evaporative process. Mass transfer within the evaporating droplet resulted in the formation of raised rings whose magnitude depended on the degree of pinning of the receding contact line. AFM of dry films at short length scales showed a radial orientation of the CNC at the free surface of the film, along with a radial height variation with a period of approximately P/2, ascribed to the anisotropic shrinkage of the chiral nematic structure.

Pure Anisotropic Hydrogel with an Inherent Chiral Internal Structure Based on the Chiral Nematic Liquid Crystal Phase of Rodlike Viruses.

Imparting ordered structures into otherwise amorphous hydrogels is expected to endow these popular materials with novel multiple-stimuli responsiveness that promises many applications. The current contribution reports a method to fabricate pure polymeric hydrogels with an inherent chiral internal structure by templating on the chiral nematic liquid crystal phase of a rodlike virus. A method was developed to form macroscopically homogeneous chiral templates by confinement induced self-assembly in the presence of monomers, cross-linkers and initiators. Polymerization induced gelation was performed without perturbing the elegant 3D chiral organization of the rodlike virus bearing double bonds. Furthermore, a suitable method was found to remove the organic virus template while keeping the desired polymeric replica intact, resulting in a pure polymeric hydrogel with a unique internal chiral feature that originates from the 3D chiral ordering of the cylindrical pores left by the virus. Multiple-stimuli responsiveness has been demonstrated and can be quantified by the change of the pitch of the chiral feature. The chiral structure endows the otherwise featureless hydrogel with a unique material property that might be used as a readout signal for sensing and acts as the basis for responsive, biomimetic nanostructured materials.

A cellulosic liquid crystal pool for cellulose nanocrystals: Structure and molecular dynamics at high shear rates

Cellulose and its derivatives, such as hydroxypropylcellulose (HPC) have been studied for a long time but they are still not well understood particularly in liquid crystalline solutions. These systems can be at the origin of networks with properties similar to liquid crystalline (LC) elastomers. The films produced from LC solutions can be manipulated by the action of moisture allowing for instance the development of a soft motor (Geng et al., 2013) driven by humidity. Cellulose nanocrystals (CNC), which combine cellulose properties with the specific characteristics of nanoscale materials, have been mainly studied for their potential as a reinforcing agent. Suspensions of CNC can also self-order originating a liquid–crystalline chiral nematic phases. Considering the liquid crystalline features that both LC-HPC and CNC can acquire, we prepared LC-HPC/CNC solutions with different CNC contents (1, 2 and 5wt.%). The effect of the CNC into the LC-HPC matrix was determined by coupling rheology and NMR spectroscopy – Rheo-NMR a technique tailored to analyse orientational order in sheared systems.

PA25 液晶場における反応性キラルドーパントの挙動(液晶化学材料,ポスター発表,2015年日本液晶学会討論会)

PA25 液晶場における反応性キラルドーパントの挙動(液晶化学材料,ポスター発表,2015年日本液晶学会討論会)

Olefin Cross‐Metathesis: a Versatile Synthetic Reaction for the Design of Janus Liquid Crystals

AbstractThe olefin cross‐metathesis reaction using the second‐generation Grubbs catalyst was employed to prepare non‐symmetrical thermotropic liquid crystals from various mesomorphic or nonmesomorphic type I and type II olefinic constructs, including linear, chiral, dendritic and ferrocenyl olefins. Smectic C, smectic A and nematic phases, as well as chiral smectic A and chiral nematic phases were observed in agreement with the structure and nature of the mesogens. The olefin cross‐metathesis proved to be a valuable chemical reaction in designing dimeric and Janus‐like thermotropic liquid crystals built from two different molecular entities.

A Twist-Bend Nematic (NTB ) Phase of Chiral Materials.

New chiral dimers consisting of a rod-like and cholesterol mesogenic units are reported to form a chiral twist-bend nematic phase (NTB *) with heliconical structure. The compressibility of the NTB phase made of bent dimers was found to be as large as in smectic phases, which is consistent with the nanoperiodic structure of the NTB phase. The atomic force microscopy observations in chiral bent dimers revealed a periodicity of about 50 nm, which is significantly larger than the one reported previously for non-chiral compounds (ca. 10 nm).

Lattice structure in liquid-crystal blue phase with various chiral concentrations

Lattice structures, including reflection lattice planes and lattice constant, of liquid-crystal blue phase I (BPI) are studied via the measurements on reflection spectrum and Kossel diagram as concentration of a chiral dopant is changed. Peaks of the reflection wavelength in BPI are mainly dominated by the lattice plane and the lattice constant, which are affected by the chiral concentration. In the chiral nematic state, as decreasing the chiral concentration the reflection peak will shift to a longer wavelength because the helical pitch linearly depends on the chiral concentration and becomes longer. However, this dependence of the chiral concentration and reflection wavelength is broken in the BPI. The reflection peak of BPI moves to a short wavelength when the chiral concentration is less due to the contraction of the lattice constant as well as helical pitch. Moreover, when the concentration of the chiral dopant increases over a certain value, a discontinuous shift in reflection peak occurs due to the production of the different lattice planes. It means that the relationship between the chiral concentration and the helical pitch in BPI is not the same as it in the chiral nematic phase and should be reconsidered.

Rod Packing in Chiral Nematic Cellulose Nanocrystal Dispersions Studied by Small-Angle X-ray Scattering and Laser Diffraction.

The packing of cellulose nanocrystals (CNC) in the anisotropic chiral nematic phase has been investigated over a wide concentration range by small-angle X-ray scattering (SAXS) and laser diffraction. The average separation distance between the CNCs and the average pitch of the chiral nematic phase have been determined over the entire isotropic-anisotropic biphasic region. The average separation distances range from 51 nm, at the onset of the anisotropic phase formation, to 25 nm above 6 vol % (fully liquid crystalline phase) whereas the average pitch varies from ≈15 μm down to ≈2 μm as ϕ increases from 2.5 up to 6.5 vol %. Using the cholesteric order, we determine that the twist angle between neighboring CNCs increases from about 1° up to 4° as ϕ increases from 2.5 up to 6.5 vol %. The dependence of the twisting on the volume fraction was related to the increase in the magnitude of the repulsive interactions between the charged rods as the average separation distance decreases.

Development and applications of cholesteric liquid crystals

The development and realisation of applications utilising the cholesteric or chiral nematic phase have benefited from the materials research work carried out by George Gray and his colleagues. His work on cholesteric materials started in the 1950s with the synthesis of cholesteryl esters and the observation in them of an unusual blue fog phase which he later studied in more detail. He went on to identify the molecular features that give rise to the characteristic cholesteric helical structure and the role of molecular structure and chirality on the properties of the cholesteric phase. This pioneering work paved the way for a wide range of applications of which a few are exemplified.

Dielectric properties and molecular motions of liquid crystal molecules in 4-(2-methylbytyl)phenyl 4-(4-octylphenyl)benzoate liquid crystal having blue phase (CE8)

Abstract Blue phase liquid crystals exhibit unique properties which are used in the new type of display. A blue-phase liquid crystal display was first presented commercially by Samsung in 2007. The blue-phase-three-color pixel display eliminates the need for color filters. This type of display uses blue-phase multi-component liquid crystal. Considering the one-component systems, it turns out that they are stable only in a very narrow range of temperatures between the isotropic and the chiral nematic phase (about 1 K). In 2005, a wide temperature range BP multi-component system was reported by researchers from the University of Cambridge. There are still several unsolved problems left. One of them is chemical stability and reliability. Therefore, the knowledge of molecular dynamics of blue phase liquid crystal is a prerequisite for understanding of blue-phase multi-component system. Understanding the molecular dynamics of a single component liquid-crystalline blue phase system can facilitate the solution of these problems. We present the molecular dynamics investigation of 4-(2-methylbytyl)phenyl 4-(4-octylphenyl)benzoate (CE8), which may be a good candidate to form materials suitable for blue-phase liquid crystal displays.