PbS nanoparticles stabilised blue phase liquid crystals

A kind of blue phase liquid crystal (BPLC), consisting of nematic liquid crystal, E7, and chiral dopants, CB15 and R1011, was investigated by doping PbS nanoparticles. The blue phase temperature range was extended from 3^oC to 4.6°C by doping PbS nanoparticles with diameters around 9.6 nm. A kind of porous texture was observed both in the forming process of PbS nanoparticles doped BPLCs as well as in the BPLCs (with/without PbS nanoparticles) under assisting electric field. The porous texture may indicate that the liquid crystals molecule should be reoriented during the formation process of PbS nanoparticles doped BPLCs.     

Dispersion of magnetic nanoparticles in a polymorphic liquid crystal

In order to enhance the phase stability of dispersions of magnetic nanoparticles (NPs) in a polymorphic liquid crystal, new ligands have been designed consisting of a terphenyl-based liquid crystalline core. The most stable dispersions were obtained with 7 nm super-paramagnetic Fe₃O₄ NPs decorated with the new ligands in place of 10 nm ferromagnetic CoFe₂O₄ spherical NPs.     

The effect of CoPt-coated reduced-graphene oxide nanosheets upon the Smectic-A to Smectic-C* phase transition of a chiral liquid crystal

ABSTRACT

We report on high-resolution calorimetry and small-angle X-ray scattering measurements along the Smectic-A to chiral Smectic-C* phase transition of the liquid crystal 4-(2-methyl butyl) phenyl 4-n-octylbiphenyl-4-carboxylate with dispersed, CoPt nanoparticle-coated reduced-graphene oxide nanosheets. The temperature dependence of heat capacity and smectic layer spacing are obtained in the vicinity of Smectic-A to chiral Smectic-C* phase transition. Though no remarkable pretransitional effects are present, the critical fits show a crossover from mean-field near a tricritical point to classical mean-field compared to pure liquid crystal. The X-ray data yield a dilation of smectic layer thickness, indicating the assembly of graphene oxide nanosheets between the smectic layers.     

Photoinduced liquid crystal blue phase by bent-shaped cis isomer of the azobenzene doped in chiral nematic liquid crystal

A photoresponsive azobenzene molecule DCAZO2 with two cholesteryl groups linked to both sides of the azobenzene group is doped in a mixture of nematic liquid crystal E7 and chiral dopant S811 (61.9 wt% E7, 36.1 wt% S811 and 2.0 wt% DCAZO2). Cooled from isotropic phase to 33.0°C, chiral nematic liquid crystal (N*LC) was formed in the sample and then the temperature was kept unchanged at 33.0°C. UV light irradiation induces the trans–cis photoisomerisation and thus an obvious phase transition. When the azobenzene groups isomerise to a cis-saturated state, the UV light was turned off and the white light was turned on at the same time. The bent-shaped cis isomer then turns back to the planar trans isomer gradually. A blue–green platelet texture representing cubic blue phase (BP) was observed and the size of the platelets was increased along with the cis–trans isomerisation. UV–vis absorption spectra indicate that the photoinduced BP exists when the isomerisation degree is between 79% and 18%, and further cis–trans isomerisation change BP back into N*LC. The large geometric structure of the cholesteryl groups and the large bent angle θ of the cis isomer are supposed to be responsible for the interesting result.     

Broadband reflective liquid crystal films induced by facile temperature-dependent coexistence of chiral nematic and TGB phase

A wide pitch gradient covering the near infrared region (750.0–2500.0 nm) were facilely obtained by simple controlling temperature difference to LC mixtures with a twist grain boundary (TGB)–N* phase transition. After the pitch gradient formed, the structure of broad reflective bandwidth was fixed through polymerisation of monomers in mixtures by UV irradiation. It was found that the temperature difference between the up and down side of the samples was critical to form wide-pitch gradient distribution. Additionally, the reflection wavelength and bandwidth of films could be adjusted by the applied temperature difference with the widest bandwidth up to 1750 nm. This simple method for the preparation of broad reflective films was expected to be used in the fields like architectural energy conservation or infrared shield.     

Facile synthesis of gold nanoparticles capped with an ammonium-based chiral ionic liquid crystal

Herein, we describe a facile synthesis of stable chiral ionic liquid crystal (ILC)-capped gold nanoparticles. A new ILC containing a chiral cholesterol moiety having a terminal triethylammonium group was synthesised which exhibited an enantiotropic lamellar mesophase. Stable, monodisperse citrate-stabilised gold nanoparticles having a size of ~60 nm were prepared and the citrate ligands on the gold nanoparticles were replaced with chiral ILC through a two-phase ligand exchange process. The resulting chiral ILC-stabilised particles were characterised using UV–visible (UV–Vis) and transmission electron microscopy (TEM) studies. Different from the citrate-stabilised nanoparticles, the ligand exchanged gold nanoparticles were dispersible in organic solvent and resulting dispersion was stable for more than observed period of 3 months. Furthermore, the chiral ILC-decorated gold nanoparticles were found to be well dispersible in a nematic host without any aggregation and induced a vertical alignment of the nematic director.     

The effect of molecular structure on the chiral random grain boundary phase

A chiral random grain boundary (RGB) phase was recently observed in a hockey-stick biphenyl-substituted 1,3,4-oxadiazole derivative. In the RGB phase, achiral molecules self-assemble into randomly oriented blocks of chiral smectic layers and the motif of the unique microstructure is attributed to the similarity of hockey-stick molecules both to bent-core and to rod-like molecules. In order to explore the effect of molecular structure on the RGB phase in detail, we systematically change the molecular design. When the flexible tail decreases, the high-temperature Smectic A (SmA) phase is replaced by a nematic phase, showing a phase sequence of Iso-N-SmA-RGB-Cryst in 2-(4-dodecyloxyphenyl)-5-biphenyl-1,3,4-oxadiazole. However, when we replace the 1,3,4-oxadiazole group by the 1,3,4-thiadiazole group, the bending angle increases in the 1,3,4-thiadiazole derivatives and the RGB phase disappears. Or when the length of the arm becomes short in naphthalene-substituted 1,3,4-oxadiazole, these molecules exhibited only normal rod-like molecules’ mesomorphism. These results will provide deep insights on the relationship of molecular structure and mesophase structural property.     

Investigations of phase transitions in liquid crystals by means of adiabatic scanning calorimetry

High-resolution calorimetric techniques have substantially contributed in characterising and understanding the delicate thermal behaviour near many phase transitions in liquid crystals. In this paper we describe a high-resolution adiabatic scanning calorimetric technique that has proven to be an important tool in discriminating between first-order and second-order phase transitions in addition to rendering high-resolution information on fluctuations-induced pretransitional specific heat capacity behaviour. The capabilities of adiabatic scanning calorimetry are illustrated with experimental results for the isotropic to nematic and the isotropic to smectic A transitions for a series of alkylcyanobiphenyl compounds. For the nematic to smectic A transition results are presented for pure compounds and mixtures of liquid crystals as well as on the effects of added non-mesogenic solutes and nanoparticles. For chiral molecules results for phase transitions involving blue phases and twist grain boundary phases are considered.     

Anomalous behaviours of the heat capacity in a liquid crystal showing a re-entrant isotropic phase

High resolution a.c. calorimetric measurements have been carried out on a liquid crystal 2-{4-[(R)-2-fluorohexyloxy]phenyl}-5-{4-[(S)-2-fluoro-2-methyldecanoyloxy]phenyl}pyrimidine (RSFPPY), determined the present measurement revealed precise temperature dependence of the heat capacity over a wide temperature range including the phase transition temperatures. The isotropic-chiral smectic C transition was anomalous in that it showed quite different behaviours depending on whether the measurement was made on heating or cooling; that is attributed to the relaxational character of the transition. A new non-transitional feature in the isotropic phase was found, corresponding to a very broad heat capacity peak over a 30 K temperature range. This indicates an existence of a new phase, possibly some kind of blue phase, at the lower temperature side of the isotropic phase. (RSFPPY), determined the present measurement revealed precise temperature dependence of     

Blue phase III widening in CE6-dispersed surface-functionalised CdSe nanoparticles

The phase transition behaviour of the chiral liquid crystal CE6 doped with spherical surface-functionalised CdSe nanoparticles has been examined by means of high-resolution adiabatic scanning calorimetry and polarising microscopy. The addition of nanoparticles results in an essentially stabilised blue phase III. The phase diagram is displayed upon heating and cooling and the enthalpy changes involved in the conversion between the blue phases are determined. The dispersion of functionalised nanoparticles is prominent for the stabilisation of blue phase III, which is potentially useful for applications, especially if applied on liquid crystals that exhibit blue phases close to room temperature.     

Strong thermal optical nonlinearity caused by CdSe nanoparticles synthesised in smectic ionic liquid crystal

Spectral and nonlinear optical properties of cadmium octanoate composites containing CdSe nanoparticles (NPs) have been studied by using optical absorption spectroscopy and laser scanning technique (Z-scan). CdSe NPs are chemically synthesised in thermotropic ionic liquid crystal (ILC) phase of cadmium octanoate which is used as nanoreactor. Anisotropic glassy nanocomposites are obtained by the rapid cooling of the ILC phase of nanocomposites to room temperature. The sizes of the CdSe NPs are determined from the absorption spectra. The thermo-optical nonlinearity of the new nanocomposites is characterised by extremely large value of the nonlinear refractive index, n₂, under relatively low-powered CW laser irradiation. This nonlinearity is caused by (1) the efficient light-induced heating due to the CdSe NPs strong exciton absorption, and (2) consequent thermal dissipation, which in turn, produces the photoelastic tensions in the glassy smectic matrix.     

The structure of acrolein in a liquid crystal phase

The (1)H NMR spectrum of a sample of acrolein dissolved in the nematic liquid crystal phase I52 has been analysed to yield 18 dipolar couplings between all the magnetic nuclei in the molecule; moreover, the (13)C and (13)C{(1)H} NMR spectra of a sample of acrolein in CDCl(3) were recorded and analysed to determine the indirect J(ij) couplings. The data were used to obtain the relative positions of the carbon and hydrogen atoms, assuming that these are independent of the conformations generated by rotation around the C--C bond through an angle phi, and to obtain a probability distribution P(phi). It has been found that in the liquid phase, the distribution is a maximum at the trans form whereas the abundance of the cis form is significantly smaller compared with that found by microwave spectroscopy or high level quantum mechanical calculations. Such calculations produced also a suitable force field needed to develop suitable strategies for vibrational correction procedure in the case of flexible molecules.     

Characterization of a new chiral antiferroelectric liquid crystal with a lateral bromo substituent

In this paper we present the characterization of a new chiral mesogen with a lateral bromo substituent. The identification of the various smectic phases is achieved by texture observation, miscibility studies and DSC. The optic and electro-optic properties are also investigated. The real part of the complex dielectric permittivity as a function of the temperature was also measured in the planar geometry for thin samples. The dielectric behaviour will be qualitatively discussed on the simple assumption of different anchorings. These results point out the importance of anchoring conditions in relation to the macroscopic properties observed in very thin cells of antiferroelectric liquid crystals.     

Magnetite nanoparticles/chiral nematic liquid crystal composites with magnetically addressable and magnetically erasable characteristics

A magnetite (Fe₃O₄) nanoparticle/chiral nematic liquid crystal (N*-LC) composite was prepared and filled into a planar treated cell. The Fe₃O₄ nanoparticles had been modified by oleic acid so that they could be better dispersed in the composite. When a magnetic field was scanned on the outer surface of the cell locally, Fe₃O₄ nanoparticles moved towards the inner surface of the cell correspondingly, and the black expected information was displayed. When the magnet was applied to the opposite outer surface, the information was erased. After polymer network walls were prepared in the composite, the resolution of the information displayed increased. Then, through the formation of hydrogen bonds between the nanoparticles and chiral pyridine compound (CPC) doped in the composite, the pitch length of the N*-LC could be adjusted by altering the intensity of the applied magnetic field. The composite doped with CPC could potentially be used as a material for a type of reflective colour paper with magnetically controllable characteristics.     

The fabrication of photosensitive self-assembly Au nanoparticles embedded in silica nanofibers by electrospinning

In this study, we demonstrated a simple, efficient, and low-cost method to fabricate large-area self-assembly Au nanoparticles (AuNPs) encapsulated within silica nanofibers (Au/SiO₂). The method is based on electrospinning and thermal decomposition of hybrid nanofibers prepared from the solution of tetraethylorthosilicate (TEOS), polyvinylpyrrolidone (PVP) and AuNPs. This study employed the electrospinning technique for the first time as a successful method for preparing a self-organized AuNP peapod chain in a silica nanofiber matrix, under mild conditions. It has the advantage of easily controlling the diameters of the silica nanofibers as well as the concentration of the AuNPs in the spinning solution. The Au/SiO₂ hybrid nanofibers fabricated by this method exhibited an obvious photoelectric response under the illumination wavelength around the Au/SiO₂ nanofibers surface plasmon resonance (SPR) absorption band, whereas no photoelectric response was observed for the pure silica fibers. The excellent characteristics of photoelectric response suggest that the electrospinning technique has a great potential for large-scale fabrication of functional nanofiber devices. The ability of coupling light responses into the nanosystems dependent on metallic nanoparticle SPR opens up new prospects for the construction of nanoscale waveguiding devices, sensors and optoelectronics.     

Polarized infrared study of a polymer network deformation in a nematic liquid crystal host

Using polarized infrared (IR) spectroscopy we have observed deformation of a polymer network in a liquid crystal host during the reorientation of the liquid crystal by an external electric field. In the system studied, containing 2% BMBB-6 polymerized at zero applied field in the host nematic liquid crystal 6CB, the observed deformation angle was between 20^o and 40^o 10^o. These experimental results provide some of the first conclusive experimental evidence that the polymer network elastically deforms as a direct result of the reorientation of the liquid crystal host.     

Gold three dimensional film electrode prepared from oppositely charged nanoparticles

Nanoparticulate gold film electrodes were prepared from oppositely charged gold nanoparticles (c.a. 6 nm diameter) by a layer-by-layer approach without application of linker molecules. This was done by alternative immersion of indium tin oxide plates into suspensions of positively and negatively charged particles. The thickness of the film and the magnitude of the characteristic surface plasmon band are proportional to the number of immersion and withdrawal steps. Up to nine double immersions and withdrawal steps can be used to systematically increase the amount of nanoparticulate gold material. The capacitive current density and current density of hydrogen peroxide reduction are proportional to the number of immersion and withdrawal steps. Highly efficient and low overpotential glucose electrooxidation in alkaline solution is demonstrated.     

Structure of the B4 liquid crystal phase near a glass surface

The B4 liquid crystal phase of bent-core molecules, a smectic phase of helical nanofilaments, is one of the most complex hierarchical self-assemblies in soft materials. We describe the layer topology of the B4 phase of mesogens in the P-n-OPIMB homologous series near the liquid crystal/glass interface. Freeze-fracture transmission electron microscopy reveals that the twisted layer structure of the bulk is suppressed, the layers instead forming a structure with periodic layer undulations, with the topography depending on the distance from the glass. The surface layer structure is modeled as parabolic focal conic arrays generated by equidistant parabolas whose foci are defect lines along the glass surface. Nucleation and growth of toric focal conics near the glass substrate is also observed. Although the growth of twisted nanofilaments, the usual manifestation of structural chirality in the B4 phase, is suppressed near the surface, the smectic layers are intrinsically chiral, and the helical filaments that form on top of them grow with specific handedness.