All-clay photonic crystals

Hierarchically structured "all-clay" 1D and 3D inverse photonic crystals were fabricated, featuring the crystalline layered microstructure of the phyllosilicate Laponite combined with crystalline macroporosity on the submicron scale. By using simple hard-templating protocols based on monodisperse polystyrene spheres, periodic layered silicate and inverse opal architectures with photonic crystal properties are accessible, which exhibit reflectivities of the stop band in excess of 50%. The combination of intrinsic chemical functionality with structural color makes such hierarchical "all-clay" architectures potential scaffolds in color-tunable chemo-optical devices.     

Spontaneous formation of chiral macrostructures in achiral hockey-stick liquid crystals

We report the synthesis and properties of a homologous series of asymmetrically substituted 4-(5-(4-benzyloxyphenyl)-1,3,4-oxadiazol-2-yl)phenyl 2-X-4-dodecyloxybenzoates, which have pronounced hockey-stick molecular architectures. The structure was varied through the lateral substitution with various groups, X (H, Me, MeO, Cl, F) in the outer benzene ring. The effect of the lateral group on liquid crystal phase behaviour was investigated by thermal optical microscopy and differential scanning calorimetry. Nematic and dark conclomerate phases were observed with both displaying macroscopically chiral domains.     

Eigenvalues of propagation through liquid crystals

Analytical expressions are given for the propagation constant through an homogeneous liquid crystal, following the 4 × 4 matrix formulation of Berreman. Also propagation through polarizers can be calculated analytically; it is a special case of a situation described by Teitler and Henvis.     

Eigenvalues of propagation through liquid crystals

Abstract

Analytical expressions are given for the propagation constant through an homogeneous liquid crystal, following the 4 × 4 matrix formulation of Berreman. Also propagation through polarizers can be calculated analytically; it is a special case of a situation described by Teitler and Henvis.     

Liquid-crystalline epoxies dispersed liquid crystals

Dispersing liquid crystal droplets in a rigid polymer matrix results in an electrically controllable light scattering medium. A polymer with high glass transition temperature phase-separated with a low molecular weight liquid-crystalline material is a good binder for polymer dispersed liquid crystals (PDLC). Main-chain liquid-crystalline epoxies were synthesized for the phase separation with low molecular weight nematic liquid crystals E7 (mixture of 4-alkyl-4′-cyanobiphenyls) and studied for their mesomorphic properties and response to an applied electrical field.     

Optical and thermal properties of Fe3O4 nanoparticle-doped cholesteric liquid crystals

A composite system of Fe₃O₄ nanoparticle-doped cholesteric liquid crystals with properties of broadband reflection and controllable temperature under high-frequency electric field is proposed. The broadband reflection can shield the near-infrared light in summer and the electromagnetic-thermal effect by the Fe₃O₄ nanoparticles can deice or defrost in winter for high transmittance and good safety. Furthermore, the thermal effect may be precisely controlled and significantly enhanced by adjusting the factors of the doped concentrations and the applied electric field parameters (duration time, magnitude and frequency). This composite system may have potential applications for multifunctional windows of architectures and vehicles.     

Electrochemical synthesis of dendritic zinc films composed of systematically varying motif crystals

Polycrystalline zinc films with new dendritic frameworks were electrodeposited from nonaqueous formamide media containing 0.01-0.3 M Zn(ClO4)2.6H2O as the Zn2+ source and 0.1 M LiClO4.3H2O as the supporting electrolyte. Formamide media offer a wider range of deposition temperatures and deposition potentials than aqueous solutions, which provides a higher degree of freedom in creating new polycrystalline architectures. The growth patterns of zinc crystals could be precisely controlled (e.g., faceted growth and dendritic growth) by changing the interplay between the growth rate and the mass transport rate. The effect of deposition potential, temperature, and Zn2+ concentration on the onset potential of dendritic growth and the detailed dendritic features were studied systematically. The zinc dendrites obtained in this study were composed of submicron-sized crystals of a uniform shape (motif crystals) that grow repetitively fused together to form three-dimensionally dispersed dendritic backbones. This unique organization achieves a remarkable physical and electrical continuity between crystals while generating high surface areas, which is difficult to accomplish simultaneously in polycrystalline films. The shape of motif crystals can be finely tuned from hexagons to fern-shaped leaves by the deposition potential applied, which in turn alters the overall degree of branching of dendritic backbones. Cyclic voltammetry of the resulting zinc electrodes with various growth patterns was carried out and discussed in conjunction with the films' morphological variation.     

Preliminary communication - The effects of bending sites on unconventionally shaped hydrogen-bonded liquid crystals

Angular mesogenic structures of hydrogen-bonded supramolecules have been constructed from a 1:1 molar ratio of 3(or 4)-decyloxybenzoic acid, MA (or PA), mixing either with trans-4-alkoxy-3'(or 4')-stilbazoles, CnM (or CnP), or with their analogous N -oxides (CnMO and CnPO) to form the hydrogen-bonded (H-bonded) complexes CnPPA, CnPMA, CnMPA, CnPOPA, CnPOMA and CnMOPA. By controlling the relative bending position of the H-bonded complexes, the variety of supramolecules offer new molecular structures of different linearities. By means of these bending effects we are able to tune the shape of the molecular architecture and thus to modify molecular packing as well as mesogenic properties. New liquid crystalline properties are introduced by the nonlinear effects of molecular geometry, and powder X-ray diffraction (XRD) patterns have confirmed their novel molecular architectures.     

Photo-induced alignment behaviour of polymerisable liquid crystals on bisazide in a polymer matrix

Photo-reactive bisazide in a polymer matrix containing acryloyl groups on the side chain was investigated as a photoalignment layer for polymerizable liquid crystals (PLC). We found the thin film of bisazide (2,6-bis(4-azidobenzylidene)-4-methyl-1-cyclohexanone) in a polymer matrix, irradiated by linearly polarised ultraviolet light (LPUVL), was able to homogeneously align PLC. The LPUVL irradiation dose changed the orientation direction of the PLC on the thin film of bisazide in the polymer matrix. In addition, the direction of the slow axis for the retardation of the photoalignment layer changed from parallel to perpendicular to the LPUVL electric field with the irradiation dose. From these results, it was suggested that the PLC was likely to be aligned along the slow axis of the retardation of the photoalignment layer. We concluded that the key mechanism that changed the direction of the slow axis in a plane was the photoreaction of azide–acrylate at low irradiation dose and that of bis(benzylidene)cyclohexanone at high irradiation dose. Although the photoalignment as a result of a simple photo cross-linking was previously little known except for photo-dimerisation, we revealed that the photoaddition of azide–acrylate is able to achieve the photoalignment.     

Creation of hollow zeolite architectures by controlled desilication of Al-zoned ZSM-5 crystals

Hollow zeolite architectures on different length scales have been obtained upon controlled desilication of Al-zoned ZSM-5 zeolites in alkaline medium. The hollow ZSM-5 crystals possess a functional Al-rich exterior and a tunable internal porosity and accessibility.     

Porous molecular crystals of calix[4]arenes

X-ray diffraction, thermogravimetric, and adsorption measurements were applied to study the thermal decomposition of the complexes of 25,26,27,28-tetrahydroxycalix[4]arene and 4-tert-butylcalix[4]arene with the solvents resulting in the formation of porous phases. Diffusion of the "guest" (solvent, gas) through the molecular crystal of calixarene-host proceeds via the consecutive formation of a series of thermodynamically unstable porous phases of the "host." Owing to the structural reorganization of calixarene, the transport of the "guest" occurs through the "host" matrix followed by complexation and formation of the thermodynamically stable structure.     

Photo-controlled diffusion in reacting liquid crystals: A new tool for the creation of complex molecular architectures

Diffusion enforced photo-assembling during polymerization of a chiralnematic monomer blend yields a cholesteric network in which the helical pitch gradually changes over the cross-section of the film. The polarization selective reflection band of cholesterics can be made much wider than those of single pitch materials and may expand over the whole visible wavelength. The paper discusses the photo-controlled diffusion process in thin films, the important process parameters and some of the properties of the molecular architectures obtained.     

Effects of nonmesomorphic substituted benzonitriles on the dielectric properties of cyanobiphenyl liquid crystals

The effects of the cyano-substituted aromatic nonmesomorphic additives N-(3,4-dicyanophenyl)-4′-nonyloxybenzamide (I), 3,4-dicyanophenyl-4′-nonyloxybenzoate (II), 3,4-dicyanophenyl-3′,4′,5′-tris-(4″-undecyloxyphenylbenzoate)benzoate (III), and 4-(6-hydroxyhexyloxy)benzonitrile (IV) on the dielectric properties of 4-hexyloxy-4′-cyanobiphenyl and a liquid-crystal mixture E3 were studied. Dielectric anisotropy, birefringence, and orientational ordering were studied to show that monocyano derivative IV most strongly increased the dielectric anisotropy of mesomorphic compositions because of its effective incorporation into the liquid crystal matrix.     

Response of nanoparticle-based one-dimensional photonic crystals to ambient vapor pressure

Herein we report an analysis of the variation of the optical properties of different nanoparticle-based one-dimensional photonic crystal architectures versus changes in the ambient vapor pressure. Gradual shift of the optical response provides us with information on the sorption properties of these structures and allow us to measure precise adsorption isotherms of these porous multilayers. The potential of nanoparticle-based one-dimensional photonic crystals as base materials for optical sensing devices is demonstrated in this way.     

Thermal growth of organic supramolecular crystals with screw dislocations

We report here a simple pathway to thermally assemble acene-based molecules into large crystals without modification of their chemical structures. Differential scanning calorimetry was used to characterize properly thermal events occurring during successive heating and cooling processes. More interestingly, observations by means of polarized light microscopy (POM) revealed that a spontaneous formation of screw dislocations within crystals during the isothermal treatment triggered a structural reorganization by forming large and well-defined spiral architectures. After this reorganization, new crystals showed an excellent ordering in both vertical and horizontal directions. Due to the richness in pi-electrons of acene-based molecules, we expect this work of importance to organic electronics, especially in the design of new molecular building blocks and investigation of their assembly into sophisticated supramolecular structures.     

SBA-15-Type Organosilica with 4-Mercapto-N,N-bis-(3-Si-propyl)butanamide for Palladium Scavenging and Cross-Coupling Catalysis

This work describes the synthesis of novel functional silica materials with difunctional thiol-amide substructures and featuring regular architectures on a mesoscopic level. The functional materials were synthesised by both one-pot co-condensation and post-grafting approaches. The thiol groups confined in the matrix were found to be efficient for palladium entrapment, leading to highly active and reusable heterogeneous catalysts for Sonogashira and Suzuki-Miyaura cross-coupling reactions. This work evidences the crucial role of both the thiol precursor and the condensation degree of the silica scaffold in view of the design of stable and reusable tailor-made mesoporous catalytic silica materials.     

Creating permanent 3D arrangements of isolated cells using holographic optical tweezers

We report the creation of permanent 3D configurations of cells, at predefined positions, within a gelatin matrix. The technique used holographic optical tweezers to manipulate individual E. coli within a solution comprising monomer precursors. The matrix was then set and after the laser beam was removed, we were able to demonstrate that the structures remained intact for many days. We were also able to demonstrate that, in the presence of appropriate nutrients, the E. coli survived within the gelatin matrix for several days. The technique could have a number of potential future applications, including the arrangement of a variety of different cell types in complex architectures, as motifs for promoting tissue differentiation and growth within the field of cell engineering.     

Indene and pseudoazulene discotic liquid crystals: a synthetic and structural study

Several new liquid-crystalline indene and pseudoazulene systems are reported. These molecules give rise to either columnar hexagonal mesophases and/or columnar plastic phases. The unique nature of these compounds stems from their non-classical discotic structure. Although the molecules have rigid aromatic cores, they lack terminal tails and instead the polarizable atoms (S, halogens) or polar groups (CN, CO) act as unusual soft parts. On the basis of many structurally related materials, we conclude that for this type of compound molecular stacking in the solid state is a prerequisite for the appearance of a columnar mesophase, although other intermolecular interactions within the layers are also important in establishing liquid-crystalline order. The behavior reported for these mesomorphic molecules opens up new possibilities in the search for related molecular interactions that might be useful for the construction of supramolecular architectures with particular properties.     

Generalized fabrication of two-dimensional non-close-packed colloidal crystals

In this paper we report a generalized templating approach for fabricating wafer-scale, two-dimensional, non-close-packed (ncp) colloidal crystals. Polymer nanocomposites consisting of monolayer ncp colloidal crystals prepared by a spin-coating process are used as sacrificial templates. After removal of the colloidal silica templates, the voids in the polymer matrix are infiltrated with other materials. By plasma-etching the polymer matrix, wafer-scale ncp colloidal crystals from a variety of functional materials can be made. This technique is scalable and compatible with standard microfabrication. Two-component colloidal arrays with complex micropatterns can also be fabricated by combining microfabrication with this templating approach. Normal-incidence reflectivity spectra of replicated titania ncp arrays agree well with theoretical prediction using Scalar Wave Approximation.     

Anisotropic cellulose-derived matrix for dispersed liquid crystals

New cellulose-derived dispersed liquid crystal free-standing thin films were prepared by a shear-casting technique from anisotropic and isotropic solutions of thermotropic (acetoxypropyl)cellulose in N,N-dimethylacetamide with different amounts of the nematic E7. For films prepared from anisotropic solutions, dispersed nematic E7 droplets of micron and submicron size were found to coexist, with the band texture characteristic of polymer liquid crystals after shearing. Mechanical properties including Young's modulus and stress-strain curves were determined along and perpendicular to the shear direction, and revealed the anisotropic behaviour of films prepared from lyotropic solutions. The nematic E7 component appears to promote chain mobility and rearrangement of the polymer matrix and to modify the viscoelastic properties of the matrix.