Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Use of an open photoacoustic cell for the thermal characterisation of liquid crystals

In this paper, we describe the use of an open cell photoacoustic configuration for the evaluation of the thermal effusivity of liquid crystals. The feasibility, precision and reliability of the method are initially established by measuring the thermal effusivities of water and glycerol, for which the effusivity values are known accurately. In order to demonstrate the use of the present method in the thermal characterization of liquid crystals, we have measured the thermal effusivity values in various mesophases of 4-cyano-4 - octyloxybiphenyl (8OCB) and 4-cyano-4 -heptyloxybiphenyl (7OCB) liquid crystals using a variable temperature open photoacoustic cell. A comparison of the measured values for the two liquid crystals shows that the thermal effusivities of 7OCB in the nematic and isotropic phases are slightly less than those of 8OCB in the corresponding phases

Self-assembled columns of fullerene

Columnar mesophases based on alternating triphenylene and hexaphenyltriphenylene moieties are exceptionally stable and able to accommodate bulky side-chain substituents within the alkyl chain continuum between the columns. This paper presents a system in which the triphenylene bears a fullerene on its side-chain and the hexaphenyltriphenylene equivalent is the aza-derivative hexakis(4-nonylphenyl)dipyrazino[2,3-f : 2'3'-h] quinoxalene, PDQ9. The mesophase formed was identified as hexagonal columnar (Col(h)) by X-ray diffraction (a = 25.2 angstrom and c = 3.5 angstrom) but, in addition to the expected peaks, there is indication of a two-dimensional hexagonal superlattice with d-spacing 59 angstrom. This superlattice is believed to arise from ordering of the fullerenes within the liquid crystal matrix. It can be explained on the assumption that, to maximise fullerene-fullerene contact, the fullerenes form chains which wrap around the central column in every group of seven columns of the triphenylene : PDQ9 Col(h) array.

Quantitative model for the kinetics of lyotropic phase transitions involving changes in monolayer curvature

We present a kinetic model for transformations between different self-assembled lipid structures. The model shows how data on the rates of phase transitions between mesophases of different geometries can be used to provide information on the mechanisms of the transformations and the transition states involved. This can be used, for example, to gain an insight into intermediate structures in cell membrane fission or fusion. In cases where the monolayer curvature changes on going from the initial to the final mesophase, we consider the phase transition to be driven primarily by the change in the relaxed curvature with pressure or temperature, which alters the relative curvature elastic energies of the two mesophase structures. Using this model, we have analyzed previously published kinetic data on the inter-conversion of inverse bicontinuous cubic phases in the 1-monoolein-30 wt% water system. The data are for a transition between QII(G) and QII(D) phases, and our analysis indicates that the transition state more closely resembles the QII(D) than the QII(G) phase. Using estimated values for the monolayer mean curvatures of the QII(G) and QII(D) phases of -0.123 nm(-1) and -0.133 nm(-1), respectively, gives values for the monolayer mean curvature of the transition state of between -0.131 nm(-1) and -0.132 nm(-1). Furthermore, we estimate that several thousand molecules undergo the phase transition cooperatively within one "cooperative unit", equivalent to 1-2 unit cells of QII(G) or 4-10 unit cells of QII(D).

Liquid crystal phase formation by biopolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

Dynamics of shear-induced orientation transitions in block copolymers

This review discusses liquid crystal phase formation by biopolymers in solution. Lyotropic mesophases have been observed for several classes of biopolymer including DNA, peptides, polymer/peptide conjugates, glycopolymers and proteoglycans. Nematic or chiral nematic (cholesteric) phases are the most commonly observed mesophases, in which the rod-like fibrils have only orientational order. Hexagonal columnar phases are observed for several systems (DNA, PBLG, polymer/peptide hybrids) at higher concentration. Lamellar (smectic) phases are reported less often, although there are examples such as the layer arrangement of amylopectin side chains in starch. Possible explanations for the observed structures are discussed. The biological role of liquid crystal phases for several of these systems is outlined. Commonly, they may serve as a template to align fibrils for defined structural roles when the biopolymer is extruded and dried, for instance in the production of silk by spiders or silkworms, or of chitin in arthropod shells. In other cases, liquid crystal phase formation may occur in vivo simply as a consequence of high concentration, for instance the high packing density of DNA within cell nuclei.

Self-assembly of an amyloid peptide fragment–PEG conjugate: lyotropic phase formation and influence of PEG crystallization

The self-assembly of PEGylated peptides containing a modified sequence from the amyloid beta peptide, YYKLVFF, has been studied in aqueous solution. Two PEG molar masses, PEG1k and PEG3k, were used in the conjugates. It is shown that both YYKLVFF–PEG hybrids form fibrils comprising a peptide core and a PEG corona. The fibrils are much longer for YYKLVFF–PEG1k, pointing to an influence of PEG chain length. The beta-sheet secondary structure of the peptide is retained in the conjugate. Lyotropic liquid crystal phases, specifically nematic and hexagonal columnar phases, are formed at sufficiently high concentration. Flow alignment of these mesophases was investigated by small-angle neutron scattering with in situ steady shearing in a Couette cell. On drying, PEG crystallization occurs leading to characteristic peaks in the X-ray diffraction pattern, and to lamellar structures imaged by atomic force microscopy. The X-ray diffraction pattern retains features of the cross-beta pattern from the beta-sheet structure, showing that this is not disrupted by PEG crystallization.

Polymer − surfactant vesicular complexes in aqueous medium

The introduction of ionic single-tailed surfactants to aqueous solutions of EO18BO10 [EO = poly(ethylene oxide), BO = poly(1,2-butylene oxide), subscripts denote the number of repeating units] leads to the formation of vesicles, as probed by laser scanning confocal microscopy. Dynamic light scattering showed that the dimensions of these aggregates at early stages of development do not depend on the sign of the surfactant head group charge. Small-angle X-ray scattering (SAXS) analysis indicated the coexistence of smaller micelles of different sizes and varying polymer content in solution. In strong contrast to the dramatic increase of size of dispersed particles induced by surfactants in dilute solution, the d-spacing of corresponding mesophases reduces monotonically upon increasing surfactant loading. This effect points to the suppression of vesicles as a consequence of increasing ionic strength in concentrated solutions. Maximum enhancements of storage modulus and thermal stability of hybrid gels take place at different compositions, indicating a delicate balance between the number and size of polymer-poor aggregates (population increases with surfactant loading) and the number and size of polymer−surfactant complexes (number and size decrease in high surfactant concentrations).

Biaxial optical properties of thermotropic random copolyesters

The optical microstructures of thin sections of two liquid crystalline polymers are examined in the polarizing microscope. The polymers are random copolyesters based on hydroxybenzoic and hydroxynaphthoic acids (B-N), and hydroxybenzoic acid and ethylene terephthalate (B-ET). Sections cut from oriented samples, so as to include the extrusion direction, show microstructures in which there is no apparent preferred orientation of the axes describing the local optical anisotropy. The absence of preferred orientation in the microstructure, despite marked axial alignment of molecular chain segments as demonstrated by X-Ray diffraction, is interpreted in terms of the polymer having biaxial optical properties. The implication of optical biaxiality is that, although the mesophases are nematic, the orientation of the molecules is correlated about three (orthogonal) axes over distances greater than a micron. The structure is classified as a multiaxial nematic.

Experimental confirmation of transformation pathways between inverse double diamond and gyroid cubic phases

A macroscopically oriented double diamond inverse bicontinuous cubic phase (QIID) of the lipid glycerol monooleate is reversibly converted into a gyroid phase (QIIG). The initial QIID phase is prepared in the form of a film coating the inside of a capillary, deposited under flow, which produces a sample uniaxially oriented with a ⟨110⟩ axis parallel to the symmetry axis of the sample. A transformation is induced by replacing the water within the capillary tube with a solution of poly(ethylene glycol), which draws water out of the QIID sample by osmotic stress. This converts the QIID phase into a QIIG phase with two coexisting orientations, with the ⟨100⟩ and ⟨111⟩ axes parallel to the symmetry axis, as demonstrated by small-angle X-ray scattering. The process can then be reversed, to recover the initial orientation of QIID phase. The epitaxial relation between the two oriented mesophases is consistent with topologypreserving geometric pathways that have previously been hypothesized for the transformation. Furthermore, this has implications for the production of macroscopically oriented QIIG phases, in particular with applications as nanomaterial templates.

Predicting sizes of hexagonal and gyroid metal nanostructures from liquid crystal templating

We describe a method to predict and control the lattice parameters of hexagonal and gyroid mesoporous materials formed by liquid crystal templating. In the first part, we describe a geometric model with which the lattice parameters of different liquid crystal mesophases can be predicted as a function of their water/surfactant/oil volume fractions, based on certain geometric parameters relating to the constituent surfactant molecules. We demonstrate the application of this model to the lamellar (LR), hexagonal (H1), and gyroid bicontinuous cubic (V1) mesophases formed by the binary Brij-56 (C16EO10)/water system and the ternary Brij-56/hexadecane/water system. In this way, we demonstrate predictable and independent control over the size of the cylinders (with hexadecane) and their spacing (with water). In the second part, we produce mesoporous platinum using as templates hexagonal and gyroid phases with different compositions and show that in each case the symmetry and lattice parameter of the metal nanostructure faithfully replicate those of the liquid crystal template, which is itself in agreement with the model. This demonstrates a rational control over the geometry, size, and spacing of pores in a mesoporous metal.

Control of nanomaterial self-assembly in ultrasonically levitated droplets

We demonstrate that acoustic trapping can be used to levitate and manipulate droplets of soft matter, in particular, lyotropic mesophases formed from selfassembly of different surfactants and lipids, which can be analyzed in a contact-less manner by X-ray scattering in a controlled gas-phase environment. On the macroscopic length scale, the dimensions and the orientation of the particle are shaped by the ultrasonic field, while on the microscopic length scale the nanostructure can be controlled by varying the humidity of the atmosphere around the droplet. We demonstrate levitation and in situ phase transitions of micellar, hexagonal, bicontinuous cubic, and lamellar phases. The technique opens up a wide range of new experimental approaches of fundamental importance for environmental, biological, and chemical research.

Microemulsões e fases líquidas cristalinas como sistemas de liberação de fármacos

A mistura de tensoativos com água, em determinadas proporções, na ausência ou na presença de substâncias lipofílicas pode formar diferentes tipos de agregados, entre os quais agregados polimorfos representados pelas microemulsões (ME) e mesofases liotrópicas - os cristais líquidos (LC), que estão intimamente ligados com a proporção e a natureza dos componentes da mistura. Nesse trabalho, foi discutido o papel desses sistemas na incorporação de fármacos com diferentes propriedades físico-químicas, influenciando fortemente a liberação, assim como a biodisponibilidade dos fármacos. Aspectos sobre a formação e a caracterização de microemulsões e cristais líquidos também foram discutidos. A análise da literatura indicou que, dependendo da polaridade do fármaco, o efeito da ME ou LC pode ser usado para otimizar o efeito terapêutico por meio do controle da velocidade ou do mecanismo de liberação do fármaco.