Claire Pizzey

Suspensions of colloidal plates in a nematic liquid crystal: a small angle x-ray scattering study

Suspensions of anisometric particles in the nematic phase of a liquid crystalline host solvent were prepared. We chose Claytone AF, a commercial quaternary ammonium surfactant treated montmorillonite, with an aspect ratio of up to 1:2000, and dimethyldioctadecylammonium bromide treated Laponite, with an aspect ratio of 1:8 as the dispersed particles. K15, a nematogenic compound (also known as 5CB), was the dispersing medium. The suspensions were characterized by small angle x-ray scattering (SAXS). The liquid crystal delaminates the clays well, but the scattering curves from Claytone suspensions have prominent first and second order pseudo Bragg peaks, indicating that stacking of clay plates has occurred. We report a model for fitting SAXS data based on Hosemanns theory for suspensions of plane parallel sheets.

Large scale structures in liquid crystal/clay colloids

Suspensions of three different clays in K15, a thermotropic liquid crystal, have been studied by optical microscopy and small angle x-ray scattering. The three clays were claytone AF, a surface treated natural montmorillonite, laponite RD, a synthetic hectorite, and mined sepiolite. The claytone and laponite were sterically stabilized whereas sepiolite formed a relatively stable suspension in K15 without any surface treatment. Micrographs of the different suspensions revealed that all three suspensions contained large scale structures. The nature of these aggregates was investigated using small angle x-ray scattering. For the clays with sheet-like particles, claytone and laponite, the flocs contain a mixture of stacked and single platelets. The basal spacing in the stacks was independent of particle concentration in the suspension and the phase of the solvent. The number of platelets in the stack and their percentage in the suspension varied with concentration and the aspect ratio of the platelets. The lath shaped sepiolite did not show any tendency to organize into ordered structures. Here the aggregates are networks of randomly oriented single rods.

Electro-induced orientational ordering of anisotropic pigment nanoparticles.

The response of anisotropic pigment particle suspensions to externally applied electric fields has been explored for possible application in reflective display technologies. Three different types of pigment particle were suspended in dodecane, using a polymeric stabilizer, and showed Schlieren textures between crossed polarizers at high concentrations (greater than 25–30 wt%), indicating the formation of colloidal nematic phases. Orientational order parameters were determined by X-ray scattering, and the influence of polydispersity on the values is discussed. X-ray scattering measurements also demonstrated a change in the structure factor consistent with the onset of a colloidal nematic phase. In addition, the pigment particles were dispersed into various liquid crystal hosts at low concentrations (less than 5 wt%) with and without the presence of mesogenic mimic stabilizers. However, the influence of these stabilizers on orientational ordering could not be confirmed. The electro-induced ordering determined via scattering was related to the electro-optical response of each suspension using a simple model. The particles in nematic hosts not only showed a high degree of orientational ordering at lower electric field strengths, but also showed a reduction in stability. Although these systems have shown strong orientational ordering, the optical response has been limited by the intrinsic shape of the pigment particles and the distribution of the transition dipoles moments within them. Nevertheless, the feasibility of developing materials for display applications has been demonstrated.

Manipulation of modified clay particles in a nematic solvent by a magnetic field

The magnetic alignment of organically modified montmorillonite platelets in magnetic fields is studied using small-angle x-ray scattering. When suspended in non-mesogenic solvents such as dodecanol the platelets are found to align parallel to the magnetic field due to the negative anisotropy of the magnetic susceptibility of the montmorillonite. Alignment of the clay in the nematic phase of 5CB was possible for sufficiently dilute samples and at sufficiently high field strengths. However, in this case the platelets aligned with their normals parallel to the field. It is argued that this is due to homeotropic anchoring of the liquid crystal at the clay particle surfaces leading to the particle orientation being slaved to the director alignment. Alignment of the 5CB director parallel to the field was only apparent at high fields and low particle concentrations, where the magnetic coherence length of the liquid crystal would be smaller than the typical size of a domain between stacks of clay platelets. A simple theoretical model is presented to aid the interpretation of the observations. The observed degree of particle alignment is often less than predicted, probably as the result of interactions between stacks of particles opposing reorientation.

Modifying the structure and flow behaviour of aqueous montmorillonite suspensions with surfactant.

Colloidal suspensions of plate-like particles undergo a variety of phase transitions. The predicted isotropic/nematic transition is often pre-empted by a sol/gel transition, especially in suspensions of the most commonly used natural swelling clay montmorillonite (MMT). A number of factors, including charge interactions, flexibility and salt concentration, may contribute to this competition. In this study, the effect of surfactant adsorption on suspensions of MMT was studied using rheology, small-angle X-ray scattering, static light scattering and optical microscopy. The addition of a polyetheramine surfactant reduced the moduli of the system and shifted the sol/gel transition to a much higher clay concentration, compared with suspensions of bare clay particles. Yet, scattering data revealed no change in suspension structure on length scales up to around a micrometre. Primary aggregates remain at this length scale and no nematic phase is formed. There is, however, a change in structure at large length scales (of order 20 μm) where light scattering indicates the presence of string-like aggregates that disappear on addition of surfactant. Microscope images of dried suspensions also revealed a string-like structure. The dried strings show strong birefringence and may consist of concentric cylinders, self-assembled from clay sheets.

Hydrophobic nanoparticles promote lamellar to inverted hexagonal transition in phospholipid mesophases.

This study focuses on how the mesophase transition behaviour of the phospholipid dioleoyl phosphatidylethanolamine (DOPE) is altered by the presence of 10 nm hydrophobic and 14 nm hydrophilic silica nanoparticles (NPs) at different concentrations. The lamellar to inverted hexagonal phase transition (Lα-HII) of phospholipids is energetically analogous to the membrane fusion process, therefore understanding the Lα-HII transition with nanoparticulate additives is relevant to how membrane fusion may be affected by these additives, in this case the silica NPs. The overriding observation is that the HII/Lα boundaries in the DOPE p-T phase diagram were shifted by the presence of NPs: the hydrophobic NPs enlarged the HII phase region and thus encouraged the inverted hexagonal (HII) phase to occur at lower temperatures, whilst hydrophilic NPs appeared to stabilise the Lα phase region. This effect was also NP-concentration dependent, with a more pronounced effect for higher concentration of the hydrophobic NPs, but the trend was less clear cut for the hydrophilic NPs. There was no evidence that the NPs were intercalated into the mesophases, and as such it was likely that they might have undergone microphase separation and resided at the mesophase domain boundaries. Whilst the loci and exact roles of the NPs invite further investigation, we tentatively discuss these results in terms of both the surface chemistry of the NPs and the effect of their curvature on the elastic bending energy considerations during the mesophase transition.

Structural Characterisation of Non-Deamidated Acidic Variants of Erwinia chrysanthemi L-asparaginase Using Small-Angle X-ray Scattering and Ion-Mobility Mass Spectrometry

PurposeErwinia chrysanthemi L-asparaginase (ErA) is an enzyme commonly used in the treatment regimen for Acute Lymphoblastic Leukaemia (ALL). Biopharmaceutical products such as ErA must be monitored for modifications such as deamidation, typically using ion-exchange chromatography (IEX). Analysis of clinical-grade ErA using native IEX resolves a number of enzymatically-active, acidic variants that were poorly characterised.MethodsErA IEX variants were isolated and fully characterised using capillary electrophoresis (cIEF), LC-MS and LC-MS/MS of proteolytic digests, and structural techniques including circular dichroism, small-angle X-ray scattering (SAXS) and ion-mobility mass spectrometry (IM-MS).ResultsLC-MS, MS/MS and cIEF demonstrated that all ErA isolates consist mainly of enzyme lacking primary-sequence modifications (such as deamidation). Both SAXS and IM-MS revealed a different conformational state in the most prominent acidic IEX peak. However, SAXS data also suggested conformational differences between the main peak and major acidic variant were minor, based on comparisons with crystal structures.ConclusionsIEX data for biopharmaceuticals such as ErA should be thoroughly characterised, as the most common modifications, such as deamidation, may be absent.

Columnar phases in liquid crystal dendrimers: variable pressure X-ray diffraction

The structures of the third and fifth generation of a liquid crystal dendrimer have been studied as a function of temperature and pressure using X-ray diffraction. The third generation LC dendrimer showed a crystal to smectic transition and increasing pressure simply increased the transition temperature. The fifth generation showed two different rectangular columnar phases and one hexagonal columnar phase. The application of pressure did not induce either of the rectangular phases to transform to a simple smectic phase, suggesting that they are slightly modified smectic phases. The hexagonal phase was more easily suppressed by the application of pressure, suggesting that the molecules are splayed into a disc-like conformation and become more cylinder-like under pressure.

Liquid Crystal Clay Composites

We report a successful method of sterically stabilising small, high aspect ratio clay platelets in a liquid crystalline host using a quaternary ammonium surfactant. Small Angle X-ray Scattering results for the dry powder 2HT-treated Laponite show that there is a monolayer of 2HT on the platelet surface. The data for the Laponite suspension in 5CB indicate free tumbling disks which do not aggregate in the nematic phase.

Electric Field Induced Orientational Order in Suspensions of Anisotropic Nanoparticles

Suspensions of anisometric dye particles in dodecane have been investigated by electro-optic methods and X-ray scattering. The suspensions have nematic like properties such as a Schlierren texture and an electro-optic response. The thin, plate-like, particles of Permanent Rubine are crystalline monodomains with a set of lattice planes spaced by 18 Å lying parallel to their largest faces. They are oriented by an electric field such that their normals tend to be perpendicular to the applied field. The stronger ordering at about 25 wt% suggests that this might be the onset of the nematic phase. A simple model shows that the electric field induced change in optical absorbance is consistent with the induced orientational order.