Alexander F. Routh

Drying of thin colloidal films

When thin films of colloidal fluids are dried, a range of transitions are observed and the final film profile is found to depend on the processes that occur during the drying step. This article describes the drying process, initially concentrating on the various transitions. Particles are seen to initially consolidate at the edge of a drying droplet, the so-called coffee-ring effect. Flow is seen to be from the centre of the drop towards the edge and a front of close-packed particles passes horizontally across the film. Just behind the particle front the now solid film often displays cracks and finally the film is observed to de-wet. These various transitions are explained, with particular reference to the capillary pressure which forms in the solidified region of the film. The reasons for cracking in thin films is explored as well as various methods to minimize its effect. Methods to obtain stratified coatings through a single application are considered for a one-dimensional drying problem and this is then extended to two-dimensional films. Different evaporative models are described, including the physical reason for enhanced evaporation at the edge of droplets. The various scenarios when evaporation is found to be uniform across a drying film are then explained. Finally different experimental techniques for examining the drying step are mentioned and the article ends with suggested areas that warrant further study.

Formation of liquid core–polymer shell microcapsules

Polymer shell microcapsules with liquid cores are used in a wide variety of industries, from food and flavour protection to inkless paper. There is a number of production methods, each with different characteristics and this article reviews a number of them. The methods considered are colloidosome formation, polymer precipitation by phase separation, polycondensation interfacial polymerisation, layer-by-layer polyelectrolyte deposition, polymer growth by surface polymerisation and copolymer vesicle formation. Each production method is described and the relative strength of each is outlined.

Release Profiles of Encapsulated Actives from Colloidosomes Sintered for Various Durations

This paper presents the formation of low temperature colloidosomes from colloidal poly(styrene-co-butyl acrylate) particles for both water-in-oil and oil-in-water systems. An investigation into the sintering conditions examines the ultimate shell morphology formed, with longer sintering times and higher sintering temperatures producing less porous microcapsules. This has been verified by the release of an encapsulated dye from the aqueous core microcapsules, in which slower release has been detected for longer sintering times. The results are subsequently fitted with a diffusion equation to give a diffusion coefficient of fluorescein through the polymeric shell of 10(-17) m(2)/s.

The effect of particle agglomeration on the formation of a surface-connected compartment induced by hydroxyapatite nanoparticles in human monocyte-derived macrophages

Agglomeration dramatically affects many aspects of nanoparticle–cell interactions. Here we show that hydroxyapatite nanoparticles formed large agglomerates in biological medium resulting in extensive particle uptake and dose-dependent cytotoxicity in human macrophages. Particle citration and/or the addition of the dispersant Darvan 7 dramatically reduced mean agglomerate sizes, the amount of particle uptake and concomitantly cytotoxicity. More surprisingly, agglomeration governed the mode of particle uptake. Agglomerates were sequestered within an extensive, interconnected membrane labyrinth open to the extracellular space. In spite of not being truly intracellular, imaging studies suggest particle degradation occurred within this surface-connected compartment (SCC). Agglomerate dispersion prevented the SCC from forming, but did not completely inhibit nanoparticle uptake by other mechanisms. The results of this study could be relevant to understanding particle–cell interactions during developmental mineral deposition, in ectopic calcification in disease, and during application of hydroxyapatite nanoparticle vectors in biomedicine.

Solidification and Ordering during Directional Drying of a Colloidal Dispersion

During drying, colloidal dispersions undergo processes such as solidification, cracking, and the draining of interstitial pores. Here we show that the solidification of polystyrene and silica dispersions, during directional drying, occurs in two separate stages. These correspond to the initial ordering and subsequent aggregation of the colloidal particles. Transitions between these stages are observed as changes in transparency and color that propagate as distinct fronts along the drying layer. The dynamics of these fronts are shown to arise from a balance between compressive capillary forces and the electrostatic and van der Waals forces described by DLVO theory. This suggests a simple method by which the maximum interparticle repulsion between particles can be measured through the optical inspection of the dynamics of a drying dispersion, under a microscope.

Evolution of mud-crack patterns during repeated drying cycles

In mud, crack patterns are frequently seen with either an approximately rectilinear or hexagonal tiling. Here we show, experimentally, how a desiccation crack pattern changes from being dominated by 90° joint angles, to 120° joint angles. Layers of bentonite clay, a few mm thick, were repeatedly wetted and dried. When dried, the layers crack. These cracks visibly close when rewetted, but a similar crack pattern forms when the layer is redried, with cracks forming along the lines of previously open cracks. Time-lapse photography was used to show how the sequence in which individual cracks open is different in each generation of drying. The geometry of the crack pattern was observed after each of 25 generations of wetting and drying. The angles between cracks were found to approach 120°, with a relaxation time of approximately 4 generations. This was accompanied by a gradual change in the position of the crack vertices, as the crack pattern evolved. A simple model of crack behavior in a layer where the positions of previously open cracks define lines of weakness is developed to explain these observations.

Bacterial quorum sensing and cell surface electrokinetic properties

The hypothesis tested in this paper is that quorum sensing influences the microbial surface electrokinetic properties. Escherichia coli MG1655 and MG1655 LuxS- mutant (lacking quorum-sensing gene for Autoinducer synthase AI-2) were used for this study. AI-2 production (or lack of) in both strains was analyzed using the Vibrio harveyi bioassay. The levels of extracellular AI-2 with and without glucose in the growth medium were consistent with previously published work. The surface electrokinetic properties were determined for each strain of E. coli MG1655 by measuring the electrophoretic mobility using a phase amplitude light-scattering (PALS) Zeta potential analyser. The findings show that the surface charge of the cells is dependent upon the stage in the growth phase as well as the ability to participate in quorum sensing. In addition, significant differences in the electrophoretic mobility were observed between both strains of E. coli. These findings suggest that quorum sensing plays a significant role in the surface chemistry of bacteria during their growth.

Encapsulation of Yeast Cells in Colloidosomes

Polymeric colloidosomes encapsulating viable Bakers yeast cells were prepared. To make the capsules, an aqueous suspension of 153 nm poly(methyl methacrylate-co-butyl acrylate) latex particles plus yeast cells is emulsified in a continuous phase of sunflower oil. By adding a small amount of ethanol to the oil phase, the latex particles at the surface of the emulsion droplets aggregate, forming the colloidosome shells. The microcapsules have been examined using optical, confocal, and scanning electron microscopies. The viability of the yeast cells was tested using fluorescent molecular probes. The encapsulated Bakers yeast cells were able to metabolize glucose from solution, although at a slower rate compared to nonencapsulated yeast. This demonstrates diffusion limitation through the colloidosome shell. The diffusive resistance could be increased by manufacturing colloidosomes with a double latex shell.

Dye diffusion from microcapsules with different shell thickness into mammalian skin

Oil-in-water microcapsules with varying shell thicknesses were fabricated via a coacervation technique, whereby evaporation of volatile solvents induced the shell-forming polymer to precipitate, phase separate and migrate to the oil/water interface to form microcapsules. These microcapsules encapsulated a lipophilic dye within their cores and were applied topically onto porcine skin for 6h. Results indicated that the dye preferentially accumulated within the skin furrows and hair follicles, though the dye did not penetrate beyond the stratum corneum. A model estimates the diffusion coefficients of dye through the microcapsule shell and within the skin to be approximately 10(-18) and 10(-16)m(2)s(-1), respectively.

Encapsulation of amylase in colloidosomes.

Aqueous core colloidosomes encapsulating the enzyme amylase were manufactured with a shell comprising polymer latex particles of diameter 153 nm. The colloidosomes were sealed with calcium carbonate by precipitation between an inner phase of Na2CO3 and an outer phase of CaCl2. This seal allowed the retention of small molecules, such as dyes, as well as larger enzyme molecules, for several months. The encapsulated material could be released by dissolution of the CaCO3 with acid, upon a large dilution in water, or by applying a sufficient shear. The degree of release could be controlled since the greater the mass of CaCO3 precipitated onto the colloidosome shell, the greater the dilution or shear required to achieve release. The calcium carbonate seal protected encapsulated amylase from the detrimental effects of components in a liquid laundry detergent for several months so that, on triggered release, the enzyme retained its high activity.