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The solvation shell is essential for the folding and function of proteins, but how it contributes to protein misfolding and aggregation has still to be elucidated. We show that the mobility of solvation shell H2O molecules influences the aggregation rate of the amyloid protein alpha-synuclein (alpha Syn), a protein associated with Parkinson's disease. When the mobility of H2O within the solvation shell is reduced by the presence of NaCl, alpha Syn aggregation rate increases. Conversely, in the presence CsI the mobility of the solvation shell is increased and alpha Syn aggregation is reduced. Changing the solvent from H2O to D2O leads to increased aggregation rates, indicating a solvent driven effect. We show the increased aggregation rate is not directly due to a change in the structural conformations of alpha Syn, it is also influenced by a reduction in both the H2O mobility and alpha Syn mobility. We propose that reduced mobility of alpha Syn contributes to increased aggregation by promoting intermolecular interactions.

We propose a method to measure the evolution of the volume fraction distribution in colloidal films during their drying process, using only the transmitted light intensity recorded with a commercial digital camera. From the Lambert-Beer law, the volume fraction of a dispersion film with a certain film thickness can be measured from the transmitted light intensity. A pseudo-absorption capacity was imparted to the transparent dispersion by adding a red dye, and the ratio of green to blue light absorbance was measured for the liquid film. For any film, the volume fraction increased spatially towards a compaction front, and the volume fraction in this region reached approximately 63.4%. The volume fraction inside the liquid region of the film also increased during drying. These trends are similar to previous results obtained using other methods. The magnification in this method can be easily changed by replacing the imaging equipment, and changes in volume fraction distribution near the drying front were observed at high magnification using different lenses. This method, based on captured photographic images, measure the two-dimensional distribution of the volume fraction, making it easy to observe changes in the volume fraction distribution caused by drying at both macroscopic and microscopic levels. It is likely that the proposed method will be difficult to apply to anisotropic particles or to larger particles which cause significant scattering.

Monomeric alpha-synuclein (aSyn) is a well characterised as a lipid binding protein. aSyn is known to form amyloid fibrils which are also localised with lipids and organelles in so called Lewy bodies, insoluble structures found in Parkinson’s disease patient’s brains. It is still unclear under which conditions the aSyn-lipid interaction can start to become pathological. Previous work to address pathological interactions has focused on using synthetic lipid membranes, which lack the complexity of physiological lipid membranes which not only have a more complex lipid composition, but also contain lipid interacting proteins. Here, we investigate how either monomeric or fibrillar aSyn interact with physiological synaptic vesicles (SV) isolated from rodent brain. Using small angle neutron scattering and high-resolution imaging we observe that aSyn fibrils disintegrate SV, whereas aSyn monomers cause clustering of SV. Furthermore, SV enhance the aggregation rate of aSyn, however increasing the SV:aSyn ratio causes a reduction in aggregation propensity. SV lipids appear as an integrated part of aSyn fibrils and while the fibril morphology differs to aSyn fibrils alone, the core fibril structure remains the same. We finally demonstrate that lipid-associated aSyn fibrils are more easily taken up into cortical i3Neurons derived from induced pluripotent stem cells. Our study sheds light on differences between interactions of aSyn with synthetic lipid vesicles and physiological SV. We show how aSyn fibrils may enhance pathology by disintegrating SV, which in turn may have fatal consequences for neurons. Furthermore, disease burden may additionally be impacted by an increased uptake of lipid-associated aSyn by neurons, leading to more SV damage and enhancing aSyn aggregation.

The strength of drilling mud filter cakes is a parameter of practical relevance during well construction. This work simulates a ‘hole punch test’ experiment to determine filter cake yield stress. The discrete element model is used to predict the energy needed to push a plunger through the cake. The theoretical data is compared with experimental measurements for cakes with varying particle size and shape. The simulations and experiments both show an increase in yield stress and required energy with decreasing cake porosity and particle size. Adhesion due to liquid bridges was found to contribute significantly to cake strength. A scaling argument is established which indicates that the resistance to plunger motion comes from the particles sheared at the edge of the plunger.

Spontaneous formation of vesicles from the self-assembly of two specific surfactants, one zwitterionic (oleyl amidopropyl betaine, OAPB) and the other anionic (Aerosol-OT, AOT), is explored in water using small-angle scattering techniques. Two factors were found to be critical in the formation of vesicles: surfactant ratio, as AOT concentrations less than equimolar with OAPB result in cylindrical micelles or mixtures of micellar structures, and salt concentration, whereby increasing the amount of NaCl promotes vesicle formation by reducing headgroup repulsions. Small-angle neutron scattering measurements reveal that the vesicles are approximately 30-40 nm in diameter, depending on sample composition. Small-angle X-ray scattering measurements suggest preferential partitioning of OAPB molecules on the vesicle inner layer to support vesicular packing. Heating the vesicles to physiological temperature (37 °C) causes them to collapse into smaller ellipsoidal micelles (2-3 nm), with higher salt concentrations (≥10 mM) inhibiting this transition. These aggregates could serve as responsive carriers for loading or unloading of aqueous cargoes such as drugs and pharmaceuticals, with temperature changes serving as a simple release/uptake mechanism.

State-of-the-art approaches for membrane cleaning scheduling have focused on the Mixed-Integer Nonlinear Programming (MINLP) formulation so far, a strategy leading to a combinatorial problem that does not capture accurately the dynamic behaviour of the system. In this work, the Reverse Osmosis (RO) cleaning scheduling problem is solved using a novel approach based on the Multistage Integer Nonlinear Optimal Control Problem (MSINOCP) formulation. The approach produces an automated solution for the membrane cleaning scheduling, which also obviates the need for any form of combinatorial optimisation. Two different simulations, for 26 and 52 periods of operation (each period with a duration of one week), are carried out to illustrate the application of the proposed framework and the total cost is 1.17 and 2.48 107 €, respectively. The RO network configuration considers 2 stages, each with 3 individual RO modules. The results show evidently that the new proposed solution framework can solve successfully this type of problems, even for large scale configurations, long time horizons and arbitrary realistic complexity of the underlying dynamic model of the RO process considered.

The spontaneous adsorption of graphene oxide (GO) sheets at the air-water interface is explored using X-ray reflectivity (XRR) measurements. As a pure aqueous dispersion, GO sheets do not spontaneously adsorb at the air-water interface due to their high negative surface potential (-60 mV) and hydrophilic functionality. However, when incorporated with surfactant molecules at optimal ratios and loadings, GO sheets can spontaneously be driven to the surface. It is hypothesised that surfactant molecules experience favourable attractive interactions with the surfaces of GO sheets, resulting in co-assembly that serves to render the sheets surface active. The GO/surfactant composites then collectively adsorb at the air-water interface, with XRR analysis suggesting an interfacial structure comprising surfactant tailgroups in air and GO/surfactant headgroups in water for a combined thickness of 30-40 Å, depending on the surfactant used. Addition of too much surfactant appears to inhibit GO surface adsorption by saturating the interface, and low loadings of GO/surfactant composites (even at optimal ratios) do not show significant adsorption indicating a partitioning effect. Lastly, surfactant chemistry is also a key factor dictating adsorption capacity of GO. The zwitterionic surfactant oleyl amidopropyl betaine causes marked increases in GO surface activity even at very low concentrations (≤0.2 mM), whereas non-ionic surfactants such as Triton X-100 and hexaethyleneglycol monododecyl ether require higher concentrations (ca. 1 mM) in order to impart spontaneous adsorption of the sheets. Anionic surfactants do not enhance GO surface activity presumably due to like-charge repulsions that prevent co-assembly. This work provides useful insight into the synergy between GO sheets and molecular amphiphiles in aqueous systems for enhancing the surface activity of GO, and can be used to inform system formulation for developing water-friendly, surface active composites based around atomically thin materials.

Colloidosomes, also known as Pickering emulsion capsules, have attracted attention for encapsulation of hydrophilic and hydrophobic actives. However, current preparation methods are limited to single core structures and require the use of modified/engineered nanoparticles for forming the shell. Here, we report a fast, simple, and versatile method for producing multi-oil core silica colloidosomes via salt-driven assembly of purely hydrophilic commercial nanoparticles dispersed within an Oil-In-Water-In-Oil (O/W/O) double emulsion template. The internal structure and overall diameter of the capsules can be adjusted by altering the primary and secondary emulsification conditions. With this approach, 7 to 35 µm diameter multicore colloidosomes containing 0.9 to 4.2 µm large oil cores were produced. The capsules can easily be functionalized depending on the type of nanoparticles used in the preparation process. Here, metal oxide nanoparticles, such as Fe3O4, TiO2 and ZnO, were successfully incorporated within the structure, conferring specific functional properties (i.e. magnetism, photocatalysis) to the final microcapsules. These capsules can also be ruptured using ultrasound, enabling easy access to the internal core environments. Therefore, we believe this work offers a promising approach for producing multicore colloidosomes with adjustable structure and functionalities for the encapsulation of hydrophobic actives.

This research is motivated by the desire to control the solids distribution during the drying of a film containing particles of two different sizes. A variety of particle arrangements in dried films has been seen experimentally, including a thin layer of small particles at the top surface. However, it is not fully understood why this would occur. This work formulates and solves a colloidal hydrodynamics model for (i) diffusion alone and (ii) diffusion plus excluded volume diffusiophoresis, to determine their relative importance in affecting the particle arrangement. The methodology followed is to derive partial differential equations (PDEs) describing the motion of two components in a drying film. The diffusive fluxes are predicted by generalising the Stokes–Einstein diffusion coefficient, with the dispersion compressibility used to produce equations valid up until close packing. A further set of novel equations incorporating diffusiophoresis is derived. The diffusiophoretic mechanism investigated in this work is the small particles being excluded from a volume around the large particles. The resulting PDEs are scaled and solved numerically using a finite volume method. The model includes the chemical potentials of the particles, allowing for incorporation of any interaction term. The relative magnitudes of the fluxes of the differently sized particles are compared using scaling arguments and via numerical results. The diffusion results, without any inter-particle interactions, predict stratification of large particles to the top surface. Addition of excluded volume diffusiophoresis introduces a downwards flux on the large particles, that can result in small-on-top stratification, thus providing a potential explanation of the experimental observations.

Pattern formation is a common occurrence in drying colloidal systems. The most common in droplets, is a ring distribution where the constituents have relocated to the edge, which is referred to as a coffee ring. This deposit is unfavourable in many manufacturing processes and is of fundamental interest. In this study, we present a model capable of predicting when a coffee ring will be observed in hard spherical particle systems. Ring profiles are found to be formed at low contact angles with the specific angle predicated upon the initial concentration of the suspension. Modelling results are in agreement with experiments using latex suspensions.

Funder: Infineum UK Ltd, A novel neutron and X-ray reflectometry sample environment is presented for the study of surface-active molecules at solid–liquid interfaces under shear. Neutron reflectometry was successfully used to characterise the iron oxide–dodecane interface at a shear rate of 7.0×102s-1 using a combination of conventional reflectometry theory coupled with the summation of reflected intensities to describe reflectivity from thicker films. Additionally, the structure adopted by glycerol monooleate (GMO), an Organic Friction Modifier, when adsorbed at the iron oxide–dodecane interface at a shear rate of 7.0×102s-1 was studied. It was found that GMO forms a surface layer that appears unaltered by the effect of shear, where the thickness of the GMO layer was found to be 24.3-10.2+9.9 Å under direct shear at 7.0×102s-1 and 25.8-5.2+4.4 Å when not directly under shear. Finally, a model to analyse X-ray reflectometry data collected with the sample environment is also described and applied to data collected at 3.0×103s-1.

Hypothesis A green approach for producing magnetic photocatalysts via direct agglomeration of commercial nanoparticles in emulsion is shown. Aggregation is attributed to charge screening by salt addition which reduces stabilising repulsive forces between particles, and different nanoparticles (TiO2, Fe3O4 and SiO2) serve to imbue the final agglomerates with desired adsorption, photodegradation and magnetic properties. Experiment Titania doped magnetic silica microbeads (TiO2/Fe3O4/SiO2) were produced at room temperature by CaCl2-induced aggregation of nanoparticles in a reverse emulsion template. The beads were characterized using optical microscopy, SEM, STEM, EDX and zeta potential measurements. The adsorption and photocatalytic properties of the system as well as its reusability were investigated using Rhodamine B and Methylene Blue as model pollutants. Results Magnetically responsive beads approximately 3–9 µm in diameter incorporating SiO2, TiO2 and Fe3O4 nanoparticles were produced. Adsorption and photodegradation properties of the beads were confirmed by bleaching solutions of Rhodamine B, Methylene Blue as well as mixtures of both dyes. Reusability of the beads after magnetic separation was demonstrated, exhibiting a dye removal efficiency greater than 93% per cycle for three consecutive cycles of UV-light irradiation. This method is simpler than conventional sol–gel methods and offers a green and easy to implement approach for producing structured functional materials.

The propensity for intrinsically disordered proteins to aggregate is heavily influenced by their surrounding environment. Here, we show that the mobility of the surrounding water molecules directly influences the aggregation rate of α-synuclein (aSyn), a protein associated with Parkinson’s disease. We observe that the addition of NaCl reduces the mobility of water, while addition of CsI increases the mobility of water. In turn, this reduces and increases the mobility of aSyn, respectively, given the change in strength and lifetime of the intermolecular forces. The reduction of aSyn mobility in the presence of NaCl ions leads to increased aggregation rates, which may be due to aggregation-competent conformations being stable for longer, thereby increasing the likelihood of establishing interactions between two adjacent monomers. In contrast, aSyn is more mobile when CsI is dissolved in the aqueous phase which leads to a reduction of successful monomeric interactions. We thus highlight the importance of the surrounding environment and describe how ion content can influence water mobility and the misfolding rate of amyloidogenic proteins, such as aSyn. By modulating the cellular environment to increase water mobility or finding small molecules to increase protein dynamics, new therapeutic targets may be found.

A green approach for producing magnetic photocatalysts via direct agglomeration of commercial nanoparticles in emulsion is shown. Aggregation is attributed to charge screening by salt addition which reduces stabilising repulsive forces between particles, and different nanoparticles (TiOTitania doped magnetic silica microbeads (TiOMagnetically responsive beads approximately 3-9 µm in diameter incorporating SiO

We report on the preparation of colloidosomes formed with a poly(methyl methacrylate-co-butyl acrylate) latex shell, sealed using calcium alginate as a novel nontoxic and biodegradable sealing agent. The aim is to encapsulate enzymes in detergent formulations. The proposed method, with vegetable oil as the continuous phase, avoids the use of harmful organic solvents. Allura Red has been used as a water-soluble dye, in the core, to analyze the influence of variables such as sodium alginate and latex concentrations on the sealing and release profiles. After formation, the capsules were dispersed in either water or propylene glycol. The capsules have been examined using optical, confocal, and scanning electron microscopies. Working with the highest sodium alginate concentration and latex volume, the encapsulation efficiency is between 60 and 80%. Propylene glycol enables a better dispersion of the capsules compared with water. Dye release data have been fitted to exponential and Michaelis-Menten-type equations, leading to kinetic parameters that allow the simulation of the release process.

Filter cakes made from model water-based drilling fluids were tested to determine cake properties such as porosity, thickness and yield stress. The effects of drilling fluid particle concentration, size distribution and shape on the properties of the resulting cakes were investigated. A hole punch tester was used to find the shear stress of the cakes, obtaining a yield stress from the measured peak force. The cake yield stress increased with increasing barite solids content in the fluid from 16.5 kPa at 3.1 vol% to 65.6 kPa at 24.8 vol%. A similar trend was observed for cakes made from calcium carbonate. Furthermore, the calcium carbonate cakes were thicker and stronger than the barite equivalents, with yield stresses increasing by between 29% and 56%. The addition of calcium carbonate particles to the existing barite network did not affect the cake thickness appreciably but gave cakes of lower porosity and higher yield stress.

© 2019 American Chemical Society. The synthesis of 2-3 μm spherical microcapsules with a polymer shell and a liquid core composed of ionic liquid (IL) ([Bmim][NTf2]) is described. These discrete IL microcapsules are prepared quickly and in large quantity in a low temperature, one pot synthesis, by a modified coacervation technique. These IL microcapsules show ability to release dye from the IL core into solution through a polymer membrane and also concentrate metal ions from solution into the microcapsules.

Colloidal films have many important applications where a layered configuration is desirable, including flexible electronics, anti-reflective coatings, and anti-microbial paints. We report stratification during evaporative film formation in binary colloidal dispersion, probed using a novel microbeam small-angle X-ray scattering (SAXS) technique. To our knowledge, SAXS approaches have not been used to experimentally obtain quantitative data of concentration profiles in multicomponent colloidal films. We measured the local scattering of a film at different vertical locations using a microfocused X-ray beam and determined particle concentrations at different film depths using a linear combination analysis of the mixed film and pure film scattering data. Using small particle size ratios ranging from 2.55 to 1.25, we experimentally observed and quantify three distinct stratification configurations: inverted small on- top, large-on-top, and no stratification. Our results show some agreement with a previously proposed stratification state diagram, although there are some limitations. Experimental verification of these stratification phenomena is critical to fully understanding the physics of particle movement and structure development during film formation, which is crucial for optimizing evaporative assembly processes for coatings., Financial support for this work was provided by the National Science Foundation through award CBET-1335787 and a Department of Education Graduate Assistance in Areas of National Need (GAANN) fellowship for A. J. C., Award P200A160163. This research used beamline 11-BM, CMS, of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract No. DE-SC0012704.

Colloidosomes have attracted considerable attention in recent years because of their potential applications in a range of industries, such as food, bioreactors and medicine. However, traditional polymer shell colloidosomes leak low molecular weight encapsulated materials due to their intrinsic shell permeability. Here, we report aqueous core colloidosomes coated with a gold shell, which make the capsules impermeable. The shells can be ruptured using ultrasound. The gold coated colloidosomes are prepared by making an aqueous core capsule with a polymer shell and then adding HAuCl4, surfactant and l-ascorbic acid to form a second shell. We propose to use the capsules as drug carriers. The gold coated colloidosomes demonstrate a low cytotoxicity and after triggering, both encapsulated doxorubicin and broken gold fragments kill cancer cells. In addition, we set up a targeting model by modifying the gold shell colloidosomes using 4,4'-dithiodibutyric acid and crosslinking them with proteins-rabbit immunoglobulin G (IgG). Label-free surface plasmon resonance was used to test the specific targeting of the functional gold shells with rabbit antigen. The results demonstrate that a new type of functional gold coated colloidosome with non-permeability, ultrasound sensitivity and immunoassay targeting could be applied to many medical applications.

Small drug molecules are widely developed and used in the pharmaceutical industry. In the past few years, loading and delivering such molecules using polymer-shell colloidosomes has attracted interest. Traditional polymer capsules fail to encapsulate low-molecular-weight materials for long times, since they are inherently porous and permeable for small molecules. In this paper, we report a method for encapsulating an anticancer drug with small molecule weight, for cell viability tests. The silver-coated colloidosomes are prepared by making an aqueous core capsule with a polymer shell and then adding AgNO3, surfactant, and l-ascorbic acid to form a second shell. The capsules are impermeable and can be triggered using ultrasound. We propose to use the capsules as drug carriers. The silver demonstrates a low cytotoxicity for up to 10 capsules per cell. After the silver shells are triggered by ultrasound, the released doxorubicin, the broken silver fragments, and the doxorubicin loading on the capsule surface all kill cells. The results demonstrate a nonpermeable silver-shell microcapsule with ultrasound sensitivity for potential medical applications.

Hypothesis Porous magnetic silica beads are promising materials for biological and environmental applications due to their enhanced adsorption and ease of recovery. This work aims to develop a new, inexpensive and environmentally friendly approach based on agglomeration of nanoparticles in aqueous droplets. The use of an emulsion as a geometrical constraint is expected to result in the formation of spherical beads with tunable composition depending on the aqueous phase content. Experiments Magnetic silica beads are produced at room temperature by colloidal destabilization induced by addition of CaCl2 to a water-in-oil emulsion containing SiO2 and Fe3O4 nanoparticles. The impact of the salt concentration, emulsification method, concentration of hydrophobic surfactant as well as silica content is presented in this paper. Findings This method enables the production of spherical beads with diameters between 1 and 9 µm. The incorporation of magnetic nanoparticles inside the bead’s structure is confirmed using Energy Dispersive X-ray spectrometry (EDX) and Scanning Transmission Electron Microscopy (STEM) and results in the production of magnetic responsive beads with a preparation yield up to 84%. By incorporating the surfactant Span 80 in the oil phase it is possible to tune the roughness and porosity of the beads.

Periodic nano- or microscale structures are used to control light, energy and mass transportation. Colloidal organization is the most versatile method used to control nano- and microscale order, and employs either the enthalpy-driven self-assembly of particles at a low concentration or the entropy-driven packing of particles at a high concentration. Nonetheless, it cannot yet provide the spontaneous three-dimensional organization of multicomponent particles at a high concentration. Here we combined these two concepts into a single strategy to achieve hierarchical multicomponent materials. We tuned the electrostatic attraction between polymer and silica nanoparticles to create dynamic supracolloids whose components, on drying, reorganize by entropy into three-dimensional structured materials. Cryogenic electron tomography reveals the kinetic pathways, whereas Monte Carlo simulations combined with a kinetic model provide design rules to form the supracolloids and control the kinetic pathways. This approach may be useful to fabricate hierarchical hybrid materials for distinct technological applications.

As all readers of this journal are aware, drug carriers are vital for safe and efficient delivery of therapeutics. Different materials, such as liposomes, metal-organic frameworks, silica particles, micelles and microcapsules can be used as drug delivery carriers. These drug delivery carriers are used to treat various diseases, such as cancers, fungal infections and muscle degeneration.

Late embryogenesis abundant (LEA) proteins comprise a diverse family whose members play a key role in abiotic stress tolerance. As intrinsically disordered proteins, LEA proteins are highly hydrophilic and inherently stress tolerant. They have been shown to stabilize multiple client proteins under a variety of stresses, but current hypotheses do not fully explain how such broad range stabilization is achieved. Here, using neutron reflection and surface tension experiments, we examine in detail the mechanism by which model LEA proteins, AavLEA1 and ERD10, protect the enzyme citrate synthase from aggregation during freeze-thaw. We find that a major contributing factor to citrate synthase aggregation is the formation of air bubbles during the freeze-thaw process. This greatly increases the air-water interfacial area, which is known to be detrimental to folded protein stability. Both model LEA proteins preferentially adsorb to this interface and compete with citrate synthase, thereby reducing surface induced aggregation. This novel surface activity provides a general mechanism by which diverse members of the LEA protein family might function to provide aggregation protection that is not specific to the client protein., Canadian Research Council for PhD studentship + ERC grant

Funder: Australian Government Research Training Program (RTP) Scholarship., Funder: Haemokinesis, Patterns in dried droplets are commonly observed as rings left after spills of dirty water or coffee have evaporated. Patterns are also seen in dried blood droplets and the patterns have been shown to differ from patients afflicted with different medical conditions. This has been proposed as the basis for a new generation of low-cost blood diagnostics. Before these diagnostics can be widely used, the underlying mechanisms leading to pattern formation in these systems must be understood. We analyse the height profile and appearance of dispersions prepared with red blood cells (RBCs) from healthy donors. The red cell concentrations and diluent were varied and compared with simple polystyrene particle systems to identify the dominant mechanistic variables. Typically, a high concentration of non-volatile components suppresses ring formation. However, RBC suspensions display a greater volume of edge deposition when the red cell concentration is higher. This discrepancy is caused by the consolidation front halting during drying for most blood suspensions. This prevents the standard horizontal drying mechanism and leads to two clearly defined regions in final crack patterns and height profile. This article is part of a discussion meeting issue ‘A cracking approach to inventing new tough materials: fracture stranger than friction’.

This article investigates the use of a commercial latex dispersion for the purpose of sand consolidation in oil wells. The aim is to consolidate sand without compromising permeability and to prevent sanding during water breakthrough. This is achieved by injecting latex dispersions into a sand-pack and relying on potassium chloride flushes, or irreducible saline water in the reservoir, to destabilize the latex onto the sand surface. This forms a latex network connecting and holding the sand grains together. The strength of the consolidation in the laboratory is determined by flowing water and oil at various flow rates and investigating the amount of sand produced. The effect of different parameters, such as the amount of latex injected, the latex salinity, and salinity of the irreducible water are discussed.

In this article, we examine the rate of film build-up and the evolution of polymer volume fraction in coagulant dipped films. The results are for nitrile and natural rubber compounds. We describe a model for the build-up of a latex film that coagulates onto a former as a wet gel and consolidates by a wet sintering process. We achieve this by applying diffusion and reaction kinetics for the coagulant transporting from a former into the latex bath. Wet sintering, the underlying mechanism for serum exudation from the wet gel, is modelled for a consolidating aggregate of latex particles. The parameters used in the models are either measured in separate experiments or are available from the literature. We compare the model predictions with the experimental results. The first, rapid, stage of film build-up is modelled successfully by simple diffusion of the coagulant cations. At longer dwell times, it is found that the reaction between coagulant and surfactant is the primary mechanism for the rate reduction. The rate of consolidation of the wet gel could be modelled reasonably well using a previously developed equation for latex film formation. The rate was chiefly dependent on the stress relaxation modulus of the polymer. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017, 55, 1633–1648

Colloidosomes can be used in a wide variety of industries, such as food, bioreactors and medicine. We report for the first time, aqueous core colloidosomes with a gold or silver shell. The diameter of the water core is from 0.7 μm to 2 μm. The formation of gold coated colloidosomes was achieved by using sodium citrate (Na₃Citrate) in the core and gold chloride (HAuCl₄) in the wash solution. The gold shell colloidosomes are covered with spherical gold particles. Silver coated colloidosomes can be prepared by using L-Ascorbic acid in the core and silver nitrate (AgNO₃) in the wash solution. Various processing parameters result in different shell morphologies. The silver shell can seal the core of the microcapsule, and the encapsulated material can be released by the addition of nitric acid.

Hypothesis Stratification or self-segregation of multicomponent particle mixtures during drying is an important phenomenon to understand for the development of single-step deposition processes for complex coatings. We hypothesize that varying the ratio of particle Peclet numbers will lead to different types of stratification behavior. Experiments Binary colloidal films of polystyrene and silica were prepared by evaporative film formation, and stratification of nanoparticles of different size ratio (7.7–1.2) was studied using microbeam small-angle X-ray scattering (SAXS). Findings SAXS spectra showed noticeable variations at different film depths, consistent with stratification. These results are quantified to obtain vertical composition profiles. We observe “sandwich”-type layered structures at different nanoparticle size ratios, which to our knowledge have not been previously observed experimentally or predicted by theory. For example, for films of larger particle size ratios (7.7–4.8), large particles are enriched at the film top and bottom, leading to a large-small-large or “LSL” behavior; while within films of smaller particle size ratio (2.2–1.2), small particles are enriched at the top and bottom of the film (small-large-small or “SLS” structures). The enrichment of particles at the top persists over several hundred particle layers and is not just a single monolayer pinned to the upper surface.

For the fabrication of P-OLED displays, using inkjet printing, it is important to control the final shape resulting from evaporation of droplets containing polymer. Due to peripheral pinning and consequent outward capillary flow, a ring-like final shape is typically observed. This is often undesirable, with a spatially uniform film usually required. Several experimental studies have shown that binary liquid inks can prevent ring formation. There is no consensus of opinion on the mechanism behind this improvement. We have developed a model for the drying of thin, binary liquid droplets, based on thin-film lubrication theory, and we solve the governing equations to predict the final shape. White-light interferometry experiments are conducted to verify the findings. In addition, we present the results of a linear stability analysis that identifies the onset of an instability driven by a difference in surface tension. If the more volatile liquid is more abundant, an instability becomes increasingly likely.

Novel atomic-level insight in boron removal and reinsertion into the framework of a HAMS-1B (H-[B]-ZSM-5) borosilicate molecular sieve was obtained by a combination of wet chemistry and one-/twodimensional B-11 solid-state NMR (SSNMR) spectroscopy. Uncalcined HAMS-1B shows only tetrahedral boron. However, three boron species are observed in B-11 SSNMR spectra of as-prepared and then calcined HAMS-1B: tetrahedral framework boron (B-[4](fr)), trigonal framework boron (B-[3](fr)), and non-framework trigonal boron (B-[3](NF)). A picture has emerged as to the origins of these three species. Trigonal boron species are formed via hydrolysis by reaction with the water formed from water release and water formed by oxidation and removal of the template during calcination. The trigonal boron species are readily removed from the framework by slurrying in water or mild acid solutions. Tetrahedral boron remains at a concentration about equal to that in the calcined sieve not slurried, indicating that it is more difficult to remove. The extent of boron removal and reinsertion is pH dependent. We demonstrate that boron is removed to a greater extent at low pH and can be reinserted when pH is increased. Boron reinsertion into the framework is proven by B-11 SSNMR on a series of B-10-B-11 exchanged borosilicate zeolites. We found that when boron is reinserted it enters at higher concentrations (similar to 40% more) as tetrahedral boron, not trigonal boron, thus reversing partial hydrolysis and removal during calcination. (C) 2015 Elsevier Inc. All rights reserved.

This article investigates the use micro-capsules, containing a gelling agent hydroxypropyl cellulose (HPC), to alter flow paths in porous media. The aim is to preferentially block-off high permeability regions, thereby diverting the flow into adjacent un-swept low permeability regions. Micro-capsules with 2–7 µm in diameter were made by polymer precipitation through solvent evaporation using poly(4-vinyl pyridine) (PVP) as the shell material. A customised flow tank was constructed to facilitate porous media flow and both single and dual permeability experiments were conducted. Even without gelling agent, the micro-capsules gradually blocked the pore throats of the glass beads network. Following acidification a drop in permeability was observed. This was because swelling of the PVP shell constricted the pore throats. The permeability drop was observed to be more significant for low permeability regions. Flowing micro-capsules through the tank with two permeability regions in parallel allowed the high permeability region to be selectively blocked.

Colloidosomes are polymer shell microcapsules. They are stable and easy to prepare and have been used to encapsulate drugs for release at specific areas in the body. Traditional polymer shell capsules cannot totally seal drugs, since they are porous, and small molecules diffuse through the polymer shell. In this paper, we report a method for encapsulating an antibiotic kanamycin using gold or silver coated colloidosomes. The colloidosomes are impermeable and can be triggered using ultrasound. To investigate the application of the capsules in a biological system, Escherichia Coli (E. coli) was chosen as a model organism. After triggering, the released antibiotic, as well as the metal shell fragments, kill E. coli. Both the silver and gold shells colloidosomes are toxic to this bacterial system and the gold coated colloidosomes can load a higher concentration of kanamycin.

Hypothesis Multicomponent coatings with layers comprising different functionalities are of interest for a variety of applications, including electronic devices, energy storage, and biomaterials. Rather than creating such a film using multiple deposition steps, we explore a single-step method to create such films by varying the particle Peclet numbers, Pe. Our hypothesis, based on recent theoretical descriptions of the stratification process, is that by varying particle size and evaporation rate such that Pe of large and small particles are above and below unity, we can create stratified films of polymeric and inorganic particles. Experiments We present AFM on the surface composition of films comprising poly(styrene) nanoparticles (diameter 25–90 nm) and silica nanoparticles (diameter 8–14 nm). Previous studies on films containing both inorganic and polymeric particles correspond to large Pe values (e.g., 120–460), while we utilize Pe ∼ 0.3–4, enabling us to test theories that have been developed for different regimes of Pe. Findings We demonstrate evidence of stratification and effect of the Pe ratio, although our results agree only qualitatively with theory. Our results also provide validation of recent theoretical descriptions of the film drying process that predict different regimes for large-on-top and small-on-top stratification.

Colloidosomes have attracted great interest in recent years because of their capability for storage and delivery of small molecules for medical and pharmaceutical applications. However, traditional polymer shell colloidosomes leak low molecular weight drugs due to their intrinsic shell permeability. Here, we report aqueous core colloidosomes with a silver shell, which seals the core and makes the shell impermeable. The silver-coated colloidosomes were prepared by reacting l-ascorbic acid in the microcapsule core with silver nitrate in the wash solution. The silver shell colloidosomes were then modified by using 4,4'-dithiodibutyric acid and cross-linked with rabbit Immunoglobulin G (IgG). Label-free surface plasmon resonance was used to test the specific targeting of the functional silver shell with rabbit antigen. To break the shells, ultrasound treatment was used. The results demonstrate that a new type of functional silver-coated colloidosome with immunoassay targeting, nonpermeability, and ultrasound sensitivity could be applied to many medical applications.

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.

Experiments explore the reduction in permeability of a porous bead pack when a suspension of thermally responsive polymer is injected and the temperature then increased above the thermal activation temperature. The change in permeability is greater with higher polymer concentration, provided that the ionic concentration of the solution is sufficient for floc formation. The time for activation of the blocking effect is within tens of seconds to minutes of when the polymer solution is heated. This is consistent with the timescale for diffusion-limited aggregation, although the detailed value depends on the geometry and polymer concentration. Dynamical experiments demonstrate that once the porous media is blocked, adding additional polymer has no effect. The mechanism for permeability reduction may be modeled in the context of a pore-network model, and we build a simple model to illustrate the permeability reduction as a function of the fraction of pores links which are blocked.

This article investigates the possibility of using micro-capsules, with a gelling agent, hydroxypropyl cellulose, in the core, during enhanced oil recovery. The aim is to block off high permeability regions of a formation known as thief zones, thereby diverting the chase injection water into adjacent unswept low permeability regions. Temperature triggered micro-capsules were made by polymer precipitation through a solvent evaporation method, with poly(lactic-co-glycolic) acid as the polymer shell. Release studies with methylene blue demonstrated the temperature induced release from these micro-capsules. A customised tank was made to allow porous media flow and single permeability experiments were conducted. Even without the gelling agent, the micro-capsules gradually blocked the ballotini pore network. However, by varying the tank temperature, a drop in permeability was observed when the capsules released their core. Experiments with two permeability regions showed that the micro-capsules clogged up the high permeability layer more than the low permeability region.

A protocol for making microcapsules with either organic or aqueous cores and various polymers for the shell is established. Release profiles are obtained, with the effect of complete and incomplete shell formation investigated. Triggered release due to environmental pH is evaluated as a method for release targeting. Results from microcapsules with poly(4-vinylpyridine) shells showed a release of methylene blue dye when the pH was below 3.5, due to swelling of the polymer. This behavior was also observed for poly(lactide-co-glycolide) microcapsules due to cleavage of ester bonds. Both polymers showed complete release after 6 h. Various active ingredients such as polyacrylamide and hydroxypropylcellulose are also encapsulated using the established protocol.