Dual-network hydrogel capsules for controlled molecular transport via pH and temperature responsiveness.

We have developed innovative core-shell hydrogel capsules with a dual-network shell structure designed for precise control of molecular transport in response to external stimuli such as pH and temperature. The capsules were fabricated using a combination of microfluidic electrospray techniques and water-in-water (w/w) core-shell droplets templating. The primary network of the shell, calcium alginate (Ca-Alg), with a pK around 3.

Interfacial colloidal assembly guided by optical tweezers and tuned via surface charge.

Hypothesis: The size, shape and dynamics of assemblies of colloidal particles optically-trapped at an air-water interface can be tuned by controlling the optical potential, particle concentration, surface charge density and wettability of the particles and the surface tension of the solution.

Experiments: The assembly dynamics of different colloidal particle types (silica, polystyrene and carboxyl coated polystyrene particles) at an air-water interface in an optical potential were systematically explored allowing the effect of surface charge on assembly dynamics to be investigated. Additionally, the pH of the solutions were varied in order to modulate surface charge in a controllable fashion.

The regulators of soil organic carbon mineralization upon lime and/or phosphate addition vary with depth.

Knowledge of the key factors regulating soil organic carbon (OC) mineralization in response to fertilizers and lime application is essential to understanding the effects of agricultural land management on soil OC preservation. Microbial community composition and OC availability to microorganisms have been proposed as the two most imperative factors controlling soil OC mineralization, although their relative importance is still under debate. Here we performed a laboratory incubation in combination with high-throughput sequencing and structural equation modeling to examine the mechanisms underlying the responses of OC mineralization in the topsoil and the subsoil of a volcanic soil (an Andosol) to the additions of lime and/or phosphate.

Complexes of β-lactoglobulin and high methyl-esterified pectin as a one-shot delivery system for reinforcing oil/water interfaces.

Electrostatic complexation of negatively charged polysaccharides with β-lactoglobulin (β-lg) has been shown to bolster the protein films at oil/water interfaces thereby improving emulsion stability. However, recent sub-phase exchange experiments demonstrated that highly charged polysaccharides such as low methyl-esterified pectin are complementary only if sequentially introduced to a pre-formed interfacial β-lg film. In this study, results of transient interfacial shear rheology show that, by using high-methylesterified pectins instead, complexes can be formed in pre-mixed solutions with β-lg at pH 4 that can lead to reinforced protein films at dodecane/water interfaces.

Depletion of HP1α alters the mechanical properties of MCF7 nuclei.

Within the nucleus of the eukaryotic cell, DNA is partitioned into domains of highly condensed, transcriptionally silent heterochromatin and less condensed, transcriptionally active euchromatin. Heterochromatin protein 1α (HP1α) is an architectural protein that establishes and maintains heterochromatin, ensuring genome fidelity and nuclear integrity. Although the mechanical effects of changes in the relative amount of euchromatin and heterochromatin brought about by inhibiting chromatin-modifying enzymes have been studied previously, here we measure how the material properties of the nuclei are modified after the knockdown of HP1α.

Lime and/or Phosphate Application Affects the Stability of Soil Organic Carbon: Evidence from Changes in Quantity and Chemistry of the Soil Water-Extractable Organic Matter.

The mechanisms by which lime and/or phosphate addition impacts the preservation of soil organic matter (OM) are poorly understood. We explored the changes in quantity and chemistry of water-extractable organic matter (WEOM) in the bulk soil and its heavy density fraction (>1.6 g/cm) of an unmanaged C-rich volcanic soil caused by lime and/or phosphate application.

Influence of particle concentration on multiple droplet formation in Pickering emulsions.

Hypothesis: Multiphase droplets form when oil and water are mixed together at the ambivalent conditions that occur close to phase inversion. In this paper we propose a mechanism for the stabilisation of multiphase droplets by a single population of particles.

Experiments: We investigated the microstructure of emulsions formed when dodecane and water are mixed in the presence of hydrophobic fumed silica nanoparticles.

Sustained-Release Injectable Hydrogel Formulations for Administration of Sodium Salicylate in Broiler Chickens.

We developed injectable hydrogels for the slow release of analgesic drugs in birds as an in vivo model of pharmacokinetics in wild avian species. Hydrogels loaded with sodium salicylate (NaSA) were injected subcutaneously in Ross broiler chickens. The hydrogels were made by dissolving sodium alginate and NaSA in water at 2 different concentrations (low, LALG; high, HALG) and then adding calcium chloride.

Droplet Fusion in Oil-in-Water Pickering Emulsions.

We have formed compound droplets made of two or more drops of immiscible oils by temporarily destabilizing Pickering oil-in-water emulsions. The emulsions used are synergistically stabilized by mixtures of cationic surfactant and negatively-charged particles. They are highly sensitive to the concentration of surfactant present in the emulsions.

Understanding the role of hydrogen bonding in the aggregation of fumed silica particles in triglyceride solvents.

Hypothesis: Fumed silica particles are thought to thicken organic solvents into gels by aggregating to form networks. Hydrogen bonding between silanol groups on different particle surfaces causes the aggregation. The gel structure and hence flow behaviour is altered by varying the proportion of silanol groups on the particle surfaces.

Controlling Pickering Emulsion Destabilisation: A Route to Fabricating New Materials by Phase Inversion.

The aim of this paper is to review the key findings about how particle-stabilised (or Pickering) emulsions respond to stress and break down. Over the last ten years, new insights have been gained into how particles attached to droplet (and bubble) surfaces alter the destabilisation mechanisms in emulsions. The conditions under which chemical demulsifiers displace, or detach, particles from the interface were established.

Nanostructuring Biomaterials with Specific Activities towards Digestive Enzymes for Controlled Gastrointestinal Absorption of Lipophilic Bioactive Molecules.

This review describes the development of novel lipid-based biomaterials that modulate fat digestion for the enhanced uptake of encapsulated lipophilic bioactive compounds (e.g. drugs and vitamins).

Destabilising Pickering emulsions by drop flocculation and adhesion.

We have investigated how emulsions of water drops coated by organoclay particles destabilise in organic solvents. The drops destabilise and the emulsions undergo a fluid-solid transition if the particles are poorly wetted by the solvent. We show that the drops adhere together and form three-dimensional networks as the fraction of the poor-quality solvent in the mixture increases.

Bioactive Hybrid Particles from Poly(D,L-lactide-co-glycolide) Nanoparticle Stabilized Lipid Droplets.

Biodegradable and bioactive hybrid particles composed of poly(D,L-lactide-co-glycolide) (PLGA) nanoparticles and medium-chain triglycerides were prepared by spray drying lipid-in-water emulsions stabilized by PLGA nanoparticles, to form PLGA-lipid hybrid (PLH) microparticles approximately 5 μm in mean diameter. The nanoparticle stabilizer was varied and mannitol was also incorporated during the preparation to investigate the effect of stabilizer charge and cryoprotectant content on the particle microstructure. An in vitro lipolysis model was used to demonstrate the particles' bioactivity by manipulating the digestion kinetics of encapsulated lipid by pancreatic lipase in simulated gastrointestinal fluid.

Controlling the enzymatic digestion of lipids using hybrid nanostructured materials.

Solid nanoparticle-lipid hybrids have been engineered by using spray drying to assemble monodisperse hydrophilic silica nanoparticles and submicron lipid (triglyceride) emulsions together into composite microparticles, which have specific activity toward enzymes. The influence of silica particle size (100-1000 nm) and emulsifier type (anionic and cationic) on the three-dimensional structure of the composite particles was investigated. The nanostructure of the hybrid particles, which is controlled by the size of the voids between the closely packed silica particles, plays a critical role in lipase action and hence lipid digestion kinetics.

Coalescence in concentrated Pickering emulsions under shear.

We have investigated the rheology of concentrated oil-in-water emulsions stabilised by silanised silica nanoparticles. The emulsions behave like highly elastic solids in response to small, uniform strains. They become unstable and begin to break down, however, on yielding.

The role of porous nanostructure in controlling lipase-mediated digestion of lipid loaded into silica particles.

The rate and extent of lipolysis, the breakdown of fat into molecules that can be absorbed into the bloodstream, depend on the interfacial composition and structure of lipid (fat) particles. A novel method for controlling the interfacial properties is to load the lipid into porous colloidal particles. We report on the role of pore nanostructure and surface coverage in controlling the digestion kinetics of medium-chain and long-chain triglycerides loaded into porous silica powders of different particle size, porosity, and hydrophobicity/hydrophilicity.

Poly(lactic-co-glycolic acid) as a particulate emulsifier.

The structure and stability of emulsions formed in the presence of nanoparticles of poly(lactic-co-glycolic acid) (PLGA) were characterised. From oil-water contact angles on PLGA films, it was deduced that particle surface hydrophobicity is linked to the oil phase polarity. Incorporation of polyvinyl alcohol molecules into the nanoparticle surfaces reduces the particle hydrophobicity sufficiently for oil-in-water emulsions to be preferentially stabilised.

Oil-in-water Pickering emulsion destabilisation at low particle concentrations.

Droplet evolution in unstable, dilute oil-in-water Pickering emulsions was characterised using a combination of light scattering, confocal microscopy and rheology. Emulsions were formed at concentrations of silanised fumed silica particles that are not sufficient to prevent destabilisation. The key result is that destabilisation initially occurs via a combination of droplet flocculation and permeation.

Formation and stability of nanoparticle-stabilised oil-in-water emulsions in a microfluidic chip.

The formation and stability of drops in the presence of nanoparticles was studied in a microfluidic device to directly observe the early stages of Pickering emulsification (low interfacial coverage). We observed several key differences between oil droplet necking and rupture in aqueous phases of nanoparticles (methylated silica) and well-characterised surfactant systems. The presence of particles did not influence drop formation dynamics and thus the size of the drops generated.

Shear-induced coalescence of oil-in-water Pickering emulsions.

This work reports on coalescence in oil-in-water Pickering emulsions subjected to simple shear flow. The emulsions were stabilized by silanized fumed silica particles forming layers a few hundred nanometers thick around drops that are tens of micrometers in size. The drop size and particle concentration in the emulsions were fixed, while the salt concentration was varied to adjust the colloidal interactions between the drops and particles.

Interfacial displacement of nanoparticles by surfactant molecules in emulsions.

The remarkable stability of nanoparticles attached to oil-water interfaces in macroemulsions hinders controlled detachment of these particles from emulsions. In this work it is shown that adding surfactant molecules which preferentially adsorb at the oil-water interface displaces nanoparticles from the interface. Surfactant adsorption at the oil-water interface is energetically favoured and readily occurs on mixing nanoparticle-stabilised oil-in-water emulsions with surfactant solutions.

Foamability of aqueous suspensions of fine graphite and quartz particles with a triblock copolymer.

The foamability of a triblock copolymer solution was strongly influenced by the presence of particles. The stability of the foam was evaluated by measuring the foam volume, the drainage of water and particles, and the bubble size as a function of time. The higher stability of foams produced with hydrophilic quartz particles, compared with hydrophobic graphite particles, was related to the presence of quartz aggregates in the lamellae and Plateau borders reducing water drainage, and therefore thin film rupture and bubble coalescence.

Structure of oil-in-water emulsions stabilised by silica and hydrophobised titania particles.

We have studied the stability and structure of emulsions formed in the presence of colloidal mixtures of partially hydrophobic titania particles and hydrophilic silica particles. On their own, the titania particles attached strongly to the oil-water interface and stabilised emulsions, while the silica particles did not attach to the interface. Adding silica particles to the titania dispersions enhanced coalescence processes during emulsion formation, except under mixing conditions that favoured particle heteroaggregation.

Effect of adding anionic surfactant on the stability of Pickering emulsions.

We investigated the structure and stability of dodecane-in-water emulsions stabilised by partially hydrophobised silica particles after dilution of the emulsions in solutions of sodium dodecyl sulfate and sodium chloride. The emulsions were stable to coalescence on dilution in salt solutions, but did cream over time. The rate and extent of creaming gradually decreased as the salt concentration in the diluted emulsion increased.