Encapsulation of Emulsion Droplets with Metal Shells for Subsequent Remote, Triggered Release.

A two-step method to encapsulate an oil core with an impermeable shell has been developed. A thin metallic shell is deposited on the surface of emulsion droplets stabilized by metal nanoparticles. This thin shell is shown to prevent diffusion of the oil from within the core of the metal-shell microcapsules when placed in a continuous phase that fully dissolves the oil. The stabilizing nanoparticles are sterically stabilized by poly(vinyl pyrrolidone) chains and are here used as a catalyst/nucleation site at the oil-water interface to grow a secondary metal shell on the emulsion droplets via an electroless deposition process. This method provides the simplest scalable route yet to synthesize impermeable microcapsules with the added benefit that the final structure allows for drastically improving the overall volume of the encapsulated core to, in this case, >99% of the total volume. This method also allows for very good control over the microcapsule properties, and here we demonstrate our ability to tailor the final microcapsule density, capsule diameter, and secondary metal film thickness. Importantly, we also demonstrate that such impermeable microcapsule metal shells can be remotely fractured using ultrasound-based devices that are commensurate with technologies currently used in medical applications, which demonstrate the possibility to adapt these microcapsules for the delivery of cytotoxic drugs.

Effects of copolymer concentration and chain length on the pH-responsive behavior of diblock copolymer micellar films.

The pH-responsive behavior of adsorbed diblock copolymer films of PDMA-PDEA (poly(2-(dimethylamino)ethyl methacrylate)-block-poly(2-(diethylamino)ethyl methacrylate)) on silica has been characterized using a quartz crystal microbalance with dissipation monitoring (QCM-D), an optical reflectometer (OR) and an atomic force microscope (AFM). The copolymer was adsorbed at pH 9 from various copolymer concentrations; QCM-D measurements indicate that the level of desorption when rinsed at pH 9 depends on the initial copolymer concentration. The adsorbed films produced at pH 9 generally have low charge densities; adjusting the solution pH to 4 results in a significant protonation of the constituent copolymers and a related interfacial structural change for the copolymer film. OR studies show no significant change during pH cycling, while QCM-D measurements indicate that the adsorbed mass and dissipation alter dramatically in response to the solution pH. The difference between the QCM-D adsorbed masses and dissipation values at pH 4 and 9 were found to be dependent on the initial copolymer concentration. This is due to differences in the initial conformations within the adsorbed copolymer layers at pH 9. The effect of the PDMA chain length on the pH-responsive behavior has also been studied; both the QCM-D adsorbed mass and dissipation of PDMA54-PDEA24 (shorter PDMA block) at pH 4 and 9 were observed to be greater than those of PDMA9X-PDEA2Y (longer PDMA block). This suggests that the normal extension of the adsorbed PDMA54-PDEA24 copolymer films is more significant than that of the PDMA9X-PDEA2Y films on silica.

The effect of surfactant chain length on the morphology of poly(methyl methacrylate) microcapsules for fragrance oil encapsulation.

The solvent evaporation method for producing microcapsules relies upon the correct wetting conditions between the three phases involved in the synthesis to allow core-shell morphologies to form. By measuring the interfacial tensions between the oil, polymer and aqueous phases, spreading coefficients can be calculated, allowing the capsule morphology to be predicted. In this work we explore the effect of surfactant chain length on capsule morphology using poly(methyl methacrylate) as the polymer and hexadecane as the core. We compared the predicted morphologies obtained using the polymer as a solid, and the polymer dissolved in dichloromethane to represent the point at which capsule formation begins. We found that using the polymer in its final, solid form gave predictions which were more consistent with our observations. The method was applied to successfully predict the capsule morphologies obtained when commercial fragrance oils were encapsulated.

The effect of molecular weight of nonadsorbing polymer on the structure of depletion-induced flocs.

This work explores the structural compactness of depletion-induced particle flocs with respect to the molecular weight of nonadsorbing polymer flocculants. Small-angle static light scattering was used to monitor the structural characteristics of the flocs, which were formed by the addition of nonadsorbing poly(acrylic acids) to a stable colloidal polystyrene latex dispersion. It was found that the floc mass fractal dimension, considered to be a measure of structural compactness, was dependent upon both the molecular weight and the concentration of the polyacid. In particular, reducing the molecular weight of the polymer at a fixed polyacid concentration resulted in higher mass fractal dimensions, despite the highly polydisperse nature of the polymer samples. This structural behavior was attributed to the lower particle sticking efficiencies upon collision. This reduced sticking ability is the result of the shallowing in the secondary potential energy well with decreasing polymer chain length, which was directly supported by atomic force microscopy data. Our results suggest that the formation of a shallower attraction well with a lower molecular weight nonadsorbing polymer is the result of the insufficiency of the increased osmotic pressure to counter-balance the short-ranged nature of the depletion interaction.

Drop penetration into porous powder beds.

The kinetics of drop penetration were studied by filming single drops of several different fluids (water, PEG200, PEG600, and HPC solutions) as they penetrated into loosely packed beds of glass ballotini, lactose, zinc oxide, and titanium dioxide powders. Measured times ranged from 0.45 to 126 s and depended on the powder particle size, viscosity, surface tensions, and contact angle. The experimental drop penetration times were compared to existing theoretical predictions by M. Denesuk et al. (J. Colloid Interface Sci.158, 114, 1993) and S. Middleman ("Modeling Axisymmetric Flows: Dynamics of Films, Jets, and Drops," Academic Press, San Diego, 1995) but did not agree. Loosely packed powder beds tend to have a heterogeneous bed structure containing large macrovoids which do not participate in liquid flow but are included implicitly in the existing approach to estimating powder pore size. A new two-phase model was proposed where the total volume of the macrovoids was assumed to be the difference between the bed porosity and the tap porosity. A new parameter, the effective porosity epsilon(eff), was defined as the tap porosity multiplied by the fraction of pores that terminate at a macrovoid and are effectively blocked pores. The improved drop penetration model was much more successful at estimating the drop penetration time on all powders and the predicted times were generally within an order of magnitude of the experimental results.

Facile synthesis of gold core-polymer shell responsive particles.

The free adsorption of an end-functionalised weak polybase, poly dimethylaminoethyl methacrylate (pDMAEMA), on the surface of colloidal gold nanoparticles (AuNPs) as a route to produce a responsive core-shell nanoparticle is explored here. Optimal conditions for the physisorption of the polymeric chains onto the colloidal nanoparticles are explored. A dense coverage is facilitated by rapidly mixing the well solvated pH responsive homopolymer, at low pH, into a relatively poor solvent environment, at higher pH, containing a stable dispersion of charge-stabilised gold nanoparticles. The rapid pH change causes the polymer chains to concurrently collapse and adsorb onto the gold nanoparticles. In order to achieve sterically stable, monodisperse and responsive core shell nanoparticles, a crucial factor is the pH difference of the systems prior to their mixing. Once adsorbed, end-functional thiol groups on the adsorbed polymer chains can form more permanent covalent attachments with the core particles. Dynamic light scattering coupled with mobility data of pH titration experiments show that the core-shell particles exhibit a responsive character consistent with the observed potentiometric titration data of the polymer. The same particles demonstrate reversible aggregation when cycled between pH extremes. This is confirmed by shifts in the SPR peak of the corresponding UV-Vis absorption profile. The ease and flexibility of this strategy for core-shell particle production, coupled with the stability and responsiveness of the product, make this a promising colloidal coating mechanism.

Incorporation of block copolymer micelles into multilayer films for use as nanodelivery systems.

This work demonstrates the potential application of stimulus responsive block copolymer micelles as triggerable delivery systems for use within multilayer films. Cationic, pH-responsive micelles of poly[2-(dimethylamino)ethyl methacrylate-block-poly(2-(diethylamino)ethyl methacrylate)] (PDMA-PDEA) were deposited on anionic polystyrene latex particles. The charge reversal of the surface and the amount of adsorbed polymer were monitored by zeta potential measurements and colloidal titrations, respectively. Prior to adsorption, the PDMA-PDEA micelles were loaded with a hydrophobic dye, and UV-vis spectroscopy was used to determine the amount of dye encapsulated within a monolayer of micelles. It was found that subtle chemical modification of the PDMA-PDEA diblock copolymer via permanent quaternization of the PDEA block results in micelles with tunable loading capacities. Multilayers of cationic micelles of partially quaternized PDMA-PDEA and anionic polyelectrolyte (poly(sodium 4-styrene sulfonate)) were deposited on the surface of polystyrene latex particles by sequential adsorption. UV-vis analysis of the dye present within the multilayer after the addition of each layer demonstrates that the micelles are sufficiently robust to retain encapsulated dye after multiple adsorption/washing cycles and can thus create a film that can be increasingly loaded with dye as more micelle layers are adsorbed. Multiple washing cycles were performed on micellar monolayers of PDMA-PDEA to demonstrate how such systems can be used to bring about triggerable release of actives. When performing several consecutive washing steps at pH 9.3, the micelle structure of the PDMA-PDEA micelles in the monolayer is retained, resulting in only a small reduction in the amount of encapsulated dye. In contrast, washing at pH 4, the structure of the micelle layers is severely disrupted, resulting in a fast release of the encapsulated dye into the bulk. Finally, if a sufficient number of micelle/homopolyelectrolyte layers are adsorbed, it is possible to selectively dissolve the latex template, resulting in hollow capsules.