Design of Thermoresponsive Polyamine Cross-Linked Perfluoropolyether Hydrogels for Imaging and Delivery Applications.

Perfluorocarbons are versatile compounds with applications in 19F magnetic resonance imaging (MRI) and chemical conjugation to drugs and pH sensors. We present a novel thermoresponsive perfluorocarbon emulsion hydrogel that can be detected by 19F MRI. The developed hydrogel contains perfluoro(polyethylene glycol dimethyl ether) (PFPE) emulsion droplets that are stabilized through ionic cross-linking with polyethylenimine (PEI). Specifically, PFPE ester undergoes hydrolysis upon contact with aqueous PEI solution, resulting in an ionic bond between the PFPE acid and charged PEI amino groups. Due to the ionic nature of the PFPE/PEI bond, potassium buffer is required to preserve the hydrogel's pH and rheological and emulsion droplet stability. The presence of the surface cross-linked PFPE droplets does not affect the hydrogel's rheological behavior, drug loading, or drug release, and the hydrogel is nontoxic. We propose that the presented hydrogel can be adapted to a broad range of biomedical imaging and delivery applications.

High-performance vitrimers from commodity thermoplastics through dioxaborolane metathesis.

Windmills, cars, and dental restoration demand polymer materials and composites that are easy to process, assemble, and recycle while exhibiting outstanding mechanical, thermal, and chemical resistance. Vitrimers, which are polymer networks able to shuffle chemical bonds through exchange reactions, could address these demands if they were prepared from existing plastics and processed with fast production rates and current equipment. We report the metathesis of dioxaborolanes, which is rapid and thermally robust, and use it to prepare vitrimers from polymers as different as poly(methyl methacrylate), polystyrene, and high-density polyethylene that, although permanently cross-linked, can be processed multiple times by means of extrusion or injection molding. They show superior chemical resistance and dimensional stability and can be efficiently assembled. The strategy is applicable to polymers with backbones made of carbon-carbon single bonds.

Three distinct open-pore morphologies from a single particle-filled polymer blend.

Ternary mixtures composed of polyisobutylene (PIB), polyethylene oxide (PEO), and silica particles yield three distinct open-pore morphologies depending on the mixture composition: (1) pendular network (particles bonded together by menisci of PEO); (2) capillary aggregate network (particles and PEO form a combined phase with strongly solid-like properties which forms a percolating network); (3) cocontinuous morphology (silica and the PEO form a highly viscous combined phase which retards interfacial tension-driven coarsening). Remarkably, interfacial tension plays altogether different roles in stabilizing these three morphologies: stabilizing the first, not affecting the second, and destabilizing the last. The first two of these morphologies appear to be generalizable to other systems, e.g. to oil/water/particle mixtures. In all three cases, the pores do not collapse even after flow, i.e. all three porous morphologies are amenable to processing.

On the rheology of pendular gels and morphological developments in paste-like ternary systems based on capillary attraction.

We investigate capillary bridging-induced gelation phenomena in silica particle suspensions and pastes, where a particle-wetting fluid is added as the third component. Increasing the wetting fluid loading in the ternary system induces a morphological transition from a pendular network to compact capillary aggregates network, with an intermediate funicular state. To our knowledge, the formation of percolated structures from compact capillary aggregates when the volume fraction of a wetting fluid approaches that of the particles is unprecedented. Such structures appear to result from the arrested coalescence of compact capillary aggregates due to the balance between the Laplace pressure and solid-like properties (yield stress, elasticity) of the aggregates. Shear-induced yielding of the ternary systems, linked to their percolating nature, is strongly influenced by the amount of wetting fluid phase. A non-monotonic dependence of the yield stress on the amount of wetting fluid is found, with the maximum yield stress obtained for a wetting fluid-to-particle volume fraction ratio of 0.2-0.3. For pendular systems, linear viscoelastic properties display a soft glassy rheological behavior above the percolation threshold (around 4 vol% particles), and complex viscosity data can be scaled using the high frequency plateau value, as well as a single characteristic relaxation time, which decreases when the particle concentration is increased. In addition, the particle concentration dependence of the yielding transition in the pendular regime appears to be efficiently described by two parameters extracted from the steady state flow curves: the yield stress and the limiting viscosity at a high shear rate. Although these non-colloidal networks result from flow-driven assembly, the scaling laws for our pendular gels are reminiscent of colloidal gels with a fractal geometry. Our studies pinpoint new pathways to create physical gels where the interparticle attraction strength is determined by capillary interactions.

Aggregation and separation in ternary particle/oil/water systems with fully wettable particles.

We report that a variety of ternary particle/liquid/liquid mixtures heavily aggregate or separate completely if (1) the particles are fully or almost fully wetted by one fluid, and (2) if the wetting fluid volume fraction is comparable to the particle volume fraction. Aggregation and separation do not happen if the particles are partially wetted by both fluids, in which case Pickering emulsions appear at all compositions. Rheological and geometric criteria for aggregation are proposed and compared with a state diagram of a ternary system composed of oil, water, and hydrophilic glass particles. Analogies are drawn to wet granulation and spherical agglomeration, two particle processing operations in which wetting phenomena are important.