Synthesis of "hard-soft" janus particles by seeded dispersion polymerization.

The majority of studies on Janus particles focus on those that show amphiphilicity, with distinct hydrophilic and hydrophobic domains. Here, we demonstrate the synthesis of a different class of Janus particles: "hard-soft" biphasic dumbbell- or peanut-shaped particles with distinct lobes of "soft" poly(n-butyl acrylate) and "hard" poly(styrene). The particles are made by seeded dispersion polymerization of butyl acrylate in the presence of poly(styrene) seed particles. Surface nucleation by capture of the oligoradicals onto the surface of the seed particles thereby forming a distinct new polymer phase is found to be the formation mechanism of these particles. The total available poly(styrene) seed surface area plays a significant role in the size and number of poly(butyl acrylate) lobes grown off a single particle. At particularly low values of the surface area, we observe the formation of multilobe particles. We further demonstrate that our synthesis method is versatile and can be extended to the submicrometer domains by using seed particles of 200 nm in diameter.

Hierarchical self-assembly of 'hard-soft' Janus particles into colloidal molecules and larger supracolloidal structures.

Here we report the self-assembly of 'hard-soft' micron-sized Janus particles into clusters in aqueous media. The assembly process is induced by the desorption of a polymeric stabiliser from the particles, that is polyvinylpyrrolidone (PVP). Upon contact through collision and coalescence of the soft polymeric lobes, the newly formed clusters adopt a minimized surface area to volume ratio, thereby forming distinct microscopic supracolloidal analogues of simple molecular valance shell electron pair repulsion (VSEPR) space-fill structures. To explain this behaviour, the colloidal stability of our particle suspensions were studied with and without an adsorbed steric surfactant. Simulations of expected cluster morphology, compared with those from cryo-SEM analysis support the mechanism of assembly driven by surface area minimization in the case of soft-soft interactions. Altering the soft lobe size with respect to the hard lobe indicates a moderate effect on number of primary particles per cluster. Additionally, higher order structures of clusters containing a number of primary particles exceeding what is possible for a 'solid' core cluster are observed. As such, we also investigated the formation of suprastructures using a high number of 'hard-soft' Janus particles and verified their effective Pickering stabilization of air bubbles.

High internal phase agar hydrogel dispersions in cocoa butter and chocolate as a route towards reducing fat content.

Reducing the fat content of chocolate formulations is a major challenge for the confectionery industry. We report the suspension of aqueous microgel agar particles of up to 80% v/v within sunflower oil, cocoa butter, and ultimately chocolate. The optimised emulsification process involves a shear-cooling step. We demonstrate the versatility of our method when applied to white, milk, and dark chocolate formulations, whilst preserving the desired polymorph V of the cocoa butter matrix. In addition, we show that this technology can be used as a strategy to disperse alcoholic beverages into chocolate confectionery.

Influence of Janus particle shape on their interfacial behavior at liquid-liquid interfaces.

We investigate the self-assembly behavior of Janus particles with different geometries at a liquid-liquid interface. The Janus particles we focus on are characterized by a phase separation along their major axis into two hemicylinders of different wettability. We present a combination of experimental and simulation data together with detailed studies elucidating the mechanisms governing the adsorption process of Janus spheres, Janus cylinders, and Janus discs. Using the pendant drop technique, we monitor the assembly kinetics following changes in the interfacial tension of nanoparticle adsorption. According to the evolution of the interfacial tension and simulation data, we will specify the characteristics of early to late stages of the Janus particle adsorption and discuss the effect of Janus particle shape and geometry. The adsorption is characterized by three adsorption stages which are based on the different assembly kinetics and different adsorption mechanisms depending on the particle shape.