Raspberry-Shaped Microgels Assembled at the Oil–Water Interface by Heterocoagulation of Complementary Microgels

Raspberry-shaped particles have attracted increasing interest due to their tunable surface morphologies and physicochemical properties. A variety of covalent and noncovalent strategies have been developed for the fabrication of raspberry-shaped particles. However, most of these strategies are complex or require precise control of solution conditions. In this work, we develop a direct approach for the fabrication of noncovalent raspberry-shaped microgels. Our strategy works through the electrostatically driven heterocoagulation of binary microgels with complementary functional groups at the oil-water interface. By introducing hexanoic acid (HA) into the oil phase, stable inverse water-in-oil (w/o) Pickering emulsions could be stabilized solely by HA-swollen microgels or self-assembled raspberry-shaped microgels. Furthermore, the formation mechanism and the interfacial properties of interfaces laden with raspberry-shaped microgels were investigated. The results indicate that HA can effectively improve the hydrophobicity and interfacial activity of microgels. In addition, raspberry-shaped microgels achieve high coverage on the droplet surface, resulting in the elastic interface and excellent stability of emulsions. We envision that these results will not only fill a knowledge gap in the field of soft matter interfacial self-assembly, but also will shed light on the rational design of raspberry-shaped soft colloids and the on-demand control of interfacial rheology. In addition, we expect that our results will contribute to wider applications of microgel-stabilized emulsions, including cascade catalysis, microreactor, and in vivo drug delivery.