Hybrid poly(N-isopropylacrylamide)-based microgels are templated from inverse Pickering emulsions, and the tunable wettability renders as-prepared emulsions with reversible feature.

Despite Pickering interfacial biocatalysis being a popular topic in biphasic biocatalysis, the development of water-in-oil (w/o) emulsion systems stabilized by single particles remains a challenge. For the first time, hydrophobized proteinaceous colloidosomes with magnetic-responsiveness are developed to function as both an enzyme carrier and emulsifier, achieving a breakthrough in protein-based w/o Pickering bioconversion. Enzyme-loaded protein colloidosomes are synthesized by a facile and mild method via emulsion templating. This system exhibits superior catalytic activity to other systems at the oil–water interface. Besides, feasible enzyme recovery and reusability ensure that this novel system can be employed as an efficient and eco-friendly recyclable platform.

Surface-segregated micelles (SSMs) with adaptive wettability have considerable potential for application in Pickering emulsions and bioanalytical technology. In this study, spherical SSMs were prepared via polymerization-induced self-assembly co-mediated with a binary mixture of macromolecular chain transfer agents: pH-responsive poly(2-(dimethylamino) ethyl methacrylate) and hydrophobic polydimethylsiloxane. Using these SSMs as the sole emulsifier, we adjusted the pH to successfully produce both water-in-oil-in-water (W/O/W) and oil-in-water-in-oil (O/W/O) multiple emulsions through a single-step emulsification process. Moreover, we demonstrated that multiple emulsion systems with adjustable pH are suitable for the development of an efficient and recyclable interfacial catalytic system. Multiple emulsion microreactors increase the area of the oil–water interface and are therefore more efficient than the commonly used O/W and W/O emulsion systems.

Particle assembly at liquid–liquid interfaces presents a promising bottom‐up strategy for creating supramolecular materials with advanced functionalities. However, the significantly lower interfacial tension observed in immiscible organic phases compared to traditional oil–water systems has hindered the effective adsorption and assembly of particles at oil–oil interfaces. In this work, a versatile and effective strategy is presented that utilizes the assembly and jamming of microgels and polymer ligands at non‐aqueous liquid–liquid interfaces to create non‐aqueous Pickering emulsions and reconfigurable droplet networks. The resulting microgel‐polymer complexes form an asymmetric interfacial bilayer with high surface coverage, which effectively minimizes interfacial energy and improves interfacial elasticity. Through a combination of systematic interfacial measurements and molecular dynamics simulations, the underlying mechanisms governing interfacial self‐assembly are elucidated. Notably, the stimuli‐responsive nature of the microgel‐polymer complexes allows for precise control over the interfacial assembly and disassembly by introducing competitive molecules. Furthermore, it is demonstrated that these non‐aqueous Pickering emulsions serve as excellent templates for the fabrication of heterogeneous organogels and microgel‐based colloidosomes through both covalent and non‐covalent crosslinking strategies. This work underscores the potential of non‐aqueous interfaces in advancing materials science and opens new avenues for developing multifunctional materials.

The preparation of monodisperse Pickering emulsions currently can only be achieved using microfluidics or membrane emulsification, limiting its widespread applications in many fields. Here, by simply introducing naturally occurring pollen grains during mechanical emulsification, it becomes extremely feasible to fabricate uniform Pickering emulsions. The process of shearing and turbulence leads to a constant reduction in the size of the droplets of the dispersed phase. The robust exine of the pollen grains in the continuous phase enables them to retain their structural integrity during emulsification, resulting in the formation of a single pollen‐in‐water‐in‐oil structure. Meanwhile, the intrinsic monodispersity of the pollen grains allows for the resulting emulsions to be similarly uniform, and they can be easily collected through centrifugation. As a result, this novel methodology achieves the effective formulation of monodisperse Pickering emulsions in an unprecedented way. Furthermore, the utilization of sporopollenin exine capsules (SECs) as a replacement for pollen, in conjunction with sol–gel interfacial engineering, enables the attainment of “yolk‐shell” dual‐shell microcapsules. This approach not only effectively addresses the issue of cargo leakage in SECs but also imparts exceptional uniformity and stability to the microcapsules.