Dynamic Assembly of Microgels and Polymers at Non‐Aqueous Liquid/Liquid Interfaces

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.