When the self-assembly of block copolymers (BCPs) occurs within a deformable emulsion droplet, BCPs can aggregate into a variety of nanoscaled particles with unique nanostructures and properties since the confinement effect can effectively break the symmetry of a structure. On the other hand, the self-assembled BCP particles can serve as the scaffolds to further direct the spatial arrangement of functional inorganic nanoparticles (NPs) via co-assembly or in situ deposition, thus generating diverse hybrid functional BCP/NP composites with enhanced properties. Here, we summarize the recent progress in the confined self-assembly of BCPs within the emulsion droplet and spatial arrangement of NPs on the resulting BCP scaffolds. This feature article focuses on the influence of multiple factors, including the oil/water interfacial properties, confinement degree, intrinsic properties of BCPs, additives, pH value, and temperature, on the nanostructures of the self-assembled BCP particles as well as the spatial arrangement of NPs on the BCP scaffolds from both experiment and simulation studies.

Well-defined polymeric particles with not only a controllable shape and internal nanostructures but also stimuli-responsive functions have attracted intensive attention because of their great potential in various fields. Herein, we created unique sieve-like particles with lattice arrayed switchable channels via the confined self-assembly of poly(4-vinylpyridine)-b-polystyrene-b-poly(4-vinylpyridine) (P4VP-b-PS-b-P4VP) triblock copolymers within the emulsion droplets and the subsequent swelling treatment in ethanol. It is worth noting that the hexagonally packed P4VP channels in the sieve-like particles are switched on and off by changing the solvent type, i.e., P4VP channels are switched on in ethanol and switched off in water, which can operate as a solvent-controlled chemical gate. Moreover, the well-defined sieve-like particles can be further used as scaffolds to guide the spatial arrangement of gold nanoparticles, which generates hybrid nanomaterials with controllable morphology and ordered spatial arrangement of AuNPs.