Shaping Block Copolymer Microparticles by pH-Responsive Core-Cross-Linked Polymeric Nanoparticles.

Block copolymer microparticles with controllable morphology have drawn widespread attention owing to their promising applications in photonic materials, energy storage, and other areas. Hence, it is highly desired to achieve a controllable transformation of microparticle morphology. In this work, we report a simple method to shape the morphology of polystyrene-block-poly(dimethylsiloxane) (PS-b-PDMS) microparticles, by employing core-cross-linked polymeric nanoparticles (CNPs) as cosurfactants which are synthesized through cross-linking P4VP segment of PS-block-poly(4-vinylpyridine) (PS-b-P4VP). The addition of pH-responsive CNPs makes the shape of pH-inert PS-b-PDMS microparticles sensitive to pH value. The PS-b-PDMS microparticles transformed from elongated Janus pupa-like particles to onion-like particles by decreasing the pH value of the aqueous phase. The deformation mechanism is investigated by changing pH value, the weight fraction of CNPs, and surfactant property. This study provides a facile strategy to deform microparticles of pH-inert BCPs by tuning pH value, which is anticipated to be applicable to other non-pH-responsive BCP microparticles.