Polymerization-Induced Hierarchical Electrostatic Self-Assembly: Scalable Synthesis of Multicompartment Polyion Complex Micelles and Their Monolayer Colloidal Nanosheets and Nanocages.

Scalable synthesis of multicompartment polyion complex (PIC) systems has been achieved via visible light-initiated RAFT polymerization of cationic monomer in the presence of anionic diblock copolymer micelles in water at 25 °C. This polymerization-induced hierarchical electrostatic self-assembly (hierarchical PIESA) implements structural hierarchy via programmable self-assembly to form multicompartment PIC micelles and their monolayer colloidal nanosheets and nanocages. The anionic micelles play decisive roles in such a hierarchical PIESA to access biologically relevant yet otherwise inaccessible multicompartment PIC systems.