Polymerization-Induced Self-Assembly of Block Copolymers for Fabricating Polymeric Nanomaterials with Inverse Morphologies

Inverse nanostructures offer unique structural features, including multicompartmental organization and high surface area, rendering them promising for applications as porous materials and for molecular separations, catalysis, and biointerfaces. However, inverse nanostructures constructed via block copolymer self-assembly suffer from low concentrations, multistep processing, limited scalability, and morphological complexity. Polymerization-induced self-assembly (PISA) offers a powerful alternative, enabling the efficient, one-pot fabrication of nanostructures with tunable morphologies at high solid contents. This review highlights recent advances in using PISA to access inverse morphologies, summarizing key parameters, including block composition, monomer design, and solvent selectivity, that govern structure formation. This review also presents several illustrative examples that demonstrate the practical applications of inverse morphologies synthesized through the PISA approach, thereby illuminating future opportunities for this innovative technique.