Synthesis of Low-Dimensional Polyion Complex Nanomaterials via Polymerization-Induced Electrostatic Self-Assembly.

Nanostructured polyion complexes (PICs) are appealing in biomaterials applications. Yet, conventional assembly suffers from the weakness in scale-up and reproducibility. Only a few low-dimensional PICs are available to date. Herein we report an efficient and scalable strategy to prepare libraries of low-dimensional PICs. It involves a visible-light-mediated RAFT polymerization of ionic monomer in the presence of a polyion of the opposite charge at 5-50 % w/w total solids concentration in water at 25 °C, namely, polymerization-induced electrostatic self-assembly (PIESA). A Vesicle, multi-compartmental vesicle, and large-area unilamellar nanofilm can be achieved in water. A long nanowire and porous nanofilm can be prepared in methanol/water. An unusual unimolecular polyion complex (uPIC)-sphere-branch/network-film transition is reported. This green chemistry offers a general platform to prepare various low-dimensional PICs with high reproducibility on a commercially viable scale under eco-friendly conditions.