Coacervate Nanoreactors: PEG Side-Chain-Assisted Compartmentalization Leads to an Oxygen-Tolerant Polymerization-Induced Electrostatic Self-Assembly
XiyuWang, QingZheng, Xinhua Lu, Yuanli Cai（蔡远利）*
State-Local Joint Engineering Laboratory forNovel Functional Polymer Materials, Suzhou Key Laboratoryof Macromolecular Design and Precision Synthesis, JiangsuEngineering Laboratory of Novel Functional PolymericMaterials, Jiangsu Key Laboratory of Advanced FunctionalPolymer Materials, College of Chemistry, ChemicalEngineering and Materials Science, Soochow University,Suzhou 215123, China
Macromolecules 2025, 58, 1245−1255
Abstract: Biomimetic synthesis represents a cutting-edge topic in chemistry/materials science. Herein, we demonstrate poly(ethylene glycol) (PEG) short side-chain-assisted monomer complex coacervation and reaction-induced polyion complex compartmentalization that lead to oxygen-tolerant polymerization-induced electrostatic self-assembly (PIESA). This is achieved by the one-pot synthesis of a PEGylated anionic polyelectrolyte and heterogeneous iterative polymerization of a cationic monomer under ecofriendly ambient, in-air aqueous photo-RAFT conditions. Simultaneous reversible all-segment-participating ternary complex coacervation and Coulombic interdomain interactions lead to coacervate nanoreactors that are capable of immediate initiation and fast reversible addition–fragmentation chain transfer reactions. Approximately 2 nm monomer complex nanoclusters act as building blocks to drive liquid–liquid phase separation. Polymerization induces hierarchical self-assembly in a droplet nucleation–fusion–fission mechanism together with PEG-crowded polyion complex compartmentalization, using nanoclusters as building blocks, mechanistically similar to liquid–liquid phase separation through supramolecular polymerization. Consequently, protein-like, one-component multicompartment coacervate nanoreactors with oxygen-tolerant well-controlled fast reactions are achieved. This work provides important implications for the efficient precise synthesis of biomimetic coacervate nanodevices of increasing complexity.
Article information: //doi.org/10.1021/acs.macromol.4c02853
