Site-Specific Polymerization-Induced Electrostatic Self-Assembly:Synthesis of Highly Charged Salt-Tolerant Polyion Complex Nanoreactors

Jie Cai, Xiyu Wang, Yuanyuan Liu, Caihui Luo, Xinhua Lu, and Yuanli Cai*（蔡远利）

State-Local Joint Engineering Laboratory for Novel Functional Polymer Materials, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, P. R. China

Macromolecules 2023, 56, 10153−10162

Abstract: We herein report a site-specific polymerization-induced electrostatic self-assembly (PIESA) that enables the precision synthesis of highly charged salt-tolerant nanoreactors. Site-specific PIESA is achieved using an anionic aromatic-aliphatic sulfonate block copolymer in photoinitiated reversible addition-fragmentation chain transfter (photo-RAFT) polymerization of a cationic monomer in water at 25 C-degrees. Preferential complexation of cationic growing chains to the aromatic sulfonate block results in not only site-specific molecular recognition but also unique salt-tolerant PIC nanoparticles. Neutral block incorporation leads to ultrafast reaction of very dilute monomer (2.0% w/w) and exclusive formation of more salt-tolerant smaller spheres or 4 nm fibril-structured 10 nm ultrathin lamellae. The ultrathin lamellae can induce a sequence-controllable ultrafast copolymerization of oppositely-charged dilute monomers with perfect shape/size preservation up to 100% conversions, and thus can be viewed as a nanoreactor. This work opened up an avenue for the precision synthesis of highly charged salt-tolerant PIC functional nanoparticles, providing a versatile platform for easy access to structural and functional complexity from simple mixtures.

链接：https://pubs.acs.org/doi/10.1021/acs.macromol.3c01849