Bioinspired Autocatalysis for Polymer Nanoparticle Synthesis: Monomer Preassembly through Liquid-Liquid Phase Separation
Ying Cao, Ran Zhang, Xiaoyue Xu,Xiyu Wang, Yuting Li, Xinhua Lu, Yuanli Cai（蔡远利）*
State-Local Joint Engineering Laboratory for Novel Functional Polymer Materials, Jiangsu Engineering Laboratory of Novel Functional Polymeric Materials, Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Macromolecules, 2024, 57, 8097−8108
Abstract: Biomimetic synthesis represents a cutting-edge topic in chemical and materials sciences. Herein, we present anapproach to bioinspired polymerization autocatalysis using a single amino acid monomer in water. Similar to biomolecularcondensates, this monomer undergoes an entropically driven liquid−liquid phase separation (LLPS)-mode self-assembly involvingdensely charged molecular clusters formation, LLPS of charged monomer clusters leading to submicron-scale droplets, crystallizationof charged monomer clusters within droplet crowding environments resulting in dynamic nanocrystals@droplets and finally lessdynamic aged-lamellae. Supramolecular chirality inversion and nanocrystal disassembly into charged monomer clusters occur upondoping of a minor RAFT agent. Autocatalysis with solvent-tuned H+-feedback and covalent-driven chirality inversion is achievedusing extremely dynamic nanocrystals@droplets. Decelerated kinetics upon deionization/ion-pairing underscore the vital importanceof LLPS for the “higher charge repulsion leads to more rapid polymerization”, yielding polymer nanoparticles with protein-likestructural complexity up to >98% conversion in 2-min-propagation period. This autocatalysis provides new insights into bioinspiredefficient synthesis of polymer nanoparticles.
链接：//pubs.acs.org/doi/10.1021/acs.macromol.4c01527
