Bioinspired Autocatalysis for Polymer Nanoparticle\nSynthesis: Monomer Preassembly through Liquid–Liquid Phase\nSeparation

Biomimetic synthesis represents a\ncutting-edge topic in chemical\nand materials sciences. Herein, we present an approach to bioinspired\npolymerization autocatalysis using a single amino acid monomer in\nwater. Similar to biomolecular condensates, this monomer undergoes\nan entropically driven liquid–liquid phase separation (LLPS)-mode\nself-assembly involving densely charged molecular clusters formation,\nLLPS of charged monomer clusters leading to submicron-scale droplets,\ncrystallization of charged monomer clusters within droplet crowding\nenvironments resulting in dynamic nanocrystals@droplets and finally\nless dynamic aged-lamellae. Supramolecular chirality inversion and\nnanocrystal disassembly into charged monomer clusters occur upon doping\nof a minor RAFT agent. Autocatalysis with solvent-tuned H<sup>+</sup>-feedback and covalent-driven chirality inversion is achieved using\nextremely dynamic nanocrystals@droplets. Decelerated kinetics upon\ndeionization/ion-pairing underscore the vital importance of LLPS for\nthe “higher charge repulsion leads to more rapid polymerization”,\nyielding polymer nanoparticles with protein-like structural complexity\nup to >98% conversion in 2-min-propagation period. This autocatalysis\nprovides new insights into bioinspired efficient synthesis of polymer\nnanoparticles.