Interfacial Liquid−Liquid Phase Separation-Driven Polymerization- Induced Electrostatic Self-Assembly
Ye Wang, Chao Li, Lei Ma, Xiyu Wang, Kai Wang, Xinhua Lu, and Yuanli Cai*（蔡远利）
State-Local Joint Engineering Laboratory for Novel Functional Polymer Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, China
Macromolecules 2021, 54, 5577--5585
Development of spatially restricted liquid−liquid phase separation (LLPS) systems emulating biomolecular condensates is a major challenge in coacervating materials science, due to lack of approaches for spatially restricted coacervation of sequence-defined zwitterionic segments resembling intrinsically disordered proteins. Herein, we present interfacial LLPS-driven polymerization-induced electrostatic self-assembly, namely, interfacial LLPS-PIESA. The asymmetric charge sequence patterning of zwitterionic growing segments is achieved via spontaneous polymerization of ion-pair monomers within a nanoparticle core−shell interface. We show that charge sequence can profoundly affect the self-coacervation, leading to droplet dispersions, dense coacervates, and free-standing hydrogels. Moreover, the interfacial LLPS-PIESA shows a programmed hierarchical condensation selfassembly mechanism involving vesicles-to-lamellae transition, interfacial self-coacervation, lamellae-to-sheets transition, layer-bylayer sheet self-assembly, spatially restricted condensation and agglomeration, and redispersing into fibril network condensates under dynamic evolving surface charge regulation. The spatially restricted asymmetric charge sequence patterning, interfacial selfcoacervation, and programmed hierarchical condensation self-assembly, all these elements can serve as the primary principles for the asymmetric charge sequence patterning design of hierarchically nanostructured condensates that emulate cellular biomolecular condensates.
链接：https://pubs.acs.org/doi/abs/10.1021/acs.macromol.1c00756