Interfacial Liquid-Liquid Phase Separation-Driven Polymerization-Induced Electrostatic Self-Assembly
Interfacial Liquid-Liquid Phase Separation-Driven Polymerization-Induced Electrostatic Self-Assembly
复制标题
界面液-液相分离驱动聚合诱导静电自组装
DOI：
10.1021/acs.macromol.1c00756
复制
发表时间：
2021
期刊：
影响因子：
5.5
通讯作者：
Cai Yuanli
中科院分区：
文献类型：
--
作者：
Wang Ye;Li Chao;Ma Lei;Wang Xiyu;Wang Kai;Lu Xinhua;Cai Yuanli
由于缺乏类似于内在无序蛋白质的序列限定的两性离子片段的空间限制凝聚的方法，模拟生物分子凝聚物的空间限制的液-液相分离（LLPS）系统的开发是凝聚材料科学中的主要挑战。在此，我们提出了界面LLPS驱动的聚合诱导静电自组装，即，界面LLPS-PIESA。两性离子生长片段的不对称电荷序列图案化是通过纳米颗粒核壳界面内离子对单体的自发聚合来实现的。我们发现，电荷序列可以深刻地影响自凝聚，导致液滴分散体，致密的凝聚体，和独立的水凝胶。此外，界面LLPS-PIESA显示出一个程序化的分层缩合自组装机制，包括囊泡到层状过渡，界面自凝聚，层状到片状过渡，逐层片状自组装，空间限制的缩合和团聚，并在动态演变的表面电荷调节下再分散成原纤维网络缩合物。空间限制的不对称电荷序列图案化、界面自凝聚和程序化的分级缩合自组装，所有这些元素可以作为模拟细胞生物分子缩合物的分级纳米结构缩合物的不对称电荷序列图案化设计的主要原则。
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 self-assembly mechanism involving vesicles-to-lamellae transition, interfacial self-coacervation, lamellae-to-sheets transition, layer-by-layer 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 self-coacervation, 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.