Yuan Chengqian, Yang Mengyao, Ren Xiaokang, Zou Qianli, Yan Xuehai
State Key Laboratory of Biochemical Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing, 100190, P. R. China.
School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing, 100049, P. R. China.
Angew Chem Int Ed Engl. 2020 Sep 28;59(40):17456-17460. doi: 10.1002/anie.202007459. Epub 2020 Aug 11.
Understanding and controlling multicomponent co-assembly is of primary importance in different fields, such as materials fabrication, pharmaceutical polymorphism, and supramolecular polymerization, but these aspects have been a long-standing challenge. Herein, we discover that liquid-liquid phase separation (LLPS) into ion-cluster-rich and ion-cluster-poor liquid phases is the first step prior to co-assembly nucleation based on a model system of water-soluble porphyrin and ionic liquids. The LLPS-formed droplets serve as the nucleation precursors, which determine the resulting structures and properties of co-assemblies. Co-assembly polymorphism and tunable supramolecular phase transition behaviors can be achieved by regulating the intermolecular interactions at the LLPS stage. These findings elucidate the key role of LLPS in multicomponent co-assembly evolution and enable it to be an effective strategy to control co-assembly polymorphism as well as supramolecular phase transitions.
在材料制造、药物多晶型和超分子聚合等不同领域，理解和控制多组分共组装至关重要，但这些方面一直是长期存在的挑战。在此，我们基于水溶性卟啉和离子液体的模型体系发现，液-液相分离（LLPS）形成富含离子簇和贫离子簇的液相是共组装成核之前的第一步。LLPS形成的液滴作为成核前体，决定了共组装体的最终结构和性质。通过调节LLPS阶段的分子间相互作用，可以实现共组装多晶型和可调谐的超分子相变行为。这些发现阐明了LLPS在多组分共组装演化中的关键作用，并使其成为控制共组装多晶型以及超分子相变的有效策略。
