Li Zhengyi, Feng Weisheng, Zhang Xing, Xu Binbin, Wang Liquan, Lin Shaoliang
Shanghai Key Laboratory of Advanced Polymeric Materials, Key Laboratory for Ultrafine Materials of Ministry of Education, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai 200237, China.
Soft Matter. 2024 Mar 20;20(12):2823-2830. doi: 10.1039/d4sm00076e.
Amphiphilic asymmetric comb-like copolymers (AACCs) exhibit distinct self-assembly behaviours due to their unique architecture. However, the synthetic difficulties of well-defined AACCs have prohibited a systematic understanding of the architecture-morphology relationship. In this work, we conducted dissipative particle dynamics simulations to investigate the self-assembly behaviours of AACCs with responsive rigid side chains in selective solvents. The effects of side chain length, number of branches, and spacers on the morphology of aggregates were investigated by mapping out morphology diagrams. Besides, the numbers and surface areas of aggregates clearly depicted the morphological transitions during the self-assembly process. Moreover, the rod-to-coil conformation transitions were simulated to explore the stimuli-responsive behaviour of the AACCs with responsive rigid side chains by adjusting the bond angle parameter of the rigid chains. The results indicated that without the support of the rigid chains, the assembly structure collapsed, leading to the tube-to-channelized micelles and one-compartment-to-multicompartment vesicle morphology transformations. The simulation results are consistent with earlier experimental results, which can provide theoretical guidance for assembly toward desired nanostructures.
两亲性不对称梳状共聚物（AACCs）由于其独特的结构而表现出独特的自组装行为。然而，结构明确的AACCs合成困难，阻碍了对结构-形态关系的系统理解。在这项工作中，我们进行了耗散粒子动力学模拟，以研究具有响应性刚性侧链的AACCs在选择性溶剂中的自组装行为。通过绘制形态图，研究了侧链长度、支链数量和间隔基对聚集体形态的影响。此外，聚集体的数量和表面积清楚地描绘了自组装过程中的形态转变。此外，通过调整刚性链的键角参数，模拟了棒状到线圈状的构象转变，以探索具有响应性刚性侧链的AACCs的刺激响应行为。结果表明，在没有刚性链支持的情况下，组装结构坍塌，导致管状到通道化胶束以及单室到多室囊泡形态的转变。模拟结果与早期实验结果一致，可为组装成所需纳米结构提供理论指导。
