Zhu Hao, Feng Weisheng, Wang Yueyao, Li Zhengyi, Xu Binbin, 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. 2025 Jan 2;21(2):255-261. doi: 10.1039/d4sm01232a.
The self-assembly behaviors of rod-coil asymmetric diblock molecular brushes (ADMBs) bearing responsive side chains in a selective solvent are investigated dissipative particle dynamics simulations. By systematically varying the polymerization degree, copolymer concentration, and side chain length, several morphological phase diagrams were constructed. ADMB assemblies exhibited a rich variety of morphologies, including cylindrical micelles, spherical micelles, nanowires, polyhedral micelles, ellipsoid micelles, and large compound micelles. The structures of the representative nanowires were analyzed in detail. A kinetics study revealed that the one-dimensional growth of nanowires follows the step-growth polymerization mechanism. Besides, by calculating the local order parameter of the rigid chains, we found that increasing the lengths of A and C side chains can promote the ordered arrangement of the rigid chains. Moreover, the rod-to-coil conformation transitions were simulated to explore the stimuli-responsive behaviors of ADMBs with responsive rigid side chains. The simulation results indicated that the volume of the assemblies expanded without the support of the rigid chains. The present work not only provides a comprehensive understanding of the self-assembly behaviors of ADMBs but also provides meaningful theoretical support for the development of novel molecular brush materials.
通过耗散粒子动力学模拟研究了在选择性溶剂中带有响应性侧链的棒-线圈不对称二嵌段分子刷（ADMBs）的自组装行为。通过系统地改变聚合度、共聚物浓度和侧链长度，构建了几个形态相图。ADMB组装体表现出丰富多样的形态，包括圆柱形胶束、球形胶束、纳米线、多面体胶束、椭球形胶束和大复合胶束。对代表性纳米线的结构进行了详细分析。动力学研究表明，纳米线的一维生长遵循逐步聚合机制。此外，通过计算刚性链的局部序参量，我们发现增加A和C侧链的长度可以促进刚性链的有序排列。此外，模拟了棒-线圈构象转变，以探索具有响应性刚性侧链的ADMBs的刺激响应行为。模拟结果表明，在没有刚性链支持的情况下，组装体的体积会膨胀。本工作不仅全面了解了ADMBs的自组装行为，还为新型分子刷材料的开发提供了有意义的理论支持。
