中文摘要：

本文聚焦于一类非传统的高分子结构,也即基于分子纳米粒子（或称纳米原子,nano-atoms）的巨型分子（giant molecules）。分子纳米粒子是具有确定化学组成、分子对称性和表面官能团的三维刚性笼状骨架结构。巨型分子是利用分子纳米粒子基元构筑的具有精确结构的高分子。受到蛋白质中结构域概念的启发,我们提出经过表面官能化修饰的分子纳米粒子可以作为合成高分子的结构域和功能域,通过逆功能分析,结合包括点击化学在内的高效化学反应,来实现巨型分子的快速模块化合成、可控组装和功能评估,并利用其中得到的构效关系,更为系统地理解材料的性质和指导材料的进一步优化设计。同时,这种新型高分子也可被看成是尺寸放大的小分子。它的许多有趣的自组装行为和相应小分子既有相似之处,又有截然不同之处。比如,巨型表面活性剂在溶液中能像小分子表面活性剂一样组装成为尾链被拉伸的胶束,在本体中则像嵌段聚合物一样形成纳米相分离的结构。这些组装展现出对于一级化学结构不同寻常的敏感性,并容易形成一些非传统的罕见相态,包括Frank-Kasper相态、在低分子量层状晶体PEO中出现的非整数折叠以及在溶液组装中出现的多级结构。因此,我们认为巨型分子作为功能材料在将来的技术领域中将具有广阔的应用前景。

英文摘要：

This review focuses on a class of unconventional macromolecules- giant molecules based on nanoatoms.Nano-atoms are 3D molecular nanoparticles （MNPs）with rigid shapes, well-defined chemical structures,and specific symmetries.Giant molecules are precise macromolecules built from molecular nanoparticles.Inspired by the domain concept in proteins, we propose that MNPs can serve as the structural and functional domains for synthetic macromolecule, allowing one to design and synthesize materials with the desired function in a modular fashion via the retro-functional analysis.The structure-property relationship gained from this process will improve our understanding of these materials and guide the optimization of the materials property.Giant molecules can also be viewed as size-amplified small-molecule analogues, exhibiting similar but also distinct selfassembly behaviors from their counterparts.For example, giant surfactants behave like small-molecule surfactants in solution, forming micelles with stretched tails and versatile morphologies, but assemble into nano-phaseseparated structures in bulk just like block copolymers.Their self-assembly exhibits unusual sensitivity to the primary chemical structures and the formation of unconventional hierarchical structures is not uncommon,including the Frank-Kasper phases, the non-integral folding in low molecular weight PEO lamellar crystals and various hierarchical structures in solution self-assembly.Therefore, we envision that giant molecules will be technically very important and receive numerous practical applications in the near future.