文章信息/Info

Title:

Precision Synthesis and Controlled Assembly of Giant Molecule Isomers

作者:

邵宇12; 楊曙光2; 張文彬1

（1. 北京大學化學與分子工程學院  軟物質科學與工程中心 高分子化學與物理教育部重點實驗室，北京 100871）
（2. 東華大學先進低維材料中心  材料科學與工程學院  纖維改性國家重點實驗室，上海 201620）

Author(s):

SHAO Yu12;  YANG Shuguang2;  ZHANG Wenbin1

（1. Key Laboratory of Polymer Chemistry & Physics of Ministry of Education, Center for Soft Matter Science and Engineering, College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, China）
（2. Center for Advanced Low�睤imension Materials, State Key Laboratory for Modification of Chemical Fibers and Polymer Materials, College of Material Science and Engineering, Donghua University, Shanghai 201620, China）

關鍵詞:

巨型分子;  分子納米粒子;  區域異構體;  POSS;  精準合成;  自組裝

Keywords:

giant molecules;  molecular nanoparticles;  regio-isomer;  POSS;  precision synthesis;  self-assembly

DOI:

10.7502/j.issn.1674-3962.2019.05.01

文獻標志碼:

A

摘要:

相對于有機小分子，合成高分子的性質通常對微小的化學結構差別不敏感，而更依賴于多個重復單元之間集合的物理作用。但是，在生物大分子中，精細的結構差別則往往決定了其折疊與功能。近年來，“巨型分子”的出現填補了這兩者間的空白。巨型分子是基于分子納米粒子的精密結構大分子，主要包括巨型表面活性劑、巨型形狀兩性體、巨型多面體以及巨型不對稱粒子等。由于其可通過點擊化學等方法模塊化構建，使得研究精密結構區別對大分子組裝的影響成為可能。總結了巨型分子異構體精準合成與可控組裝的典型案例，著重探討了區域異構現象對其多層次組裝行為的具體影響及其分子機制，揭示了精確的一級結構在大分子組裝中的重要性。

Abstract:

Compared with small molecules, the properties of synthetic polymers are not sensitive to the minute difference in their primary chemical structures, but rather depend on the collective interaction among monomers. Nonetheless, biomacromolecules exhibit an extraordinary sensitivity to the fine structural differences. The gap between these two categories has been filled with the emerging “giant molecules” over the past decade. Giant molecules are precise macromolecules based on molecular nanoparticles with rigid 3D framework, including but not limited to giant surfactants, giant shape amphiphiles, giant polyhedra, and giant molecular Janus particles. Their synthesis can be facilitated by click chemistry and other highly efficient chemical transformations with excellent atom economy. It is thus possible to study the influence of minute structural differences on their final assembly and properties. This review summarizes the relevant work on the difference between various isomers of giant molecules, especially regio�瞚somers. The molecular mechanism behind the distinct phase behaviors are thoroughly discussed, which reveals how the atomic precision on primary chemical structure dominates hierarchical assembly and how the difference propagates and gets amplified across different length scales.