香港大学Stoddart, J. Fraser团队报道了动态超分子扭棱立方体。相关研究成果于2025年1月8日发表在《自然》。

模拟球形生物包膜（如病毒衣壳和铁蛋白）的上层结构和性质，为理解其手性组装和在生命系统中的功能作用提供了可行的途径。然而，具有类似于生物包封剂的机械性能，和客体结合属性的人造多面体的立体特异性组装，仍然是一个艰巨的挑战。

该文中，研究人员报告了由12个螺旋大环组成的，动态超分子扭棱立方体的立体特异性组装，这些大环由144个弱C-H氢键连接在一起。对映体纯的扭棱立方体，外径为5.1nm，含有2712个原子和体积为62153的手性空腔。左手和右手扭棱立方体的立体特异性组装，是通过分级手性转移协议实现的，该协议通过非对映选择性结晶进行了简化。

除了可逆的光致变色行为外，扭棱立方体在结晶状态下还表现出可光控制的弹性和硬度。扭棱立方体可以同时容纳许多小客体分子，并将两种不同的客体分子分别封装在其框架中独特的隔间内。

该研究扩大了人工超分子组装的范围，以模拟球形生物大分子的手性超结构、动态特征和结合特性，并建立了一种构建具有可光控制机械性能的晶体材料的方案。

附：英文原文

Title: Dynamic supramolecular snub cubes

Author: Wu, Huang, Wang, Yu, orevi, Luka, Kundu, Pramita, Bhunia, Surojit, Chen, Aspen X.-Y., Feng, Liang, Shen, Dengke, Liu, Wenqi, Zhang, Long, Song, Bo, Wu, Guangcheng, Liu, Bai-Tong, Yang, Moon Young, Yang, Yong, Stern, Charlotte L., Stupp, Samuel I., Goddard, William A., Hu, Wenping, Stoddart, J. Fraser

Issue&Volume: 2025-01-08

Abstract: Mimicking the superstructures and properties of spherical biological encapsulants such as viral capsids1 and ferritin2 offers viable pathways to understand their chiral assemblies and functional roles in living systems. However, stereospecific assembly of artificial polyhedra with mechanical properties and guest-binding attributes akin to biological encapsulants remains a formidable challenge. Here we report the stereospecific assembly of dynamic supramolecular snub cubes from 12 helical macrocycles, which are held together by 144 weak C–H hydrogen bonds3. The enantiomerically pure snub cubes, which have external diameters of 5.1nm, contain 2,712 atoms and chiral cavities with volumes of 6,2153. The stereospecific assembly of left- and right-handed snub cubes was achieved by means of a hierarchical chirality transfer protocol4, which was streamlined by diastereoselective crystallization. In addition to their reversible photochromic behaviour, the snub cubes exhibit photocontrollable elasticity and hardness in their crystalline states. The snub cubes can accommodate numerous small guest molecules simultaneously and encapsulate two different guest molecules separately inside the uniquely distinct compartments in their frameworks. This research expands the scope of artificial supramolecular assemblies to imitate the chiral superstructures, dynamic features and binding properties of spherical biomacromolecules and also establishes a protocol for construction of crystalline materials with photocontrollable mechanical properties.

DOI: 10.1038/s41586-024-08266-3

Source: https://www.nature.com/articles/s41586-024-08266-3