美国普林斯顿大学Link, A. James报道了仅由多肽组成的机械联锁分子的动态共价自组装策略。相关研究成果于2021年8月23日发表于国际一流学术期刊《自然—化学》。

机械联锁分子（MIM），如轮烷和链烷，从合成角度和作为分子机器简单原型的作用引起了化学家的注意。尽管自然界中存在实例，但大多数合成MIM是由人工构件制成，并在有机溶剂中组装而成。从天然生物分子合成MIMs仍然是一项极具挑战性的工作。

该文中，研究人员报告了一种仅由肽制成的联锁分子的合成策略，即机械联锁肽（MIPs）。全肽、半胱氨酸修饰的构建块在水中自组装，生成由多种不同的轮烷、链烷和菊花链以及更奇特的结构组成的二硫键动态组合文库。包含两个肽大环的[2]链烷的详细NMR光谱和质谱表征表明，该结构具有丰富的构象动力学，使人联想到蛋白质折叠。因此，MIPs可以作为完全合成MIM和自然界中发现的MIM之间的桥梁。

附：英文原文

Title: Dynamic covalent self-assembly of mechanically interlocked molecules solely made from peptides

Author: Schrder, Hendrik V., Zhang, Yi, Link, A. James

Issue&Volume: 2021-08-23

Abstract: Mechanically interlocked molecules (MIMs), such as rotaxanes and catenanes, have captured the attention of chemists both from a synthetic perspective and because of their role as simple prototypes of molecular machines. Although examples exist in nature, most synthetic MIMs are made from artificial building blocks and assembled in organic solvents. The synthesis of MIMs from natural biomolecules remains highly challenging. Here, we report on a synthesis strategy for interlocked molecules solely made from peptides, that is, mechanically interlocked peptides (MIPs). Fully peptidic, cysteine-decorated building blocks were self-assembled in water to generate disulfide-bonded dynamic combinatorial libraries consisting of multiple different rotaxanes, catenanes and daisy chains as well as more exotic structures. Detailed NMR spectroscopy and mass spectrometry characterization of a [2]catenane comprising two peptide macrocycles revealed that this structure has rich conformational dynamics reminiscent of protein folding. Thus, MIPs can serve as a bridge between fully synthetic MIMs and those found in nature.

DOI: 10.1038/s41557-021-00770-7

Source: https://www.nature.com/articles/s41557-021-00770-7