University of Bordeaux, CBMN (UMR 5248), Institut Européen de Chimie et Biologie, 2 rue Escarpit, 33600, Pessac, France.
CNRS, CBMN (UMR 5248), France.
Angew Chem Int Ed Engl. 2016 Jun 6;55(24):6848-52. doi: 10.1002/anie.201601156. Epub 2016 Apr 21.
Disulfide bridge formation was investigated in helical aromatic oligoamide foldamers. Depending on the position of thiol-bearing side chains, exclusive intramolecular or intermolecular disulfide bridging may occur. The two processes are capable of self-sorting, presumably by dynamic exchange. Quantitative assessment of helix handedness inversion rates showed that bridging stabilizes the folded structures. Intermolecular disulfide bridging serendipitously yielded a well-defined, C2 -symmetrical, two-helix bundle-like macrocyclic structure in which complete control over relative handedness, that is, helix-helix handedness communication, is mediated remotely by the disulfide bridged side chains in the absence of contacts between helices. MM calculations suggest that this phenomenon is specific to a given side chain length and requires disulfide functions.
研究了螺旋状芳香寡酰胺折叠物中的二硫键形成。根据含巯基侧链的位置，可能会发生专有的分子内或分子间二硫键桥接。这两个过程能够自我分类，可能是通过动态交换。对螺旋手性反转速率的定量评估表明，桥接稳定了折叠结构。分子间二硫键桥接偶然产生了一种定义明确的、C2 对称的、双螺旋束状大环环状结构，其中相对手性（即螺旋-螺旋手性通讯）完全由二硫键桥接的侧链远程控制，而螺旋之间没有接触。MM 计算表明，这种现象是特定于给定的侧链长度的，并且需要二硫键功能。
