Selective Dynamic Assembly of Disulfide Macrocyclic Helical Foldamers with Remote Communication of Handedness.
Selective Dynamic Assembly of Disulfide Macrocyclic Helical Foldamers with Remote Communication of Handedness.
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DOI：
10.1002/anie.201601156
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发表时间：
2016-06
影响因子：
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通讯作者：
Christos Tsiamantas;Xavier de Hatten;C. Douat;B. Kauffmann;V. Maurizot;H. Ihara;M. Takafuji;N. Metzler‐Nolte;I. Huc
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文献类型：
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作者：
Christos Tsiamantas;Xavier de Hatten;C. Douat;B. Kauffmann;V. Maurizot;H. Ihara;M. Takafuji;N. Metzler‐Nolte;I. Huc
研究了螺旋芳香低聚酰胺折叠体中二硫桥的形成。取决于含巯基侧链的位置，可能发生排他性的分子内或分子间二硫键桥接。这两个过程能够自我排序，大概是通过动态交换。螺旋旋向反转率的定量评估表明，桥接稳定的折叠结构。分子间二硫键桥接偶然产生了一个明确的，C2-对称的，两个螺旋的斜纹状大环结构，其中完全控制相对手性，即螺旋-螺旋手性通信，是远程介导的二硫键桥接的侧链在螺旋之间的接触的情况下。MM计算表明，这种现象是特定于一个给定的侧链长度，并需要二硫键功能。
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.