Side-Chain-Driven Dual Structural System of Poly-Arylopeptide: Selective Helical Formation Derived from Aromatic Ring Flips on the Backbone
Side-Chain-Driven Dual Structural System of Poly-Arylopeptide: Selective Helical Formation Derived from Aromatic Ring Flips on the Backbone
复制标题
侧链驱动的多芳基肽双结构体系：主链上芳香环翻转选择性螺旋形成
DOI：
10.1021/acsmacrolett.9b00249
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Kiyotaka Onitsuka
中科院分区：
文献类型：
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作者：
Yuki Ishido;Naoya Kanbayashi;Taka-aki Okamura;Kiyotaka Onitsuka
提出了一种制备大分子双结构体系的方法，该方法涉及将主链上的不对称芳环翻转。以前，我们报道了一种非天然的多肽含有一个芳香环的肽骨架上，称为聚“芳肽”。在本文中，我们使用2，6-萘环作为轴向不对称间隔基，其具有两个几何异构体，antiandsyn，以产生双重结构性质。两种几何异构体之间的微小能量差可以通过将2，6_亚萘基单元并入多肽主链中来放大，这产生了用于形成两种特定全局结构（即，31-螺旋或41-螺旋）偏向一侧几何异构体，这取决于侧链。此外，在加入少量添加剂后，31-螺旋可以转换为41-螺旋，表明从相同序列的构象转换。发展双螺旋系统利用基本的分子几何形状，可以作为一个设计平台，合成聚合物。
A methodology for producing dual structural systems of macromolecules, which involves flipping the unsymmetrical aromatic rings on the main chain is presented. Previously, we reported a non-natural polypeptide containing an aromatic ring on the peptide backbone, called a poly “arylopeptide”. Herein, we used 2,6-naphthalene rings as axially unsymmetrical spacers, which has two geometrical isomers,antiandsyn, to create dual structural properties. The miniscule energy difference between the two geometrical isomers can be amplified by incorporating the 2,6-naphthylene units into the polypeptide backbone, which creates a thermodynamic driving force for the formation of two specific global structures (i.e., 31-helix or 41-helix) biased toward one side geometrical isomer depending on the side chain. Additionally, the 31-helix can be switched to the 41-helix upon addition of a small amount of additives, indicating a conformational conversion from an identical sequence. The developmental dual helical systems exploit basic molecular geometry and can serve as a design platform for synthetic polymers.