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Simultaneous Fabrication of P and M Helices in One‐component Chiral System by Methanol‐Water Mediated Dual Assembly Pathway
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2024-11-19 , DOI: 10.1002/anie.202417876
Laiben Gao, Kaikai Yang, Chao Xing, Biyan Lin, Changli Zhao, Xiaoqiu Dou, Chuan Liang Feng

The synergetic evolution of multiple chiral structures stemmed from same building units is ubiquitous in nature and vital to living systems, but achieving it in artificial systems remains a challenge. Herein, we report a methanol‐water mediated dual assembly pathway strategy for simultaneous construction of P and M helices in one‐component chiral system. The conformation of l‐phenylaniline derivates (LBpyF) is controlled to folded state in CH3OH due to the hydrogen bonds as well as C‐H···π interaction between LBpyF and CH3OH. Addition of H2O into above CH3OH solution of LBpyF results in the simultaneous occurrence of two self‐assembly pathways and double networks of P and M helices were therefore formed, due to the synchronous process of 1) self‐assembly of folded LBpyF into M‐helices and 2) H2O induced unfolding of folded LBpyF molecules followed by self‐assembly of them into P‐helices. The bipyridine core, phenyl ring, amide unit all adapted into different stacking modes in M‐helices and P‐helices, and energy analysis indicated that the minority M‐helices were more thermodynamically favored products. This study provides an approach to explore synergetic evolution of multiple chiral structures by manipulating the multiple assembly pathway.

中文翻译:


通过甲醇-水介导的双组装途径在单组分手性系统中同时制备 P 和 M 螺旋



源自同一建筑单元的多个手性结构的协同进化在自然界中无处不在,对生命系统至关重要,但在人工系统中实现它仍然是一个挑战。在此,我们报道了一种甲醇-水介导的双组装途径策略,用于在单组分手性系统中同时构建 P 和 M 螺旋。由于氢键以及 C-H···π LBpyF 和 CH3OH 之间的相互作用。将 H 2 O 添加到上述 LBpyF 的 CH3OH 溶液中导致两个自组装途径同时发生,因此形成了 P 和 M 螺旋的双网络,因为 1) 折叠的 LBpyF 自组装成 M 螺旋和 2) H2O 诱导折叠的 LBpyF 分子展开,然后将它们自组装成 P 螺旋。联吡啶核、苯基环、酰胺单元都适应了 M-螺旋和 P-螺旋的不同堆叠模式,能量分析表明少数 M-螺旋是热力学上更有利的产物。本研究提供了一种通过操纵多个组装途径来探索多个手性结构的协同进化的方法。
更新日期:2024-11-19
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