具有分子口袋的超分子聚合物的溶剂酸盐驱动动力学立体变异
Chidambar Kulkarni1, Peter A Korevaar1, Karteek K Bejagam
1Laboratory of Macromolecular and Organic Chemistry and Institute for Complex Molecular Systems (ICMS), Eindhoven University of Technology , P.O. Box 513, 5600 MB Eindhoven, The Netherlands.
Journal of the American Chemical Society
|September 12, 2017
概括
这项研究证明了在自组装的冠二氧化物中对螺旋逆转的热力学控制. 组件中的分子口袋捕获溶剂分子,引发螺旋组织的变化.
科学领域:
- 超分子化学
- 有机化学
- 材料科学
背景情况:
- 控制合成系统中的螺旋组织对于电子旋转过器和人工酶等应用来说至关重要.
- 在热力学控制下实现螺旋逆转并了解其分子基础仍然是一个挑战.
研究的目的:
- 在热力学控制下呈现螺旋逆转 (立体突变) 的新系统.
- 阐明在自组装系统中驱动这种立体突变的分子机制.
主要方法:
- 用3,5-二氧化基替代 (CBI-35CH) 合成冠二氧化基 (CBI) 衍生物
- 在不同温度下使用各种溶剂进行手术研究.
- 显式溶剂分子动力学模拟.
主要成果:
- 在CBI-35CH中由于自组合中的"分子口袋"的形成而观察到立体突变.
- 在低温 (263 K) 时,溶剂分子在这些口袋中合或形成酸盐,引发了螺旋反转.
- 分子动力学模拟证实了螺旋组合,分子口袋和溶剂组织之间的相互作用.
结论:
- 自组建构件的分子设计可以控制溶剂的组织.
- 这种有组织的溶剂组织, 反过来又决定了超分子组合的螺旋结构.
- 证明了实现超分子螺旋的热力学控制的途径.
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