具有可切换动力学,性和封装特征的刺激反应分子囊
Lei Zhiquan1, Han Xie1, Sarah E Border1
1Department of Chemistry & Biochemistry , The Ohio State University , 100 West 18th Avenue , Columbus , Ohio 43210 , United States.
Journal of the American Chemical Society
|August 14, 2018
概括
这项研究引入了一种能够绑定小客人的新分子囊. 质子化增强了它的预组织和结合亲和力,证明了对潜在的分子机器的异质效应.
科学领域:
- 超分子化学
- 有机化学
- 材料科学
背景情况:
- 分子囊被研究为它们的宿主-客人化学.
- 控制囊动态和预组织对于识别属性至关重要.
研究的目的:
- 准备和描述一个新型分子囊 (1) 带有三二甲基胺 (TPA) 盖.
- 研究1号囊及其质子形式的形态动态和客体识别.
- 在分子机器中探索体行为和潜在的应用.
主要方法:
- 分子囊的合成和表征 1.
- 实验方法:可变温度1H NMR光谱.
- 理论方法:分子力学 (MM) 和密度函数理论 (DFT) 的计算.
主要成果:
- 囊1表现出较差的预组织,TPA盖的动态P-M立体化 (ΔG‡ < 8 kcal/ mol).
- 囊1对小客体具有较弱的结合亲和力 (Ka < 7 M-1).
- 囊1的质子化产生了 [1·H]-Cl,它具有更高的预组织性,并表现出显著增强的客体结合亲缘关系 (Ka = 100-400 M-1).
- 质子体表现出诱导适合结合机制,涉及轴延长和化环扭曲.
- 解质/重质循环是可逆的,释放和重新结合客体.
结论:
- 质子化导致囊结构,动态和客人识别特性发生显著变化.
- 囊1的全性行为为开发智能功能材料和分子机器提供了一个独特的平台.
- 这项研究强调了分子识别中预组织和构造动态的重要性.
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