合物合作性和间隔长度对双价伪素组合热力学和动力学的影响
Wei Jiang1, Karol Nowosinski, Nora L Löw
1Institut für Chemie und Biochemie, Freie Universität Berlin, Takustrasse 3, 14195 Berlin, Germany.
Journal of the American Chemical Society
|December 24, 2011
概括
皇冠氨基伪素表明,间隔器长度显著影响结合强度和形成速度. 较短的间距增强了合作性,但减缓了线程,揭示了复杂的多价值效应.
科学领域:
- 超分子化学 超分子化学
- 有机化学 有机化学
- 物理化学 物理化学
背景情况:
- 皇冠氨伪素是分子组件,在分子机器和传感中具有潜在的应用.
- 了解链接器 (间隔器) 长度对结合热力学和动力学的影响,对于设计先进的超分子系统至关重要.
研究的目的:
- 合成和表征具有不同间隔长度的同型和异型冠状氨基伪.
- 调查间隔器长度对酸盐合作性的影响,结合热力学和分子内线程的动力学.
主要方法:
- 皇冠-氨基伪的合成.
- 使用核磁共振 (NMR) 光谱和电子喷射电离质谱法 (ESI-MS) 进行表征.
- 结合事件的热力学和动力学分析.
主要成果:
- 间隔器长度显著影响酸盐合作性;较短的间隔器由于非无辜的间隔器贡献,显示出更强的合作性.
- 间距长度的微妙变化导致结合亲和力和有效度的实质性变化.
- 较短的间距创造了紧张的过渡结构,减缓了分子内线程过程,而较长的间距减少了体应变,但增加了体惩罚.
结论:
- 间隔剂在皇冠氨伪素中的作用是复杂的和"非无辜的",显著影响结合热力学和动力学.
- 假设灵活链的简单模型不足以准确地描述多价值结合.
- 为结合强度优化间隔器可能会损害伪多素形成的速度,突出了分子设计中的权衡.
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