确定水中的键结构与近距离环境对比,以测试长度和稳定性之间的关系
Paul A Sigala, Eliza A Ruben, Corey W Liu
1§Intense Pulsed Neutron Source, Argonne National Laboratory, Argonne, Illinois 60439, United States.
Journal of the American Chemical Society
|April 15, 2015
概括
键强度主要是由溶剂与单个分子的相互作用决定的,而不是键本身. 这一发现澄清了生物系统中的键能量.
科学领域:
- 生物化学 生物化学
- 化学物理 化学物理
- 结构生物学 结构生物学
背景情况:
- 键对于生物分子结构和功能至关重要.
- 了解键的能量是理解生物分子行为的关键.
- 现有的模型提出溶剂对离合组的影响,或者键本身解释了能量差异.
研究的目的:
- 通过实验和计算来区分两个关于溶剂对键能量效应的拟议模型.
- 为了确定溶剂诱导的键结构变化或分离组的稳定是主导因素.
主要方法:
- 中子晶体学以确定精确的键长度.
- 核磁共振 (NMR) 光谱检测键环境.
- 量子力学计算以建模键潜在能量表面.
主要成果:
- 在各种溶剂 (晶体,,,水) 中,O-H··O键的长度和潜在能量表面几乎相同.
- 尽管在溶剂 (>8 kcal/mol) 中键形成能量 (ΔGf) 的显著差异,但结构参数基本保持不变.
- 这表明,键内的依赖溶剂的结构变化并不是能量差异的主要驱动因素.
结论:
- 模型II,它假定主导溶剂对键结构和结合后的潜在能量的影响,在很大程度上被排除在外.
- 这些发现强烈支持模型I,其中与分离的捐助者和接受者群体的溶剂相互作用主要决定了键形成能量.
- 这澄清了键的基本原理,对生物学和化学工程有影响.
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