与酶活性位点相关的共价效应的振动控制
Benjamin W Stein1,2, Jing Yang1, Regina Mtei1
1Department of Chemistry and Chemical Biology , The University of New Mexico , MSC 032060, 1 University of New Mexico , Albuquerque , New Mexico 87131 , United States.
Journal of the American Chemical Society
|September 13, 2018
概括
过渡金属迪烯复合体表现出独特的电子结构和由伪约翰-泰勒效应驱动的折叠扭曲. 这项研究将这些扭曲与酶中的电子转移联系起来.
科学领域:
- 无机化学 无机化学
- 计算化学的计算化学
- 生物化学 生物化学
背景情况:
- 滴立烯复合物在酶中起着至关重要的作用.
- 了解它们的电子结构是它们反应性的关键.
研究的目的:
- 研究Cp2M (二) 复合物的电子结构 (M = Ti,V,Mo).
- 阐明dithiolene折叠对电子转移和还原潜力的贡献.
- 解释这些系统中的伪约翰-泰勒 (PJT) 效应.
主要方法:
- 多技术光谱学研究:共振拉曼,磁性圆形二重化,电子磁共振和紫外线光电子光谱 (UPS).
- 理论上的计算. 理论上的计算.
- 对不同金属中心 (Ti,V,Mo) 的光谱数据进行比较.
主要成果:
- 滴立烯折叠扭曲的大小与金属-联结体共价相关.
- 伪约翰-泰勒 (PJT) 效应驱动了观察到的折叠角度扭曲.
- Cp2Mo (bdt) 的UPS显示了由PJT活性扭曲主导的振动渐进.
- 金属和硫轨道之间的微小能量差异可以实现显著的电子和几何变化.
结论:
- PJT效应是过渡金属dithiolenes的电子和几何灵活性的核心.
- 这些发现提供了对酶中电子转移机制的洞察.
- 综合光谱和理论方法对于研究振动合具有强大作用.
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