Zn-His-Bkb与Zn-His-[Asp/Glu]三元组对Zn核稳定性和反应性的不同影响
Yen-Lin Lin1, Yu-Ming Lee, Carmay Lim
1Institute of Biomedical Sciences, Academia Sinica, Taipei 115, Taiwan ROC.
Journal of the American Chemical Society
|August 11, 2005
概括
在部位的胺 (His) 与结构部位的骨干碳基或催化部位的碳酸盐相互作用. 本研究解释了这些偏好基于溶剂可访问性和位点组成,影响芯稳定性和反应性.
科学领域:
- 生物化学和分子生物学
- 计算化学计算化学
- 生物有机化学 生物有机化学
背景情况:
- 结合的histidine (His) 通常在结构部位与骨干碳基相互作用.
- 在催化部位中,His通常与酸/酸 (Asp/Glu) 碳酸盐相互作用.
- 控制这种差异性相互作用的因素尚未完全理解.
研究的目的:
- 阐明了决定选择Zn结合的第二伴侣的因素.
- 为了比较骨干碳酸和Asp/Glu碳酸盐对Zn-core稳定性和反应性的贡献.
主要方法:
- 使用密度函数理论 (DFT) 的系统研究.
- 连续介电计算以评估相对贡献.
- 对溶剂可访问性和 Zn-核心组成的分析.
主要成果:
- 脊柱碳基稳定了结构部位的埋藏,阴离子Zn核心,解释了Zn-His-Asp/Glu三合体的缺失.
- Asp/Glu碳酸盐通过增加HOMO能量,OH-反应性,电子转移和复合稳定性来增强催化 Zn-核心.
- Asp/Glu碳酸盐可能通过质子化His.促进产品在催化位点的释放.
结论:
- 第二层合作伙伴的选择是由溶剂可访问性和 Zn-core 特性决定的.
- 骨干碳基因在结构性部位中受青,而Asp/Glu碳酸盐在催化部位中具有优势.
- 这些相互作用对于结构性和催化金属酶的独特功能至关重要.
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