几何结构和电子结构对O-O裂变的贡献以及在血铜氧化酶中产生的中间体
Andrew W Schaefer1, Antonio C Roveda1, Anex Jose1
1Department of Chemistry , Stanford University , Stanford , California 94305 , United States.
Journal of the American Chemical Society
|June 1, 2019
概括
血铜氧化酶 (HCOs) 使用质子启动的O-O键裂解机制,对于高效的氧减和质子是至关重要的. 这一过程涉及从氨酸转移到氧联体,从而使随后的电子转移成为可能.
科学领域:
- 生物化学
- 酵素学
- 生物有机化学
背景情况:
- 血铜氧化酶 (HCO) 是催化氧化成水的关键金属酶.
- 了解HCO中的O-O键裂解机制是阐明它们在质子中的催化效率和作用的关键.
研究的目的:
- 在血铜氧化酶中研究O-O键裂变的详细机制.
- 使用酶中间体和合成模型结合实验和计算方法.
- 阐明关键PM中间体的结构和电子特性.
主要方法:
- 实验数据与计算研究的整合.
- 酶中间体的分析和合成的血铜氧化酶的模型.
- 研究质子转移途径和电子合机制.
主要成果:
- 一个由质子启动的O-O裂变机制被确定,涉及从交叉连接的氨酸转移到过氧联体.
- 多个结相互作用降低了氨酸pKa,促进了质子转移.
- PM中间体具有与CuII-OH结合的FeIVH,具有特定的反铁磁和铁磁合相互作用.
结论:
- 从氨酸的质子转移之前和速度限制O-O键裂变,与动力学数据一致.
- 对于O-O裂变至关重要的空间布局也通过超交换途径促进了电子转移.
- 描述的PM中间体提供了对HCO中O2减少和质子的机制的关键见解.
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