超越结构:替代的素作为[NiFe]化酶的机制模型
Jeffrey W Slater1, Sean C Marguet1, Haleigh A Monaco1
1The Ohio State University , 100 West 18th Avenue , Columbus , Ohio 43210 , United States.
Journal of the American Chemical Society
|July 19, 2018
概括
替代的素 (NiRd) 通过类似于[NiFe]酶的机制催化的产生. 这种强大的系统显示出氧气不敏感,为燃料电池和进化提供了优势.
科学领域:
- 生物有机化学
- 催化剂
- 生物物理
背景情况:
- 在温和的条件下开发强大的分子系统是具有挑战性的.
- 替代的rubredoxin (NiRd) 模仿[NiFe]酶的活性位点,并表现出类似的催化活性.
- 之前没有阐明NiRd的催化机制.
研究的目的:
- 研究由NiRd催化的进化的机制.
- 将NiRd机制与原生[NiFe]酶进行比较.
- 通过蛋白质工程确定优化 NiRd 活动的策略.
主要方法:
- 定量蛋白膜电化学
- 光学和振动光谱学
- 密度函数理论 (DFT) 的计算
- 分子动力学 (MD) 模拟
主要成果:
- 质子合电子转移对于NiRd催化是至关重要的.
- 酸连接体作为质子化位点,在中心减少之前.
- 速度限制步骤涉及通过醇逆转的分子内质子转移,形成Ni (III) -化物种.
- 与原生酶不同,NiRd催化对氧气不敏感.
- 蛋白质突变改变了活性和速度决定的步骤,强调了外部协调球的作用.
结论:
- NiRd使用类似于[NiFe]酶的机制,涉及酸盐质子化.
- 这一发现表明酸盐在原生酶功能中的潜在作用.
- NiRd的氧气不敏感性和可调节的活性为燃料电池和有氧进化提供了应用的机会.
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