在多铜氧化中,对3型对的两电子还原与一电子氧化相比,是多铜氧化
Christian H Kjaergaard1, Stephen M Jones1, Sébastien Gounel2
1†Department of Chemistry, Stanford University, Stanford, California 94305, United States.
Journal of the American Chemical Society
|June 16, 2015
概括
多铜氧化酶 (MCOs) 使用三核铜集群来减少O2. 休息氧化 (RO) 的形式.
科学领域:
- 生物化学 生物化学
- 生物有机化学 生物有机化学
背景情况:
- 多铜氧化酶 (MCOs) 使用三核铜集群 (TNC) 催化O2降解为H2O.
- 存在两种休息形式:替代休息 (AR) 和氧化休息 (RO).
- 高电位电子捐赠者可以减少MCO中的所有铜位.
研究的目的:
- 研究高潜力MCOs的RO形式的减少机制.
- 阐明T1铜位点在减少T3双核铜位点中的作用.
- 了解MCO还原激活过程中转稳态的形成.
主要方法:
- 对MCOs进行光谱评价.
- 密度函数理论 (DFT) 的计算.
- 分析跨国公司内部的电子传输路径.
主要成果:
- 在RO形式中的T3双核铜位通过T1铜位可减小.
- 减少过程是通过两电子过程进行的,形成一个超稳定的半减少的T3状态.
- 减少的T3位点的氧化产生了热力学偏好的AR形式.
- DFT计算突出显示了蛋白质骨干在活性部位调节中的作用.
结论:
- 高电位MCO的RO形式经历了T3位点的独特的两电子减小.
- 一个转移稳定的半减T3状态对于完全的还原激活至关重要.
- 蛋白质结构积极控制铜氧化还原状态和催化活性.
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