在 [4Fe-4S] 集群中插入三坐标
Majed S Fataftah1, Daniel W N Wilson1, Zachary Mathe2
1Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
ACS central science
|October 28, 2024
概括
研究人员展示了电子转移如何组装复杂的-铁-硫化物集群,模仿一氧化碳脱酶 (CODH) 的活性位点. 这揭示了形成 [1Ni-4Fe-4S] 和 [2Ni-3Fe-4S] 星团的新途径,突出了这些系统中Ni1+的生存能力.
科学领域:
- 生物有机化学 生物有机化学
- 金属酶活性部位的合成.
- - 铁 - 硫集群组件组件
背景情况:
- 金属酶在温和条件下催化关键的氧化还原反应,包括CO2/CO相互转换.
- 厌氧一氧化碳脱酶 (CODH) 使用一个独特的[NiFe3S4]-Feu集群,具有三坐标位.
- 对于CODH C集群的自然组装机制,人们对其了解甚少.
研究的目的:
- 调查与CODH C集群相关的-铁-硫集群的组装.
- 探索电子转移在推动复杂金属酶活性位形成中的作用.
- 为了证明Ni1+在铁硫集群环境中的可行性.
主要方法:
- 使用Ni0前体和[Fe4S4]3+集群合成新的-铁-硫集群.
- 通过磁力测量,电子磁共振 (EPR),Mössbauer和X射线吸收光谱学进行表征.
- 使用密度函数理论 (DFT) 计算进行理论验证.
主要成果:
- 电子转移驱动Ni0插入[Fe4S4]3+,形成一个 [1Ni-4Fe-4S]集群与外部Ni1+.
- 对Ni0前体的修改导致了两个Ni原子的插入和一个Fe的弹出,形成了前所未有的 [2Ni-3Fe-4S] 集群.
- 两种合成集群均具有三坐标金属位点和Ni在+1氧化状态,通过光谱和DFT确认.
结论:
- 氧化驱动的转化可以组装复杂的,核度更高的-铁-硫集群.
- 1+是铁硫集群框架内稳定且可行的氧化状态.
- 这些发现为CODH C集群活跃站点的潜在组装路径提供了洞察力.
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