Role of Enzymes in the Biosynthesis of Hydrogenase H cluster

酶在氢化酶 H 簇生物合成中的作用

• 批准号: 2102222
• 金额: --
• 依托单位: University of Southampton
• 依托单位国家: 英国
• 项目类别: Studentship
• 财政年份: 2018
• 资助国家: 英国
• 起止时间: 2018 至 无数据
• 项目状态: 已结题
• 来源: https://gtr.ukri.org/projects?ref=studentship-2102222
• 关键词: Role; Enzymes; Biosynthesis; Hydrogenase; cluster

Hydrogenases are a potential source of environmentally benign bioenergy, using complex cofactors to catalyze the reversible reduction of protons to form hydrogen. The most active subclass, the [FeFe]-hydrogenases, is dependent on a metallocofactor, the H cluster, that consists of a two iron subcluster ([2Fe]H) bridging to a classical cubane cluster ([4Fe-4S]H). The ligands coordinating to the diiron subcluster include an azadithiolate, three carbon monoxides, and two cyanides. To assemble this complex cofactor, three maturase enzymes, HydG, HydE and HydF are required. The biosynthesis of the diatomic ligands proceeds by an unusual fragmentation mechanism, and structural studies in combination with spectroscopic analysis have started to provide insights into the HydG mediated assembly of a [2Fe]H subcluster precursor. An organometallic intermediate CysFe(CO)2CN, is proposed as the product of HydG. It functions as a synthon for subsequent H-cluster assembly. Studies will focus on understanding the chemical mechanisms of H cluster assembly. Structural studies will concentrate on understanding substrate binding to the active site of HydG. Spectroscopic and biochemical studies will focus on characterising the organometallic intermediate generated by HydG and elucidating the subsequent steps required for hydrogenase activation

氢酶是一种潜在的环境友好的生物能源，它使用复杂的辅因子催化质子的可逆还原形成氢。最活跃的亚类是[FeFe]-氢酶，它依赖于一个金属辅因子H簇，它由一个连接到经典立方烷簇([4Fe-4S]H)的双铁亚簇([2Fe]H)组成。与二铁亚簇配位的配体包括一个氮杂硫酸酯、三个一氧化碳和两个氰化物。要组装这种复杂的辅因子，需要三种成熟酶：HydG、Hyde和HydF。双原子配体的生物合成是通过一种不寻常的裂解机制进行的，结构研究结合光谱分析已经开始为HydG介导的[2Fe]H亚簇前体的组装提供了见解。金属有机中间体CysFe(CO)2CN是HydG的产物。它作为后续H-簇组装的合成子发挥作用。研究将集中在了解H团簇组装的化学机制上。结构研究将集中在了解底物与HydG活性部位的结合。光谱和生化研究将集中于表征HydG产生的有机金属中间体，并阐明氢酶激活所需的后续步骤