当前位置：
X-MOL 学术
›
J. Am. Chem. Soc.
›
论文详情
Our official English website, www.x-mol.net, welcomes your
feedback! (Note: you will need to create a separate account there.)
[FeFe]-Hydrogenase Oxygen Inactivation Is Initiated at the H Cluster 2Fe Subcluster
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2015-01-29 , DOI: 10.1021/ja510169s Kevin D. Swanson 1 , Michael W. Ratzloff 2 , David W. Mulder 2 , Jacob H. Artz 1 , Shourjo Ghose 1 , Andrew Hoffman 1 , Spencer White 1 , Oleg A. Zadvornyy 1 , Joan B. Broderick 1 , Brian Bothner 1 , Paul W. King 2 , John W. Peters 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2015-01-29 , DOI: 10.1021/ja510169s Kevin D. Swanson 1 , Michael W. Ratzloff 2 , David W. Mulder 2 , Jacob H. Artz 1 , Shourjo Ghose 1 , Andrew Hoffman 1 , Spencer White 1 , Oleg A. Zadvornyy 1 , Joan B. Broderick 1 , Brian Bothner 1 , Paul W. King 2 , John W. Peters 1
Affiliation
|
The [FeFe]-hydrogenase catalytic site H cluster is a complex iron sulfur cofactor that is sensitive to oxygen (O2). The O2 sensitivity is a significant barrier for production of hydrogen as an energy source in water-splitting, oxygenic systems. Oxygen reacts directly with the H cluster, which results in rapid enzyme inactivation and eventual degradation. To investigate the progression of O2-dependent [FeFe]-hydrogenase inactivation and the process of H cluster degradation, the highly O2-sensitive [FeFe]-hydrogenase HydA1 from the green algae Chlamydomonas reinhardtii was exposed to defined concentrations of O2 while monitoring the loss of activity and accompanying changes in H cluster spectroscopic properties. The results indicate that H cluster degradation proceeds through a series of reactions, the extent of which depend on the initial enzyme reduction/oxidation state. The degradation process begins with O2 interacting and reacting with the 2Fe subcluster, leading to degradation of the 2Fe subcluster and leaving an inactive [4Fe-4S] subcluster state. This final inactive degradation product could be reactivated in vitro by incubation with 2Fe subcluster maturation machinery, specifically HydF(EG), which was observed by recovery of enzyme activity.
中文翻译：
[FeFe]-氢化酶氧失活在 H 簇 2Fe 亚簇处启动
[FeFe]-氢化酶催化位点 H 簇是一种复杂的铁硫辅助因子，对氧 (O2) 敏感。O2 敏感性是生产氢作为水分解、含氧系统中的能源的重要障碍。氧气直接与 H 簇反应，导致酶快速失活并最终降解。为了研究依赖于 O2 的 [FeFe]-氢化酶失活的进展和 H 簇降解的过程，来自绿藻莱茵衣藻的高度 O2 敏感的 [FeFe]-氢化酶 HydA1 暴露于规定浓度的 O2，同时监测损失的活动和伴随的 H 团簇光谱特性的变化。结果表明H簇降解通过一系列反应进行，其程度取决于初始酶还原/氧化状态。降解过程开始于 O2 与 2Fe 亚簇相互作用和反应，导致 2Fe 亚簇降解并留下非活性 [4Fe-4S] 亚簇状态。通过与 2Fe 亚簇成熟机制，特别是 HydF(EG) 一起孵育，可以在体外重新激活这种最终的非活性降解产物，这是通过酶活性的恢复观察到的。
更新日期：2015-01-29
中文翻译：
[FeFe]-氢化酶氧失活在 H 簇 2Fe 亚簇处启动
[FeFe]-氢化酶催化位点 H 簇是一种复杂的铁硫辅助因子，对氧 (O2) 敏感。O2 敏感性是生产氢作为水分解、含氧系统中的能源的重要障碍。氧气直接与 H 簇反应，导致酶快速失活并最终降解。为了研究依赖于 O2 的 [FeFe]-氢化酶失活的进展和 H 簇降解的过程，来自绿藻莱茵衣藻的高度 O2 敏感的 [FeFe]-氢化酶 HydA1 暴露于规定浓度的 O2，同时监测损失的活动和伴随的 H 团簇光谱特性的变化。结果表明H簇降解通过一系列反应进行，其程度取决于初始酶还原/氧化状态。降解过程开始于 O2 与 2Fe 亚簇相互作用和反应，导致 2Fe 亚簇降解并留下非活性 [4Fe-4S] 亚簇状态。通过与 2Fe 亚簇成熟机制，特别是 HydF(EG) 一起孵育，可以在体外重新激活这种最终的非活性降解产物，这是通过酶活性的恢复观察到的。
京公网安备 11010802027423号