CO Disrupts the Reduced H-Cluster of FeFe Hydrogenase. A Combined DFT and Protein Film Voltammetry Study

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• 作者：Carole Baffert ; Luca Bertini ; Thomas Lautier ; Claudio Greco ; Kateryna Sybirna ; Pierre Ezanno ; Emilien Etienne ; Philippe Soucaille ; Patrick Bertrand ; Herv茅 Bottin ; Isabelle Meynial-Salles ; Luca De Gioia ; Christophe L茅ger
• 刊名：Journal of the American Chemical Society
• 出版年：2011
• 出版时间：February 23, 2011
• 年：2011
• 卷：133
• 期：7
• 页码：2096-2099
• 全文大小：796K
• 年卷期：v.133,no.7(February 23, 2011)
• ISSN：1520-5126

文摘

Carbon monoxide is often described as a competitive inhibitor of FeFe hydrogenases, and it is used for probing H₂ binding to synthetic or in silico models of the active site H-cluster. Yet it does not always behave as a simple inhibitor. Using an original approach which combines accurate electrochemical measurements and theoretical calculations, we elucidate the mechanism by which, under certain conditions, CO binding can cause permanent damage to the H-cluster. Like in the case of oxygen inhibition, the reaction with CO engages the entire H-cluster, rather than only the Fe₂ subsite.