Spectroscopic Investigations of [FeFe] Hydrogenase Maturated with [57Fe2(adt)(CN)2(CO)4]2鈥?/sup>

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• 作者：Ryan Gilbert-Wilson ; Judith F. Siebel ; Agnieszka Adamska-Venkatesh ; Cindy C. Pham ; Edward Reijerse ; Hongxin Wang ; Stephen P. Cramer ; Wolfgang Lubitz ; Thomas B. Rauchfuss
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：July 22, 2015
• 年：2015
• 卷：137
• 期：28
• 页码：8998-9005
• 全文大小：591K
• ISSN：1520-5126

文摘

The preparation and spectroscopic characterization of a CO-inhibited [FeFe] hydrogenase with a selectively ⁵⁷Fe-labeled binuclear subsite is described. The precursor [⁵⁷Fe₂(adt)(CN)₂(CO)₄]^{2鈥?/sup> was synthesized from the 57Fe metal, S_8, CO, (NEt₄)CN, NH₄Cl, and CH₂O. (Et₄N)₂[57Fe₂(adt)(CN)₂(CO)₄] was then used for the maturation of the [FeFe] hydrogenase HydA1 from Chlamydomonas reinhardtii, to yield the enzyme selectively labeled at the [2Fe]_H subcluster. Complementary 57Fe enrichment of the [4Fe-4S]_H cluster was realized by reconstitution with 57FeCl₃ and Na₂S. The H_ox-CO state of [257Fe]_H and [457Fe-4S]_H HydA1 was characterized by M枚ssbauer, HYSCORE, ENDOR, and nuclear resonance vibrational spectroscopy.}