Carbon Monoxide as an Intrinsic Ligand to Iron in the Active Site of the Iron−Sulfur-Cluster-Free Hydrogenase H2-Forming Methylenetetrahydromethanopterin Dehydrogenase As Revealed by Infrared Spectroscopy

The iron−sulfur-cluster-free hydrogenase Hmd (H2-forming methylenetetrahydromethanopterin dehydrogenase) from methanogenic archaea has recently been found to contain one iron associated tightly with an extractable cofactor of yet unknown structure. We report here that Hmd contains intrinsic CO bound...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2004-11, Vol.126 (43), p.14239-14248
Main Authors: Lyon, Erica J, Shima, Seigo, Boecher, Reinhard, Thauer, Rudolf K, Grevels, Friedrich-Wilhelm, Bill, Eckhard, Roseboom, Winfried, Albracht, Simon P. J
Format: Article
Language:English
Subjects:
Analytical, structural and metabolic biochemistry
Archaeal Proteins - chemistry
Archaeal Proteins - metabolism
Binding Sites
Binding, Competitive
Biological and medical sciences
Carbon Isotopes
Carbon Monoxide - chemistry
Carbon Monoxide - metabolism
Cyanides - chemistry
Cyanides - metabolism
Enzymes and enzyme inhibitors
Fundamental and applied biological sciences. Psychology
Hydrogen - chemistry
Hydrogen-Ion Concentration
Iron Compounds - chemistry
Iron Compounds - metabolism
Light
Methanobacteriaceae - enzymology
Oxidoreductases
Oxidoreductases Acting on CH-NH Group Donors - chemistry
Oxidoreductases Acting on CH-NH Group Donors - metabolism
Oxygen - chemistry
Pterins - chemistry
Pterins - metabolism
Spectrophotometry, Infrared
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Summary:The iron−sulfur-cluster-free hydrogenase Hmd (H2-forming methylenetetrahydromethanopterin dehydrogenase) from methanogenic archaea has recently been found to contain one iron associated tightly with an extractable cofactor of yet unknown structure. We report here that Hmd contains intrinsic CO bound to the Fe. Chemical analysis of Hmd revealed the presence of 2.4 ± 0.2 mol of CO/mol of iron. Fourier transform infrared spectra of the native enzyme showed two bands of almost equal intensity at 2011 and 1944 cm-1, interpreted as the stretching frequencies of two CO molecules bound to the same iron in an angle of 90°. We also report on the effect of extrinsic 12CO, 13CO, 12CN-, and 13CN- on the IR spectrum of Hmd.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja046818s