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Kinetic evidence that carbon monoxide dehydrogenase catalyzes the oxidation of carbon monoxide and the synthesis of acetyl-CoA at separate metal centers

Journal Article · · Journal of the American Chemical Society; (United States)
DOI:https://doi.org/10.1021/ja00077a093· OSTI ID:5175553
; ; ;  [1]
  1. Univ. of Nebraska, Lincoln, NE (United States)
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This communication describes pre-steady-state kinetic studies of the reaction of CO with carbon monoxide dehydrogenase (CODH). It is shown that CO rapidly binds to center C. The [center C]-CO complex is oxidized to CO[sub 2] as electron transfer occurs to center B. A second mole of CO binds to center A of CODH, resulting in the formation of a [Ni-Fe-S]-CO complex. This species is kinetically competent as an intermediate in the synthesis of acetyl-CoA. However, it is formed much too slowly to implicate it as an intermediate in the oxidation of CO to CO[sub 2]. Our results from kinetic studies demonstrate that CO oxidation and acetyl-CoA synthesis occur at separate sites on CODH. It appears that center C binds CO and electrons are transferred to centers A and B as CO[sub 2] is formed. Reductive activation of center C allows it to form a stable complex with CO. The NiFeC complex then serves as the precursor of the carbonyl group of acetyl-CoA. 23 refs., 2 figs.
OSTI ID:
5175553
Journal Information:
Journal of the American Chemical Society; (United States), Journal Name: Journal of the American Chemical Society; (United States) Vol. 115:24; ISSN JACSAT; ISSN 0002-7863
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400102 -- Chemical & Spectral Procedures
550200* -- Biochemistry
550700 -- Microbiology
59 BASIC BIOLOGICAL SCIENCES
BACTERIA
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON MONOXIDE
CARBON OXIDES
CATALYSIS
CHALCOGENIDES
CHEMICAL REACTIONS
CLOSTRIDIUM
COMPLEXES
ELECTRON TRANSFER
ENZYMES
IRON COMPLEXES
MICROORGANISMS
NICKEL COMPLEXES
ORGANIC COMPOUNDS
ORGANOMETALLIC COMPOUNDS
OXIDATION
OXIDES
OXYGEN COMPOUNDS
PROTEINS
SPECTROSCOPY
SYNTHESIS
TRANSITION ELEMENT COMPLEXES