1.2.5.3: aerobic carbon monoxide dehydrogenase
This is an abbreviated version!
For detailed information about aerobic carbon monoxide dehydrogenase, go to the full flat file.
Reaction
Synonyms
aerobic Mo/Cu-containing CO dehydrogenase, Carbon monoxide dehydrogenase, CO dehydrogenase, CODH, CoxS, coxSML, CutL, CutM, CutS, EC 1.2.2.4, EC 1.2.3.10, Mo-CODH, Mo-Cu carbon monoxide dehydrogenase, Mo/Cu CODH, MoCu-CODH, molybdenum- and copper-containing carbon monoxide dehydrogenase, molybdenum- and copper-dependent CO dehydrogenase, molybdenum-containing carbon monoxide dehydrogenase, molybdenum-containing CO dehydrogenase, molybdenum-copper carbon monoxide dehydrogenase, molybdenum-copper CO dehydrogenase, molybdenum/copper-containing carbon monoxide dehydrogenase, molybdoenzyme carbon monoxide dehydrogenase
ECTree
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Reaction
Reaction on EC 1.2.5.3 - aerobic carbon monoxide dehydrogenase
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CO + a quinone + H2O = CO2 + a quinol
CO initially binds rapidly to the enzyme, possibly at the Cu(I) of the active site, prior to undergoing oxidation. A Mo(V) species exhibits strong coupling to the copper of the active center, the rate-limiting step of overall turnover is likely in the reductive half-reaction
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CO + a quinone + H2O = CO2 + a quinol
hypothetical reaction mechanism, overview
CO + a quinone + H2O = CO2 + a quinol
proposed reaction mechanisms for CO dehydrogenase, the rate-limiting step for overall turnover resides in the reductive half-reaction, reoxidation of reduced enzyme by quinones occurs at the FAD site
CO + a quinone + H2O = CO2 + a quinol
reaction mechanism that initially involves nucleophilic attack of a Mo=O oxo on the carbon center of Cu(I)-CO, resulting in a 5-membered cyclic m2-e(2) CO2-bridged Mo(VI)-Cu(I)-Cys complex I that can bind HO-/H2O to yield 1-OH. This is followed by a second nucleophilic attack on the activated mu2-nu2 CO2 carbon centre of 1-OH to yield a Mo(IV)-bicarbonate product complex, 1-P. This second nucleophilic attack is suggested based on electronic structure description of cyclic m2-e(2) CO2-bridged Mo(VI)-Cu(I)-Cys complex I, which possesses a bent and activated CO2 bound to the Mo and Cu ions. Proposed catalytic cycle for CODH that avoids formation of a stable C-S bonded cyclic m2-e(2) CO2-bridged Mo(VI)-Cu(I)-Cys complex II
CO + a quinone + H2O = CO2 + a quinol
reaction mechanism that initially involves nucleophilic attack of a Mo=O oxo on the carbon center of Cu(I)-CO, resulting in a 5-membered cyclic m2-e(2) CO2-bridged Mo(VI)-Cu(I)-Cys complex I that can bind HO-/H2O to yield 1-OH. This is followed by a second nucleophilic attack on the activated mu2-nu2 CO2 carbon centre of 1-OH to yield a Mo(IV)-bicarbonate product complex, 1-P. This second nucleophilic attack is suggested based on our electronic structure description of cyclic m2-e(2) CO2-bridged Mo(VI)-Cu(I)-Cys complex I, which possesses a bent and activated CO2 bound to the Mo and Cu ions. Proposed catalytic cycle for CODH that avoids formation of a stable C-S bonded cyclic m2-e(2) CO2-bridged Mo(VI)-Cu(I)-Cys complex II