Structure, Function, and Mechanism of the Nickel Metalloenzymes, CO Dehydrogenase, and Acetyl-CoA Synthase

Can, Mehmet; Armstrong, Fräser A.; Ragsdale, Stephen W.

doi:10.1021/cr400461p

Cited by 521 publications

(602 citation statements)

References 237 publications

(498 reference statements)

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“…CO dehydrogenases are enzymes that employ a NiFe 4 S 4 active site to catalyze the reversible oxidation of CO to CO 2 [14]. * To whom correspondance should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Reliable estimation of the kinetic parameters of redox enzymes by taking into account mass transport towards rotating electrodes in protein film voltammetry experiments

Merrouch

Hadj-Saïd

Léger

et al. 2017

Electrochimica Acta

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Reliable estimation of the kinetic parameters of redox enzymes by taking into account mass transport towards rotating electrodes in protein film voltammetry experiments. Electrochimica Acta, Elsevier, 2017Elsevier, , 245, pp.1059Elsevier, -1064Elsevier, . 10.1016Elsevier, /j.electacta.2017 AbstractIn Protein Film Voltammetry, a redox enzyme is immobilized on a rotating electrode in a configuration allowing fast, direct electron transfer. This technique is used to probe the mechanism of enzymes by quantitatively interpreting the response in current as a function of the experimental conditions. Limitation by mass transport of the substrate towards the electrode may obscure important features and complicate the analysis of the enzymatic response, so much so that the enzyme has high activity. In this work, we derive equations taking into account mass transport of substrate, for the steady-state current generated by an enzyme following Michaelis-Menten kinetics and immobilized onto a hydrodynamic (e.g. rotating) electrode. We use these equations to model the current response of films of CO-dehydrogenase, a metalloenzyme that catalyzes the oxidation of CO, to transient exposures to its gaseous substrate. We show that neglecting transport yields poor fits and overestimated, unreliable, values of K m (even when using the Koutecky-Levich approximation), whereas taking into account transport yields much better fits and more reliable parameters. We reinterpret previously published data by taking into account transport limitations.

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“…CO dehydrogenases are enzymes that employ a NiFe 4 S 4 active site to catalyze the reversible oxidation of CO to CO 2 [14]. * To whom correspondance should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Reliable estimation of the kinetic parameters of redox enzymes by taking into account mass transport towards rotating electrodes in protein film voltammetry experiments

Merrouch

Hadj-Saïd

Léger

et al. 2017

Electrochimica Acta

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“…This survey is especially important because late metal (Ni and Cu) sulfides are found in a variety of metalloenzyme active sites, including the NiFe and MoCu CO dehydrogenases (CODH), 9,12 the "orange protein complex", 13 and N 2 O reductase (N 2 OR), [14][15][16] where they are known to play both catalytic 9 and structural roles, 14,17 yet our understanding of late metal sulfide (and thiolate) reactivity is still relatively limited. 18 , an observation that may have implications for our understanding of the reactions between NO and sulfur-containing metallo-proteins in vivo.…”

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confidence: 99%

Reactivity of a Nickel Sulfide with Carbon Monoxide and Nitric Oxide

Hartmann

Hayton

2016

J. Am. Chem. Soc.

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“…Obviously, CO electrons and electrons of the hydrogen/formate pool were not equilibrated but existed in separate pools. The CO pool may be associated with the nickel centers of CO dehydrogenase/ acetate synthase that is essential in homoacetogenic acetate formation and syntrophic or aceticlastic acetate degradation (Can et al 2014) and is not used for interspecies electron transfer.…”

Section: Discussionmentioning

confidence: 99%

Biogas process parameters—energetics and kinetics of secondary fermentations in methanogenic biomass degradation

Montag

Schink

2015

Appl Microbiol Biotechnol

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Pool sizes of short-chain fatty acids (formate, acetate, propionate, and butyrate), hydrogen, and carbon monoxide were assayed in digesting sludge from four different methanogenic reactors degrading either sewage sludge or agricultural products and wastes at pH 8.0 and 40 or 47°C. Free reaction energies were calculated for the respective degradation reactions involved, indicating that acetate, propionate, and butyrate degradation all supplied sufficient energy (−10 to −30 kJ per mol reaction) to sustain the microbial communities involved in the respective processes. Pools of formate and hydrogen were energetically equivalent as electron carriers. In the sewage sludge reactor, homoacetogenic acetate formation from H 2 and CO 2 was energetically feasible whereas syntrophic acetate oxidation appeared to be possible in two biogas reactors, one operating at enhanced ammonia content (4.5 g NH 4 + -N per l) and the other one at enhanced temperature (47°C). Maximum capacities for production of methanogenic substrates did not exceed the consumption capacities by hydrogenotrophic and aceticlastic methanogens. Nonetheless, the capacity for acetate degradation appeared to be a limiting factor especially in the reactor operating at enhanced ammonia concentration.

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Structure, Function, and Mechanism of the Nickel Metalloenzymes, CO Dehydrogenase, and Acetyl-CoA Synthase

Cited by 521 publications

References 237 publications

Reliable estimation of the kinetic parameters of redox enzymes by taking into account mass transport towards rotating electrodes in protein film voltammetry experiments

Reliable estimation of the kinetic parameters of redox enzymes by taking into account mass transport towards rotating electrodes in protein film voltammetry experiments

Reactivity of a Nickel Sulfide with Carbon Monoxide and Nitric Oxide

Biogas process parameters—energetics and kinetics of secondary fermentations in methanogenic biomass degradation

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