2023
DOI: 10.1021/jacs.3c01772
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Characterization of Methyl- and Acetyl-Ni Intermediates in Acetyl CoA Synthase Formed during Anaerobic CO2 and CO Fixation

Abstract: The Wood−Ljungdahl Pathway is a unique biological mechanism of carbon dioxide and carbon monoxide fixation proposed to operate through nickel-based organometallic intermediates. The most unusual steps in this metabolic cycle involve a complex of two distinct nickel−iron−sulfur proteins: CO dehydrogenase and acetyl-CoA synthase (CODH/ACS). Here, we describe the nickel-methyl and nickel-acetyl intermediates in ACS completing the characterization of all its proposed organometallic intermediates. A single nickel s… Show more

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Cited by 10 publications
(11 citation statements)
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“…However, in the methylated state the K d drops to 12 nM, probably due to the immediate insertion of the CO into the NiÀ CH 3 bond. [17] This is about 8-times lower than the K d of hemoglobin determined here (Figure S5). Still, even such a low affinity of the methylated A-cluster for CO is insufficient to explain the observed kinetics: due to the approximately 14-fold excess of hemoglobin over ACS in the assays (assuming a degree of maturation of 50 % for ACS), Hb-CO should still be able to compete with methylated ACS for CO binding.…”
Section: What Is the Advantage Of A Bifunctional Complex?contrasting
confidence: 54%
“…However, in the methylated state the K d drops to 12 nM, probably due to the immediate insertion of the CO into the NiÀ CH 3 bond. [17] This is about 8-times lower than the K d of hemoglobin determined here (Figure S5). Still, even such a low affinity of the methylated A-cluster for CO is insufficient to explain the observed kinetics: due to the approximately 14-fold excess of hemoglobin over ACS in the assays (assuming a degree of maturation of 50 % for ACS), Hb-CO should still be able to compete with methylated ACS for CO binding.…”
Section: What Is the Advantage Of A Bifunctional Complex?contrasting
confidence: 54%
“…Renewed interest in the ACS active site signifies the necessity for new model compounds in the development of catalysts that can valorize CO 2 into fuels. 34–36 Ongoing studies will leverage the knowledge obtained in this study towards bimetallic activation of small molecules.…”
Section: Discussionmentioning
confidence: 99%
“…Im methylierten Zustand sinkt der K d jedoch auf 12 nM, was wahrscheinlich auf die sofortige Einbindung des CO in die Ni-CH 3 -Bindung zurückzuführen ist. [17] Dies ist etwa 8-mal niedriger als der hier ermittelte K d von Hämoglobin (Abbildung S5). Doch selbst eine so geringe Affinität des methylierten A-Clusters für CO reicht nicht aus, um die beobachtete Kinetik zu erklären: Aufgrund des etwa 14-fachen Überschusses von Hämoglobin gegenüber ACS in den Assays (unter der Annahme eines Besetzungsgrades von 50 % für ACS) sollte Hämoglobin immer noch mit methyliertem ACS um die CO-Bindung konkurrieren können.…”
Section: Was Ist Der Vorteil Eines Bifunktionalen Komplexes?unclassified