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Cited by 27Metalloenzymes and iron-sulfur proteinsCO2 Reduction Techniques and CatalystsOrganometallic Complex Synthesis and Catalysis

Characterization of Methyl- and Acetyl-Ni Intermediates in Acetyl CoA Synthase Formed during Anaerobic CO 2 and CO Fixation

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Can, Mehmet, Abernathy, Macon J., Wiley, Seth, Griffith, Claire, James, Christopher D., Xiong, Jin, Guo, Yisong, Hoffman, Brian M. +2 more·2023·Journal of the American Chemical Society
DOI 10.1021/jacs.3c01772PMC PMC10311460
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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 site (Ni p ) within the A cluster of ACS undergoes major geometric and redox changes as it transits the planar Ni p, tetrahedral Ni p –CO and planar Ni p –Me and Ni p –Ac intermediates. We propose that the Ni p intermediates equilibrate among different redox states, driven by an electrochemical–chemical (EC) coupling process, and that geometric changes in the A-cluster linked to large protein conformational changes control entry of CO and the methyl group.

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  • In the acetyl-CoA pathway of H2-dependent acetogens and methanogens, CoFeS catalyzes a cobamide-dependent cobalt-to-nickel methyl transfer reaction essential for acetyl-CoA synthesis.

    “In the acetyl‐CoA pathway of H2‐dependent acetogens (bacteria) and H2‐dependent methanogens (archaea), the corrinoid iron–sulphur protein (CoFeS) catalyzes a cobamide‐dependent cobalt‐to‐nickel methyl transfer reaction that is essential for acetyl‐CoA synthesis [52, 53]”

    From Evidence for corrin biosynthesis in the last universal common ancestor (2025) · cites this paper as [53]

    The Results (Methylated Intermediate of ACS; page not provided) identify methyl-CFeSP as a methyl donor and report transfer of its methyl group to nickel in ACS. But the paper describes ACS, not CoFeS, as the enzyme undergoing methylation; it does not establish the claim for H2-dependent acetogens and methanogens specifically. (LLM, conf=0.86)

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Cited by

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Authors
Can, M., Abernathy, M. J., Wiley, S., Griffith, C., James, C. D., Xiong, J., Guo, Y., Hoffman, B. M., Ragsdale, S. W., & Sarangi, R.
Affiliations
  • Ankara Medipol Üniversitesi (TR)
  • SLAC National Accelerator Laboratory (US)
  • National Laboratory of the Rockies (US)
  • University of Michigan (US)
  • Northwestern University (US)
  • Carnegie Mellon University (US)
Corresponding author
  • Ragsdale, Stephen W.
  • Sarangi, Ritimukta
ORCID
Venue
Journal of the American Chemical Society
Publisher
American Chemical Society (ACS)
Published
2023-06-12
Volume
145
Issue
25
Pages
13696-13708
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
DOI
10.1021/jacs.3c01772
PMC
PMC10311460
OpenAlex
W4380291217
Cited by
27
References
1
Citations by year
2026: 9 · 2025: 8 · 2024: 10
FWCI
1.29
Type
journal article
Language
en
Open access
Licence
Locations
  • Journal of the American Chemical Society (publishedVersion, cc-by-nc-nd)
  • PubMed Central (publishedVersion, cc-by-nc-nd)
  • PubMed (publishedVersion)
  • OSTI OAI (U.S. Department of Energy Office of Scientific and Technical Information) (submittedVersion)
Funders
  • Basic Energy Sciences
  • National Institute of General Medical Sciences (GM125924, R35-GM141758)
Topics
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › Metalloenzymes and iron-sulfur proteins
  • Physical Sciences › Energy › Renewable Energy, Sustainability and the Environment › CO2 Reduction Techniques and Catalysts
  • Physical Sciences › Chemistry › Organic Chemistry › Organometallic Complex Synthesis and Catalysis
Keywords
acetyl-CoA synthase, Wood-Ljungdahl pathway, CO2 fixation, CO dehydrogenase, A-cluster, protein conformational change
MeSH terms
Acetyl Coenzyme A, Aldehyde Oxidoreductases, Anaerobiosis, Carbon Dioxide, Carbon Monoxide, Iron-Sulfur Proteins, Nickel, Nitric Oxide Synthase

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