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 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 equil

SUBMITTER: Can M 

PROVIDER: S-EPMC10311460 | biostudies-literature | 2023 Jun

REPOSITORIES: biostudies-literature