One-carbon chemistry of oxalate oxidoreductase captured by X-ray crystallography
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Gibson-2016-One-carbon chemistry.pdf
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Author(s)
Pierce, Elizabeth
Can, Mehmet
Ragsdale, Stephen W.
Gibson, Marcus Ian
Chen, Yang-Ting
Johnson, Aileen C.
Drennan, Catherine L.
Date Issued
January 2016
Journal
Proceedings of the National Academy of Sciences
Publisher
National Academy of Sciences (U.S.)
Citation
Gibson, Marcus I., Percival Yang-Ting Chen, Aileen C. Johnson, Elizabeth Pierce, Mehmet Can, Stephen W. Ragsdale, and Catherine L. Drennan. “One-Carbon Chemistry of Oxalate Oxidoreductase Captured by X-Ray Crystallography.” Proc Natl Acad Sci USA 113, no. 2 (December 28, 2015): 320–325. © 2016 National Academy of Sciences.
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Final published version
Abstract
Thiamine pyrophosphate (TPP)-dependent oxalate oxidoreductase (OOR) metabolizes oxalate, generating two molecules of CO[subscript 2] and two low-potential electrons, thus providing both the carbon and reducing equivalents for operation of the Wood−Ljungdahl pathway of acetogenesis. Here we present structures of OOR in which two different reaction intermediate bound states have been trapped: the covalent adducts between TPP and oxalate and between TPP and CO[subscript 2]. These structures, along with the previously determined structure of substrate-free OOR, allow us to visualize how active site rearrangements can drive catalysis. Our results suggest that OOR operates via a bait-and-switch mechanism, attracting substrate into the active site through the presence of positively charged and polar residues, and then altering the electrostatic environment through loop and side chain movements to drive catalysis. This simple but elegant mechanism explains how oxalate, a molecule that humans and most animals cannot break down, can be used for growth by acetogenic bacteria.
MIT Department
Massachusetts Institute of Technology. Department of Biology
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1073/pnas.1518537113
