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The active site structure and catalytic mechanism of arsenite oxidase

Journal Article · · Scientific Reports
 [1];  [2];  [3];  [4];  [5]
  1. Univ. College London (United Kingdom). Division of Biosciences. Inst. of Structural and Molecular Biology; DOE/OSTI
  2. Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Anatomy and Cell Biology; Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Geological Sciences. Molecular and Environmental Sciences Research Group
  3. Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Geological Sciences. Molecular and Environmental Sciences Research Group
  4. Univ. College London (United Kingdom). Division of Biosciences. Inst. of Structural and Molecular Biology
  5. Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Geological Sciences. Molecular and Environmental Sciences Research Group; Univ. of Saskatchewan, Saskatoon, SK (Canada). Dept. of Chemistry
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Arsenite oxidase is thought to be an ancient enzyme, originating before the divergence of the Archaea and the Bacteria. We have investigated the nature of the molybdenum active site of the arsenite oxidase from the Alphaproteobacterium Rhizobium sp. str. NT-26 using a combination of X-ray absorption spectroscopy and computational chemistry. Our analysis indicates an oxidized Mo(VI) active site with a structure that is far from equilibrium. We propose that this is an entatic state imposed by the protein on the active site through relative orientation of the two molybdopterin cofactors, in a variant of the Rây-Dutt twist of classical coordination chemistry, which we call the pterin twist hypothesis. We discuss the implications of this hypothesis for other putatively ancient molybdopterin-based enzymes.
Research Organization:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
Grant/Contract Number:
AC02-76SF00515
OSTI ID:
1624289
Journal Information:
Scientific Reports, Journal Name: Scientific Reports Journal Issue: 1 Vol. 7; ISSN 2045-2322
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English

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Cited By (3)

Catalytic properties of the metal ion variants of mandelate racemase reveal alterations in the apparent electrophilicity of the metal cofactor journal January 2019
Structural and mechanistic analysis of the arsenate respiratory reductase provides insight into environmental arsenic transformations journal August 2018
Phylogenomic analysis reveals the basis of adaptation of Pseudorhizobium species to extreme environments posted_content July 2019

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