A long-lived, substrate-hydroxylating peroxodiiron(III/III) intermediate in the amine oxygenase, AurF, from Streptomyces thioluteus.

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  • Author(s): Korboukh VK;Korboukh VK; Li N; Barr EW; Bollinger JM Jr; Krebs C
  • Source:
    Journal of the American Chemical Society [J Am Chem Soc] 2009 Sep 30; Vol. 131 (38), pp. 13608-9.
  • Publication Type:
    Journal Article; Research Support, N.I.H., Extramural; Research Support, Non-U.S. Gov't
  • Language:
    English
  • Additional Information
    • Source:
      Publisher: American Chemical Society Country of Publication: United States NLM ID: 7503056 Publication Model: Print Cited Medium: Internet ISSN: 1520-5126 (Electronic) Linking ISSN: 00027863 NLM ISO Abbreviation: J Am Chem Soc Subsets: MEDLINE
    • Publication Information:
      Publication: Washington, DC : American Chemical Society
      Original Publication: Easton, Pa. [etc.]
    • Subject Terms:
      4-Aminobenzoic Acid/*chemistry ; Ferric Compounds/*chemistry ; Nitrobenzoates/*chemistry ; Oxygenases/*chemistry ; Streptomyces/*enzymology; Catalysis ; Enzyme Stability ; Oxidation-Reduction
    • Abstract:
      The amine oxygenase AurF from Streptomyces thioluteus catalyzes the six-electron oxidation of p-aminobenzoate (pABA) to p-nitrobenzoate (pNBA). In this work, we have studied the reaction of its reduced Fe(2)(II/II) cofactor with O(2), which results in generation of a peroxo-Fe(2)(III/III) intermediate. In the absence of substrate, this intermediate is unusually stable (t(1/2) = 7 min at 20 degrees C), allowing for its accumulation to almost stoichiometric amounts. Its decay is accelerated approximately 10(5)-fold by the substrate, pABA, implying that it is the complex that effects the two-electron oxidation of the amine to the hydroxylamine. The nearly quantitative conversion of pABA to pNBA by solutions containing an excess of the intermediate suggests that it may also be competent for the two subsequent two-electron oxidations leading to the product.
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    • Grant Information:
      R01 GM055365 United States GM NIGMS NIH HHS; R01 GM055365-10 United States GM NIGMS NIH HHS; GM-55365 United States GM NIGMS NIH HHS
    • Accession Number:
      0 (Ferric Compounds)
      0 (Nitrobenzoates)
      EC 1.13.- (Oxygenases)
      TL2TJE8QTX (4-Aminobenzoic Acid)
    • Publication Date:
      Date Created: 20090908 Date Completed: 20091207 Latest Revision: 20211020
    • Publication Date:
      20231215
    • Accession Number:
      PMC2772654
    • Accession Number:
      10.1021/ja9064969
    • Accession Number:
      19731912