TY - JOUR
T1 - A long-lived, substrate-hydroxylating peroxodiiron(III/III) intermediate in the amine oxygenase, AurF, from Streptomyces thioluteus
AU - Korboukh, Victoria Korneeva
AU - Li, Ning
AU - Barr, Eric W.
AU - Bollinger, J. Martin
AU - Krebs, Carsten
PY - 2009
Y1 - 2009
N2 - (Chemical Equation Presented) 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 Fe2(II/II) cofactor with O2, which results in generation of a peroxo-Fe2(III/III) intermediate. In the absence of substrate, this intermediate is unusually stable (t1/2 = 7 min at 20°C), allowing for its accumulation to almost stoichiometric amounts. Its decay is accelerated 105-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.
AB - (Chemical Equation Presented) 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 Fe2(II/II) cofactor with O2, which results in generation of a peroxo-Fe2(III/III) intermediate. In the absence of substrate, this intermediate is unusually stable (t1/2 = 7 min at 20°C), allowing for its accumulation to almost stoichiometric amounts. Its decay is accelerated 105-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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U2 - 10.1021/ja9064969
DO - 10.1021/ja9064969
M3 - Article
C2 - 19731912
AN - SCOPUS:70349736097
SN - 0002-7863
VL - 131
SP - 13608
EP - 13609
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 38
ER -