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Literature summary for 1.13.12.16 extracted from

  • Francis, K.; Gadda, G.
    Inflated kinetic isotope effects in the branched mechanism of Neurospora crassa 2-nitropropane dioxygenase (2009), Biochemistry, 48, 2403-2410.
    View publication on PubMed

Organism

Organism UniProt Comment Textmining
Neurospora crassa
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Substrates and Products (Substrate)

Substrates Comment Substrates Organism Products Comment (Products) Rev. Reac.
nitroethane + O2 The kinetic isotope effect on the second-order rate constant for nitronate formation, kcat/Km, decreases from an upper limiting value of 23 at low pH to a lower limiting value of 11 at high pH. The difference in the kinetic isotope effects arises from the branching of an enzyme-ethylnitronate reaction intermediate through oxidative and nonoxidative turnover. This branching is isotope sensitive due to a kinetic isotope effect on nitronate release rather than on flavin reduction. The kinetic isotope effect on ethylnitronate release arises from the deprotonation of histidine 196, which provides electrostatic interactions with the nitronate to keep it bound in the active site for oxidation. The isotope effect on branching results in an inflation of the kinetic isotope observed for the nonoxidative pathway to values that are larger than the intrinsic values associated with C-H bond cleavage Neurospora crassa acetaldehyde + HNO2
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