Direct Detection of Oxygen Intermediates in the Non-Heme Fe Enzyme Taurine/α-Ketoglutarate Dioxygenase
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- 8 January 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (4) , 1022-1023
- https://doi.org/10.1021/ja039113j
Abstract
The reaction of substrate-bound taurine/α-ketoglutarate dioxygenase with O2 has been studied using cryogenic continuous-flow spectroscopy. Transient absorption spectra acquired at −38 °C show an exponential decay of a 318-nm chromophore with an apparent rate of 1.3 s-1. The observed optical changes and their kinetics are consistent with the profile of an Fe(IV) species detected recently by Mössbauer spectroscopy (Price et al., Biochemistry 2003, 42, 7497−7508). Resonance Raman measurement upon excitation at 363.7 nm reveal at least two oxygen isotope-sensitive vibrations at 821/787 cm-1 and 583/555 cm-1 for 16O and 18O derivatives, respectively. An additional mode is likely to be obscured by an ethylene glycol vibration at 865 cm-1 and/or 1089 cm-1. The 821 cm-1 vibration is assigned to the stretching mode of Fe(IV)O species on the basis of its frequency and isotopic shift amplitude. The 583 cm-1 band is likely to originate from an Fe−O2 precursor of the Fe(IV)O species, although its structural details are unclear at present.Keywords
This publication has 10 references indexed in Scilit:
- The First Direct Characterization of a High-Valent Iron Intermediate in the Reaction of an α-Ketoglutarate-Dependent Dioxygenase: A High-Spin Fe(IV) Complex in Taurine/α-Ketoglutarate Dioxygenase (TauD) from Escherichia coliBiochemistry, 2003
- End-On and Side-On Peroxo Derivatives of Non-Heme Iron Complexes with Pentadentate Ligands: Models for Putative Intermediates in Biological Iron/Dioxygen ChemistryInorganic Chemistry, 2003
- Crystallographic and Spectroscopic Characterization of a Nonheme Fe(IV)=O ComplexScience, 2003
- X-ray Crystal Structure of Escherichia coli Taurine/α-Ketoglutarate Dioxygenase Complexed to Ferrous Iron and Substrates,Biochemistry, 2002
- Resonance Raman spectra and biological significance of high-valent iron(IV,V) porphyrinsCoordination Chemistry Reviews, 2002
- The iron(II) and 2-oxoacid-dependent dioxygenases and their role in metabolism (1967 to 1999)Natural Product Reports, 2000
- Geometric and Electronic Structure/Function Correlations in Non-Heme Iron EnzymesChemical Reviews, 1999
- Detailed Spectroscopic and Theoretical Studies on [Fe(EDTA)(O2)]3-: Electronic Structure of the Side-on Ferric−Peroxide Bond and Its Relevance to ReactivityJournal of the American Chemical Society, 1998
- Dioxygen activation and bond cleavage by mixed-valence cytochrome c oxidaseProceedings of the National Academy of Sciences, 1998
- Characterization of α-Ketoglutarate-dependent Taurine Dioxygenase from Escherichia coliJournal of Biological Chemistry, 1997