EXAFS spectroscopic evidence for an Fe=O unit in the Fe(IV) intermediate observed during oxygen activation by taurine:α-ketoglutarate dioxygenase

Pamela J. Riggs-Gelasco, John C. Price, Robert B. Guyer, Jessica H. Brehm, Eric W. Barr, Joseph M. Bollinger, Jr., Carsten Krebs

Research output: Contribution to journalArticle

222 Citations (Scopus)

Abstract

The Fe(II)- and α-ketoglutarate-dependent dioxygenases catalyze hydroxylation reactions of considerable biomedical and environmental significance. Recently, the first oxidized iron intermediate in the reaction of a member of this family, taurine:α-ketoglutarate dioxygenase (TauD), was detected and shown to be a high-spin Fe(IV) complex. In this study we have used X-ray absorption spectroscopy to demonstrate the presence of a short (1.62 Å) interaction between the iron and one of its ligands in the Fe(IV) intermediate but not in the Fe(II) starting complex. The detection of this interaction strongly corroborates the hypothesis that the intermediate contains an Fe=O structural motif.

Original languageEnglish (US)
Pages (from-to)8108-8109
Number of pages2
JournalJournal of the American Chemical Society
Volume126
Issue number26
DOIs
StatePublished - Jul 7 2004

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Dioxygenases
Taurine
Iron
X-Ray Absorption Spectroscopy
Chemical activation
Oxygen
Hydroxylation
X ray absorption spectroscopy
Ligands

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "EXAFS spectroscopic evidence for an Fe=O unit in the Fe(IV) intermediate observed during oxygen activation by taurine:α-ketoglutarate dioxygenase",
abstract = "The Fe(II)- and α-ketoglutarate-dependent dioxygenases catalyze hydroxylation reactions of considerable biomedical and environmental significance. Recently, the first oxidized iron intermediate in the reaction of a member of this family, taurine:α-ketoglutarate dioxygenase (TauD), was detected and shown to be a high-spin Fe(IV) complex. In this study we have used X-ray absorption spectroscopy to demonstrate the presence of a short (1.62 {\AA}) interaction between the iron and one of its ligands in the Fe(IV) intermediate but not in the Fe(II) starting complex. The detection of this interaction strongly corroborates the hypothesis that the intermediate contains an Fe=O structural motif.",
author = "Riggs-Gelasco, {Pamela J.} and Price, {John C.} and Guyer, {Robert B.} and Brehm, {Jessica H.} and Barr, {Eric W.} and {Bollinger, Jr.}, {Joseph M.} and Carsten Krebs",
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EXAFS spectroscopic evidence for an Fe=O unit in the Fe(IV) intermediate observed during oxygen activation by taurine:α-ketoglutarate dioxygenase. / Riggs-Gelasco, Pamela J.; Price, John C.; Guyer, Robert B.; Brehm, Jessica H.; Barr, Eric W.; Bollinger, Jr., Joseph M.; Krebs, Carsten.

In: Journal of the American Chemical Society, Vol. 126, No. 26, 07.07.2004, p. 8108-8109.

Research output: Contribution to journalArticle

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AU - Riggs-Gelasco, Pamela J.

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AU - Guyer, Robert B.

AU - Brehm, Jessica H.

AU - Barr, Eric W.

AU - Bollinger, Jr., Joseph M.

AU - Krebs, Carsten

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AB - The Fe(II)- and α-ketoglutarate-dependent dioxygenases catalyze hydroxylation reactions of considerable biomedical and environmental significance. Recently, the first oxidized iron intermediate in the reaction of a member of this family, taurine:α-ketoglutarate dioxygenase (TauD), was detected and shown to be a high-spin Fe(IV) complex. In this study we have used X-ray absorption spectroscopy to demonstrate the presence of a short (1.62 Å) interaction between the iron and one of its ligands in the Fe(IV) intermediate but not in the Fe(II) starting complex. The detection of this interaction strongly corroborates the hypothesis that the intermediate contains an Fe=O structural motif.

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