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; J. Martin Bollinger; Carsten Krebs

doi:10.1021/ja048255q

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, J. Martin Bollinger, Carsten Krebs

Research output: Contribution to journal › Article › peer-review

282 Scopus citations

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 language	English (US)
Pages (from-to)	8108-8109
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	126
Issue number	26
DOIs	https://doi.org/10.1021/ja048255q
State	Published - Jul 7 2004

All Science Journal Classification (ASJC) codes

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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@article{69fc2fbc90394258a7c70d117b74f551,

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, {J. Martin} and Carsten Krebs",

year = "2004",

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doi = "10.1021/ja048255q",

language = "English (US)",

volume = "126",

pages = "8108--8109",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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

Research output: Contribution to journal › Article › peer-review

TY - JOUR

T1 - EXAFS spectroscopic evidence for an Fe=O unit in the Fe(IV) intermediate observed during oxygen activation by taurine:α-ketoglutarate dioxygenase

AU - Riggs-Gelasco, Pamela J.

AU - Price, John C.

AU - Guyer, Robert B.

AU - Brehm, Jessica H.

AU - Barr, Eric W.

AU - Bollinger, J. Martin

AU - Krebs, Carsten

PY - 2004/7/7

Y1 - 2004/7/7

N2 - 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.

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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DO - 10.1021/ja048255q

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VL - 126

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 26

ER -

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

Abstract

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