In the absence of its substrate, the auto-reduction of the high-valent bis-Fe(IV) state of the dihaem enzyme MauG is coupled to oxidative damage of a methionine residue. Transient kinetic and solvent isotope effect studies reveal that this process occurs via two sequential long-range electron transfer (ET) reactions from methionine to the haems. The first ET is coupled to proton transfer (PT) to the haems from solvent via an ordered water network. The second ET is coupled to PT at the methionine site and occurs during the oxidation of the methionine to a sulfoxide. This process proceeds via Compound I- and Compound II-like haem intermediates. It is proposed that the methionine radical is stabilized by a two-centre three-electron (2c3e) bond. This provides insight into how oxidative damage to proteins may occur without direct contact with a reactive oxygen species, and how that damage can be propagated through the protein.
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K-Ras4B membrane-anchored dimers in the cell. Dimerization can take place through helical (left) and beta-sheet (right) interfaces. The major (front) and minor (back) conformations are shown. For further details please see pp. 1719–1732. Image kindly provided by Ruth Nussinov. - PDF Icon PDF LinkFront Matter
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Research Article|
June 10 2016
Mechanism of protein oxidative damage that is coupled to long-range electron transfer to high-valent haems
Zhongxin Ma;
Zhongxin Ma
*Burnett School of Biomedical Sciences, College of Medicine, University of Central Florida, Orlando, FL 32827, U.S.A.
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Heather R. Williamson;
Heather R. Williamson
*Burnett School of Biomedical Sciences, College of Medicine, University of Central Florida, Orlando, FL 32827, U.S.A.
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Victor L. Davidson
Victor L. Davidson
1
*Burnett School of Biomedical Sciences, College of Medicine, University of Central Florida, Orlando, FL 32827, U.S.A.
1To whom correspondence should be addressed (email victor.davidson@ucf.edu).
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Publisher: Portland Press Ltd
Received:
February 01 2016
Revision Received:
April 11 2016
Accepted:
April 12 2016
Accepted Manuscript online:
April 13 2016
Online ISSN: 1470-8728
Print ISSN: 0264-6021
© 2016 The Author(s). published by Portland Press Limited on behalf of the Biochemical Society
2016
Biochem J (2016) 473 (12): 1769–1775.
Article history
Received:
February 01 2016
Revision Received:
April 11 2016
Accepted:
April 12 2016
Accepted Manuscript online:
April 13 2016
Citation
Zhongxin Ma, Heather R. Williamson, Victor L. Davidson; Mechanism of protein oxidative damage that is coupled to long-range electron transfer to high-valent haems. Biochem J 15 June 2016; 473 (12): 1769–1775. doi: https://doi.org/10.1042/BCJ20160047
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