SOEs (sulfite-oxidizing enzymes) are physiologically vital and occur in all forms of life. During the catalytic cycle, the five-co-ordinate square pyramidal oxo-molybdenum active site passes through the Mo(V) state, and intimate details of the structure can be obtained from variable frequency pulsed EPR spectroscopy through the hyperfine and nuclear quadrupole interactions of nearby magnetic nuclei. By employing variable spectrometer operational frequencies, it is possible to optimize the measurement conditions for difficult quadrupolar nuclei of interest (e.g. 17O, 33S, 35Cl and 37Cl) and to simplify the interpretation of the spectra. Isotopically labelled model Mo(V) compounds provide further insight into the electronic and geometric structures and chemical reactions of the enzymes. Recently, blocked forms of SOEs having co-ordinated sulfate, the reaction product, were detected using 33S (I=3/2) labelling. This blocking of product release is a possible contributor to fatal human sulfite oxidase deficiency in young children.
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December 2008
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Conference Article|
November 19 2008
Structures and reaction pathways of the molybdenum centres of sulfite-oxidizing enzymes by pulsed EPR spectroscopy
John H. Enemark;
John H. Enemark
1
1Department of Chemistry, University of Arizona, 1306 E. University Blvd, Tucson, AZ 85721-0041, U.S.A.
1To whom correspondence should be addressed (email jenemark@u.arizona.edu).
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Andrei V. Astashkin;
Andrei V. Astashkin
1Department of Chemistry, University of Arizona, 1306 E. University Blvd, Tucson, AZ 85721-0041, U.S.A.
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Arnold M. Raitsimring
Arnold M. Raitsimring
1Department of Chemistry, University of Arizona, 1306 E. University Blvd, Tucson, AZ 85721-0041, U.S.A.
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Publisher: Portland Press Ltd
Received:
June 04 2008
Online ISSN: 1470-8752
Print ISSN: 0300-5127
© The Authors Journal compilation © 2008 Biochemical Society
2008
Biochem Soc Trans (2008) 36 (6): 1129–1133.
Article history
Received:
June 04 2008
Citation
John H. Enemark, Andrei V. Astashkin, Arnold M. Raitsimring; Structures and reaction pathways of the molybdenum centres of sulfite-oxidizing enzymes by pulsed EPR spectroscopy. Biochem Soc Trans 1 December 2008; 36 (6): 1129–1133. doi: https://doi.org/10.1042/BST0361129
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