Journal
COORDINATION CHEMISTRY REVIEWS
Volume 255, Issue 9-10, Pages 1055-1084Publisher
ELSEVIER SCIENCE SA
DOI: 10.1016/j.ccr.2011.01.056
Keywords
Molybdenum enzymes; Tungsten enzymes; Spectroscopic characterization; X-ray absorption spectroscopy; Electron paramagnetic resonance spectroscopy; Coordination structure; Sulfite oxidase family; DMSO reductase family; Xanthine oxidase family
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Funding
- Natural Sciences and Engineering Research Council of Canada
- Canadian Institutes of Health Research (CIHR)
- Saskatchewan Health Research Foundation (SHRF)
- University of Saskatchewan
- Canada Foundation for Innovation
- Canada Research Chair
- DOE Office of Biological and Environmental Research
- National Institutes of Health, National Center for Research Resources [P41RR001209]
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Molybdenum and tungsten are the only second and third-row transition elements with a known function in living systems. Molybdenum fulfills functional roles in enzyme systems in almost all living creatures, from bacteria through plants to invertebrates and mammals, while tungsten takes the place of molybdenum in some prokaryotes, especially the hyperthermophilic archaea. The enzymes contain the metal bound by an unusual sulfur-containing cofactor. Despite possessing common structural elements, the enzymes are remarkable in the range of different chemical reactions that are catalyzed, although almost all are two-electron oxidation-reduction reactions in which an oxygen atom is transferred to or from the molybdenum. The functional roles filled by molybdenum enzymes are equally diverse; for example, they play essential roles in microbial respiration, in the uptake of nitrogen in green plants, in controlling insect eye color, and in human health. Spectroscopic studies, in particular electron paramagnetic resonance and X-ray absorption spectroscopy, have played an essential role in our understanding of the active site structures and catalytic mechanisms of the molybdenum and tungsten enzymes. This review summarizes the role spectroscopy has played in the state of our knowledge of the molybdenum and tungsten enzymes, with particular regard to structural information on the molybdenum sites. (C) 2011 Elsevier B.V. All rights reserved.
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