title: Electronic structure contributions to reactivity in xanthine oxidase family enzymes.
abstract: We review the xanthine oxidase (XO) family of pyranopterin molybdenum enzymes with a specific emphasis on electronic structure contributions to reactivity. In addition to xanthine and aldehyde oxidoreductases, which catalyze the two-electron oxidation of aromatic heterocycles and aldehyde substrates, this mini-review highlights recent work on the closely related carbon monoxide dehydrogenase (CODH) that catalyzes the oxidation of CO using a unique Mo-Cu heterobimetallic active site. A primary focus of this mini-review relates to how spectroscopy and computational methods have been used to develop an understanding of critical relationships between geometric structure, electronic structure, and catalytic function.
authors.affiliation: Department of Chemistry and Chemical Biology, University of New Mexico, MSC03 2060, 300 Terrace St. NE, Albuquerque, NM, 87131, USA.
authors.forename: Benjamin W
authors.initials: BW
authors.lastname: Stein
authors.forename: Martin L
authors.initials: ML
authors.lastname: Kirk
mesh_terms: D000445:Aldehyde Oxidoreductases / Q000737:chemistry*; D002384:Catalysis; D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D004583:Electrons; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D009097:Multienzyme Complexes / Q000737:chemistry*; D010084:Oxidation-Reduction; D011487:Protein Conformation; D019820:Xanthine / Q000737:chemistry; D014969:Xanthine Oxidase / Q000737:chemistry* / Q000145:classification / Q000378:metabolism
chemical_list: D009097:Multienzyme Complexes; D019820:Xanthine; D008982:Molybdenum; D014969:Xanthine Oxidase; D000445:Aldehyde Oxidoreductases; C019823:carbon monoxide dehydrogenase