title: Radical S-adenosyl-L-methionine chemistry in the synthesis of hydrogenase and nitrogenase metal cofactors.
abstract: Nitrogenase, [FeFe]-hydrogenase, and [Fe]-hydrogenase enzymes perform catalysis at metal cofactors with biologically unusual non-protein ligands. The FeMo cofactor of nitrogenase has a MoFe7S9 cluster with a central carbon, whereas the H-cluster of [FeFe]-hydrogenase contains a 2Fe subcluster coordinated by cyanide and CO ligands as well as dithiomethylamine; the [Fe]-hydrogenase cofactor has CO and guanylylpyridinol ligands at a mononuclear iron site. Intriguingly, radical S-adenosyl-L-methionine enzymes are vital for the assembly of all three of these diverse cofactors. This minireview presents and discusses the current state of knowledge of the radical S-adenosylmethionine enzymes required for synthesis of these remarkable metal cofactors.
authors.affiliation: From the Department of Chemistry and Biochemistry, Montana State University, Bozeman, Montana 59717.
authors.forename: Amanda S
authors.initials: AS
authors.lastname: Byer
authors.affiliation: From the Department of Chemistry and Biochemistry, Montana State University, Bozeman, Montana 59717.
authors.forename: Eric M
authors.initials: EM
authors.lastname: Shepard
authors.affiliation: From the Department of Chemistry and Biochemistry, Montana State University, Bozeman, Montana 59717.
authors.forename: John W
authors.initials: JW
authors.lastname: Peters
authors.affiliation: From the Department of Chemistry and Biochemistry, Montana State University, Bozeman, Montana 59717 jbroderick@chemistry.montana.edu.
authors.forename: Joan B
authors.initials: JB
authors.lastname: Broderick
mesh_terms: D000818:Animals; D003067:Coenzymes / Q000096:biosynthesis*; D005609:Free Radicals / Q000737:chemistry*; D006801:Humans; D008670:Metals / Q000737:chemistry*; D008745:Methylation; D011496:Protein Methyltransferases / Q000378:metabolism*; D012436:S-Adenosylmethionine / Q000737:chemistry / Q000378:metabolism*
chemical_list: D003067:Coenzymes; D005609:Free Radicals; D008670:Metals; D012436:S-Adenosylmethionine; D011496:Protein Methyltransferases
keywords: Hydrogenase; Iron-Sulfur Protein; Nitrogenase; Radical; S-Adenosylmethionine (SAM)