title: Reversible H atom abstraction catalyzed by the radical S-adenosylmethionine enzyme HydG.
abstract: The organometallic H-cluster at the active site of [FeFe]-hydrogenases is synthesized by three accessory proteins, two of which are radical S-adenosylmethionine enzymes (HydE, HydG) and one of which is a GTPase (HydF). In this work we probed the specific role of H atom abstraction in HydG-catalyzed carbon monoxide and cyanide production from tyrosine. The isotope distributions of 5'-deoxyadenosine and p-cresol were evaluated using deuterium-labeled tyrosine substrates in H2O and D2O. The observation of multiply deuterated 5'-deoxyadenosine and deuterated S-adenosylmethionine when the reaction is carried out in D2O provides evidence for a 5'-deoxyadenosyl radical-mediated abstraction of a hydrogen atom from a solvent-exchangeable position as a reversible event.
authors.affiliation: Department of Chemistry and Biochemistry, Montana State University , Bozeman, Montana 59717, United States.
authors.forename: Benjamin R
authors.initials: BR
authors.lastname: Duffus
authors.forename: Shourjo
authors.initials: S
authors.lastname: Ghose
authors.forename: John W
authors.initials: JW
authors.lastname: Peters
authors.forename: Joan B
authors.initials: JB
authors.lastname: Broderick
mesh_terms: D001426:Bacterial Proteins / Q000737:chemistry / Q000378:metabolism*; D002248:Carbon Monoxide / Q000378:metabolism; D002384:Catalysis; D020134:Catalytic Domain; D003013:Clostridium / Q000737:chemistry / Q000378:metabolism*; D003486:Cyanides / Q000378:metabolism; D006859:Hydrogen / Q000378:metabolism; D006864:Hydrogenase / Q000737:chemistry / Q000378:metabolism*; D008958:Models, Molecular; D012436:S-Adenosylmethionine / Q000378:metabolism*; D014443:Tyrosine / Q000378:metabolism
chemical_list: D001426:Bacterial Proteins; D003486:Cyanides; D014443:Tyrosine; D012436:S-Adenosylmethionine; D002248:Carbon Monoxide; D006859:Hydrogen; D006864:Hydrogenase
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