title: SkfB Abstracts a Hydrogen Atom from Cα on SkfA To Initiate Thioether Cross-Link Formation.
abstract: Sulfur to α-carbon thioether-containing peptides (sactipeptides) are ribosomally synthesized post-translationally modified peptides with bacteriocidal activities. The thioether cross-link, which is required for biological activity, is installed by a member of the radical S-adenosyl-l-methionine (SAM) superfamily in the peptide substrate. Herein, we show that the radical SAM enzyme, SkfB, utilizes the 5'-deoxyadenosyl radical generated from the reductive cleavage of SAM to abstract a hydrogen atom from the α-carbon of the amino acid at position 12 in the substrate, SkfA, to initiate the installation of a thioether cross-link. The insights from this work can be applied to all radical SAM sactipeptide maturases.
authors.affiliation: Chemistry Department, University of Utah , Salt Lake City, Utah 84112, United States.
authors.forename: Nathan A
authors.initials: NA
authors.lastname: Bruender
authors.affiliation: Chemistry Department, University of Utah , Salt Lake City, Utah 84112, United States.
authors.forename: Vahe
authors.initials: V
authors.lastname: Bandarian
mesh_terms: D001412:Bacillus subtilis / Q000378:metabolism; D001426:Bacterial Proteins / Q000737:chemistry* / Q000378:metabolism*; D003432:Cross-Linking Reagents; D006859:Hydrogen / Q000378:metabolism; D007506:Iron-Sulfur Proteins / Q000737:chemistry / Q000378:metabolism; D010455:Peptides / Q000737:chemistry* / Q000378:metabolism*; D012436:S-Adenosylmethionine / Q000378:metabolism; D013440:Sulfides / Q000737:chemistry / Q000378:metabolism*
chemical_list: D001426:Bacterial Proteins; D003432:Cross-Linking Reagents; D007506:Iron-Sulfur Proteins; D010455:Peptides; D013440:Sulfides; D012436:S-Adenosylmethionine; D006859:Hydrogen