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Introduction to glycyl radical enzymes. (A) Domain map of PFL showing the GRD (red) and conserved cysteines on the Cys loop (pink). *Only PFLs and TdcEs are known to have a two-cysteine motif on the Cys loop. (B) Pyruvate formate lyase structure (PDB ID: 1H18) showing the GRE homodimer. Inset shows 10-stranded β-barrel, Gly, and Cys loops. (C) Reaction scheme of AdoMet cleavage by GRE-AEs. (D) Conserved catalytic mechanism of GREs. (E) The glycine that houses the radical cofactor is buried in the GRD (red) and must flip out of the active site for post-translational radical installation by the AE. Site of glycyl radical is indicated with a black star.