1.1.3.46 structures of Hmo and its mutants in complex with physiological/nonphysiological substrates, products and inhibitors 1.1.3.46 structures of wild-type and mutant Y128F with and without substrate. Cofactor FMNox possesses an electrophilic/nucleophilic duality. In the Y128F mutant the active-site perturbation ensemble facilitates the polarization of FMNox to a nucleophilic ylide, which is in a position to act on an alpha-ketoacid, forming an N5-acyl-FMNred dead-end adduct. In four-electron oxidation of mutant Y128F, an intramolecular disproportionation reaction via an N5-alkanol-FMNred C'alpha carbanion intermediate may account for the ThDP/PLP/NADPH-independent oxidative decarboxylation reaction