title: Firefly luciferase produces hydrogen peroxide as a coproduct in dehydroluciferyl adenylate formation.
abstract: Firefly luciferase catalyzes the synthesis of H2O2 from the same substrates as the bioluminescence reaction: ATP and luciferin (D-LH2). About 80% of the enzyme-bound intermediate D-luciferyl adenylate (D-LH2-AMP) is oxidized into oxyluciferin, and a photon is emitted during this reaction. The enzyme pathway responsible for the generation of H2O2 is a side reaction in which D-LH2-AMP is oxidized into dehydroluciferyl adenylate (L-AMP). Like the bioluminescence reaction, the luciferase-catalyzed synthesis of H2O2 and L-AMP is a stereospecific process, involving only the natural D enantiomer. However, the intramolecular electron transfer postulated as essential to the light emission process is not involved in this side reaction.
authors.affiliation: Centro de Investigação em Química, Departamento de Química, Faculdade de Ciências, Universidade do Porto, R. Campo Alegre 687, 4169-007 Porto, Portugal.
authors.forename: Hugo
authors.initials: H
authors.lastname: Fraga
authors.forename: Diogo
authors.initials: D
authors.lastname: Fernandes
authors.forename: Jiri
authors.initials: J
authors.lastname: Novotny
authors.forename: Rui
authors.initials: R
authors.lastname: Fontes
authors.forename: Joaquim C G
authors.initials: JC
authors.lastname: Esteves da Silva
mesh_terms: D000255:Adenosine Triphosphate / Q000378:metabolism; D000818:Animals; D002851:Chromatography, High Pressure Liquid; D049454:Firefly Luciferin / Q000378:metabolism*; D006861:Hydrogen Peroxide / Q000032:analysis / Q000378:metabolism*; D049409:Luciferases, Firefly / Q000378:metabolism*; D008954:Models, Biological; D015394:Molecular Structure; D010084:Oxidation-Reduction; D010100:Oxygen / Q000378:metabolism
chemical_list: C107793:dehydroluciferin; D049454:Firefly Luciferin; D000255:Adenosine Triphosphate; D006861:Hydrogen Peroxide; D049409:Luciferases, Firefly; D010100:Oxygen