title: Why is firefly oxyluciferin a notoriously labile substance?
abstract: The chemistry of firefly bioluminescence is important for numerous applications in biochemistry and analytical chemistry. The emitter of this bioluminescent system, firefly oxyluciferin, is difficult to handle. The cause of its lability was clarified while its synthesis was reinvestigated. A side product was identified and characterized by NMR spectroscopy and X-ray crystallography. The reason for the lability of oxyluciferin is now ascribed to autodimerization of the coexisting enol and keto forms in a Mannich-type reaction.
authors.affiliation: Department Chemie, Technische Universität München, Lichtenbergstrasse 4, 85748 Garching b. München (Germany).
authors.forename: Oleg V
authors.initials: OV
authors.lastname: Maltsev
authors.forename: Naba K
authors.initials: NK
authors.lastname: Nath
authors.forename: Panče
authors.initials: P
authors.lastname: Naumov
authors.forename: Lukas
authors.initials: L
authors.lastname: Hintermann
mesh_terms: D000818:Animals; D018360:Crystallography, X-Ray; D019281:Dimerization; D048888:Fireflies / Q000737:chemistry* / Q000378:metabolism; D007211:Indoles / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry; D008352:Mannich Bases / Q000737:chemistry; D008968:Molecular Conformation; D011719:Pyrazines / Q000737:chemistry*; D013997:Time Factors
chemical_list: D007211:Indoles; D007659:Ketones; D008352:Mannich Bases; D011719:Pyrazines; C014730:oxyluciferin
keywords: bioorganic chemistry; heterocycles; luminescence; natural products; structure elucidation