title: Mechanistic aspects of alloxan diabetogenic activity: a key role of keto-enol inversion of dialuric acid on ionization.
abstract: The inversion of the keto-enol stability order of dialuric acid on ionization was calculated and verified experimentally. The radical cations in both forms were characterized. The spectrum of the keto form was observed upon direct ionization of dialuric acid under matrix conditions, whereas the enol form was formed upon a sequential electron-proton-proton attachment to alloxan under acidic aqueous condition. Facilitation of the one-electron oxidation of dialuric acid upon its enolization can result in a more effective formation of superoxide radical anion in the process of its auto-oxidation. This process is discussed in reference to the alloxan diabetogenic action. Both neutral keto and enol forms are energetically close, and under favorable conditions, the auto-oxidation of dialuric acid could involve participation of the enol form.
authors.affiliation: Institute of Applied Radiation Chemistry, Technical University of Lodz, Poland.
authors.forename: Małgorzata
authors.initials: M
authors.lastname: Czerwiñska
authors.forename: Adam
authors.initials: A
authors.lastname: Sikora
authors.forename: Piotr
authors.initials: P
authors.lastname: Szajerski
authors.forename: Jan
authors.initials: J
authors.lastname: Adamus
authors.forename: Andrzej
authors.initials: A
authors.lastname: Marcinek
authors.forename: Jerzy
authors.initials: J
authors.lastname: Gebicki
authors.forename: Paweł
authors.initials: P
authors.lastname: Bednarek
mesh_terms: D000496:Alloxan / Q000737:chemistry* / Q000378:metabolism; D000818:Animals; D001463:Barbiturates / Q000737:chemistry* / Q000378:metabolism; D003921:Diabetes Mellitus, Experimental / Q000139:chemically induced / Q000378:metabolism; D007477:Ions; D015394:Molecular Structure; D013057:Spectrum Analysis; D013237:Stereoisomerism
chemical_list: D001463:Barbiturates; D007477:Ions; C004718:dialuric acid; D000496:Alloxan