Oxygen uptake upon photolysis of 1,4-benzoquinones and 1,4-naphthoquinones in air-saturated aqueous solution in the presence of formate, amines, ascorbic acid, and alcohols.
The effects of oxygen in the photoreduction of 1,4-benzoquinone (BQ), 1,4-naphthoquinone (NQ), and a series of derivatives were studied in aqueous solution in the presence of acetonitrile and formate, aliphatic amines, e.g., EDTA or triethylamine, ascorbic acid, and alcohols, e.g., methanol or 2-propanol. The quinone triplet state is quenched, whereby the semiquinone and donor radicals are formed which react subsequently with oxygen. The overall reaction is oxidation of the donors and conversion of oxygen via the hydroperoxyl/superoxide radical into hydrogen peroxide. The quantum yield (Phi-O2) of this oxygen uptake changes in 2-propanol-water (1:10) from <0.01 for BQ to Phi-O2 = 0.5-0.8 for NQ. Generally Phi-O2 increases with increasing donor concentration. The specific properties of quinone structure, the radical equilibria and reactivity, and the concentration dependences are discussed.
Görner
Helmut
H
Max-Planck-Institut für Bioanorganische Chemie, D-45413 Mülheim an der Ruhr, Germany.
D000433:1-Propanol / Q000737:chemistry; D000438:Alcohols / Q000737:chemistry*; D000588:Amines / Q000737:chemistry*; D001205:Ascorbic Acid / Q000737:chemistry*; D016227:Benzoquinones / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods*; D004583:Electrons; D005561:Formates / Q000737:chemistry*; D006861:Hydrogen Peroxide / Q000737:chemistry; D008956:Models, Chemical; D009285:Naphthoquinones / Q000737:chemistry*; D010100:Oxygen / Q000737:chemistry*; D011809:Quinones / Q000737:chemistry; D013997:Time Factors; D014867:Water / Q000737:chemistry*
D000438:Alcohols; D000588:Amines; D016227:Benzoquinones; D005561:Formates; D009285:Naphthoquinones; D011809:Quinones; D014867:Water; C030544:formic acid; D000433:1-Propanol; D006861:Hydrogen Peroxide; D001205:Ascorbic Acid; C035342:1,4-naphthoquinone; D010100:Oxygen