The chemistry of flavines and flavorproteins. Photoreduction of flavines by amino acids.
1. Flavines are photoreduced through their triplet states by amines and amino acids (e.g. EDTA and dl-phenylglycine). The anaerobic photoreduction of FMN and several other flavines with dl-phenylglycine was analysed in terms of a detailed kinetic scheme. 2. The reaction produces equimolar amounts of benzaldehyde, carbon dioxide and reduced flavine. 3. The sensitivity of the rates to substituents in the dl-phenylglycine can be described by a Hammett rho-value of -1.1. 4. Phenylacetic acid behaves differently from dl-phenylglycine or benzylamine towards a series of flavines. 5. The photoreductions are quenched by several aromatic compounds. From the effects of light-intensity and temperature, and by comparison with potassium iodide quenching, it is concluded that inhibition by the aromatic compounds is not simply a collisional process. 6. FAD reacts more slowly than FMN both in the photoreduction and in dark reduction by NADH. Urea and dimethyl sulphoxide decrease the intramolecular interaction in FAD, but they have no effect on the rate of dark reduction of FAD compared with FMN. In contrast, the photoreduction of FAD is quicker in urea.
D000447:Aldehydes; D001555:Benzene Derivatives; D002245:Carbon Dioxide; D004121:Dimethyl Sulfoxide; D004492:Edetic Acid; D005486:Flavin Mononucleotide / Q000528:radiation effects*; D005182:Flavin-Adenine Dinucleotide / Q000528:radiation effects; D005415:Flavins / Q000528:radiation effects*; D005998:Glycine; D007700:Kinetics; D008027:Light; D009243:NAD; D010084:Oxidation-Reduction; D010648:Phenylacetates; D011193:Potassium Iodide; D012256:Riboflavin / Q000528:radiation effects; D012701:Serotonin; D013696:Temperature; D014364:Tryptophan; D014508:Urea
D000447:Aldehydes; D001555:Benzene Derivatives; D005415:Flavins; D010648:Phenylacetates; D009243:NAD; D002245:Carbon Dioxide; D005182:Flavin-Adenine Dinucleotide; D011193:Potassium Iodide; D012701:Serotonin; D005486:Flavin Mononucleotide; D014364:Tryptophan; D014508:Urea; D004492:Edetic Acid; D005998:Glycine; D012256:Riboflavin; D004121:Dimethyl Sulfoxide