Effect of pH, Buffer, and Viscosity on the Photolysis of Formylmethylflavin: A Kinetic Study

The kinetics of the photolysis of formylmethylflavin, a major intermediate product in the aerobic and anaerobic photolysis of riboflavin, was studied in the pH range 2.0-11.0. Formylmethylflavin and its photoproducts, lumichrome and lumiflavin, were determined in degraded solutions using a specific multicomponent spectrophotometric method. The photolysis of formylmethylflavin in alkaline medium takes place by first-order kinetics and the rate constants (kobs) at pH 7.5-11.0 range from 0.27 x 10(-4) to 3.88 x 10(-4) and 0.36 x 10(-4) to 5.63 x 10(-4) s(-1) under aerobic and anaerobic conditions respectively. In acid medium, the photolysis involves a second- order mechanism and the rate constants at pH 2.0-7.0 range from 1.37 to 2.11 and 2.03 to 2.94M(-1) s(-1) under aerobic and anaerobic conditions respectively. The rate-pH profiles for the photolysis reactions indicate the highest rate of formylmethylflavin degradation is at, pH 4 and above pH 10. In the alkaline region, the increase in rate with pH is due to higher reactivity of the flavin triplet state. The photolysis of formylmethylflavin is catalyzed by phosphate ions and is affected by the solvent viscosity.