Effects of inorganic ions on the photolysis of propranolol in FA solution

Photolysis of the widely used beta-blocker propranolol (PRO) was investigated in the presence of fulvic acid (FA) and inorganic ions under simulated solar irradiation. PRO undergoes direct photolysis proceeding mainly via degradation of the triplet excited state, ³PRO*. FA and inorganic ions inhibited photolysis of PRO in the order of FA > Fe³⁺ > Cl^- > Ca²⁺ > Mg²⁺ > NO₃^- > K⁺. An antagonistic effect between FA and inorganic ions toward the suppression of PRO photolysis was exhibited. The binding behaviors of PRO, FA, and inorganic ions were examined through fluorescence quenching experiments, which showed that inorganic ions affected the binding between FA and PRO through competing for the binding sites of FA or PRO. The correlation analysis demonstrated a positive correlation between the binding constant (K_OC) of FA-PRO and the inhibition rate of FA on PRO photolysis. The observed rate constants of photolysis (k_obs) have opposite correlations with the concentration of singlet oxygen (¹O₂). These findings strongly suggest that inorganic ions decrease the inhibition effect of FA on PRO photolysis via restraining the complexation of FA-PRO and production of ¹O₂.