Elucidating Direct Photolysis Mechanisms of Different Dissociation Species of Norfloxacin in Water and Mg(2+) Effects by Quantum Chemical Calculations

The study of pollution due to combined antibiotics and metals is urgently needed. Photochemical processes are an important transformation pathway for antibiotics in the environment. The mechanisms underlying the effects of metal-ion complexation on the aquatic photochemical transformation of antibiotics in different dissociation forms are crucial problems in science, and beg solutions. Herein, we investigated the mechanisms of direct photolysis of norfloxacin (NOR) in different dissociation forms in water and metal ion Mg(2+) effects using quantum chemical calculations. Results show that different dissociation forms of NOR had different maximum electronic absorbance wavelengths (NOR(2+) < NOR(0) < NOR(+)) and showed different photolysis reactivity. Analysis of transition states (TS) and reaction activation energies (E(a)) indicated NOR(+) generally underwent loss of the piperazine ring (C10–N13 bond cleavage) and damage to piperazine ring (N13–C14 bond cleavage). For NOR(2+), the main direct photolysis pathways were de-ethylation (N7–C8 bond cleavage) and decarboxylation (C2–C5 bond cleavage). Furthermore, the presence of Mg(2+) changed the order of the wavelength at maximum electronic absorbance (NOR(+)-Mg(2+) < NOR(0)-Mg(2+) < NOR(2+)-Mg(2+)) and increased the intensities of absorbance peaks of all three dissociation species of NOR, implying that Mg(2+) played an important role in the direct photolysis of NOR(0), NOR(+), and NOR(2+). The calculated TS results indicated that the presence of Mg(2+) increased E(a) for most direct photolysis pathways of NOR, while it decreased E(a) for some direct photolysis pathways such as the loss of the piperazine ring and the damage of the piperazine ring of NOR(0) and the defluorination of NOR(+).