Ultraviolet photolysis of metformin: mechanisms of environmental factors, identification of intermediates, and density functional theory calculations

Abstract

As a commonly used anti-diabetic drug, metformin (MEF) is frequently detected in different water bodies which pose a potential threat to human health and the ecological environment. In this study, oxidative degradation of MEF under ultraviolet (UV) light was studied, and its influencing factors, photolysis mechanism, and intermediates identification carried out as well. The results showed that the hydroxyl radical contributed 73% during the 6 h MEF photolysis process among the reactive oxygen species (ROS). In addition, triplet excited-state organic matter and singlet oxygen also played a role in the photolysis process. The reaction rates of hydroxyl radical and singlet oxygen with MEF are (6.45 ± 0.4) × 109 and (5.4 ± 0.7) × 106L·(mols)-1, respectively. By calculating the light screening effect of environmental factors, it is found that the presence of NO3- and Cl- had a greater excitation effect on ROS than the screening effect, and generally promoted the photolysis rates of MEF from 90.3 to 193.5% and from 16.1 to 80.6% during the 6-h reaction process, respectively. For bicarbonate and fulvic acid, the light screening effects were dominant and inhibited photolysis rates by 10-52% and 13-71%, respectively. The results demonstrated that the photoreactivity of environmental factors in water is the cause of the different photodegradation rates of MEF. The oxidative degradation product of MEF under UV light was detected by UPLC/Q-TOF as methylbiguanide (MBG), 2,4-diamino-1,3,5-triazine (2,4-DAT), biguanide (BGN), 1,1-dimethylguanidine (1,1-DiMBG), 4-amino-2-imino-1-methyl-1,2-dihydro-1, 3,5-triazine (4,2,1-AIMT), and 2-amino-4-methylamino-1,3,5-triazine (2,4-AMT). The result which showed that the primary sites of ∙OH attacked is consistent with that of density functional theory calculation. Graphical abstract.