Photoproducts of tetracycline and oxytetracycline involving self-sensitized oxidation in aqueous solutions: Effects of Ca2+ and Mg2+

Tetracyclines constitute one of the most important antibiotic families and represent a classic example of phototoxicity. The photoproducts of tetracyclines and their parent compounds have potentially adverse effects on natural ecosystem. In this study, the self-sensitized oxidation products of tetracycline (TC) and oxytetracycline (OTC) were determined and the effects of Ca²⁺ and Mg²⁺on self-sensitized degradation were investigated. The Ca²⁺ and Mg²⁺ in the natural water sample accounted for enhancement (pH 7.3) and inhibition (pH 9.0) of photodegradation of TC and OTC due to the formation of metal-ions complexes. The formation of Mg²⁺ complexes was unfavorable for the photodegradation of the tetracyclines at both pH values. In contrast, the Ca²⁺ complexes facilitated the attack of singlet oxygen (¹O₂) arising from self-sensitization at pH 7.3 and enhanced TC photodegradation. For the first time, self-sensitized oxidation products of TC and OTC were verified by quenching experiments and detected by LC/ESI-DAD-MS. The products had a nominal mass 14 Da higher than the parent drugs (designated M+14), which resulted from the ¹O₂ attack of the dimethylamino group on the C-4 atom of the tetracyclines. The presence of Ca²⁺ and Mg²⁺ also affected the generation of M+14 due to the formation of metal-ions complexes with TC and OTC. The findings suggest that the metal-ion complexation has significant impact on the self-sensitized oxidation processes and the photoproducts of tetracyclines.