Characterization of intermediate compounds formed upon photoinduced degradation of quinolones by high-performance liquid chromatography/high-resolution multiple-stage mass spectrometry.
The paper deals with the photocatalytic transformation of two antibacterial agents, ofloxacin and ciprofloxacin, under simulated solar irradiation using titanium dioxide as photocatalyst. The investigation involved monitoring decomposition of the drugs, identifying intermediate compounds, assessing mineralization, and evaluating the toxicity of drug derivatives. High-resolution mass spectrometry was employed to assess evolution of the photocatalyzed process over time. Respectively 15 and 8 main species were identified after transformation of ofloxacin and ciprofloxacin. Through the full analysis of MS and MSn spectra and a comparison with parent drug fragmentation pathways, the different isomers were characterized. In the ofloxacin molecule, the initial transformation attacks are confined to the piperazine moiety and to the methyl groups, while the fluoroquinolone core is unmodified. Conversely, ciprofloxacin degradation involves two parts of the molecule: the piperazinic moiety and the quinolone moiety. All these intermediates are easily degraded and by 4 h mineralization is complete. Toxicity assays using Vibrio fischeri prove that neither ciprofloxacin nor its intermediates exhibit acute toxicity. In ofloxacin the secondary degradation products exhibit toxicity; a correlation exists between the evolution of the intermediate compounds and the toxicity connected to them.
Calza
Paola
P
Dipartimento di Chimica Analitica, Università di Torino, via P. Giuria 5, 10125 Torino, Italy. paola.calza@unito.it
Medana
Claudio
C
Carbone
Francesco
F
Giancotti
Valeria
V
Baiocchi
Claudio
C
D002851:Chromatography, High Pressure Liquid / Q000379:methods*; D003198:Computer Simulation; D008027:Light; D008956:Models, Chemical; D008958:Models, Molecular; D008968:Molecular Conformation / Q000528:radiation effects; D015363:Quinolones / Q000737:chemistry* / Q000528:radiation effects*; D011829:Radiation Dosage; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
D015363:Quinolones