Photo-oxidative degradation of doxorubicin with siloxane MOFs by exposure to daylight.

Doxorubicin (DOX) is a chemotherapeutic agent from anthracycline class, which acts unselectively on all cells; thus, it may have genotoxic and/or mutagenic effects and cause serious environmental problems. Herein, the decomposition of a diluted solution of DOX hydrochloride for injection has been investigated under photo-oxidative conditions, in ambient light and without pH modification, using hydrogen peroxide as oxidizing agent and hydrophobic siloxane-based metal-organic frameworks (MOFs) as heterogeneous catalysts. The kinetics of the photodegradation process was followed by UV-Vis spectroscopy and by ESI-MS. According to UV-Vis data, two pseudo-first-order kinetic steps describe the process, with rate constants in the order of 10-3-10-2 min-1 for the rate-determining one. ESI-MS provided more accurate information, with a rate constant of 2.6 · 10-2 min-1 calculated from the variation of DOX ion abundance. Complete decomposition of DOX was achieved after 120 min in the shade and after only 20 min by exposure to sunlight. The analysis of the residual waters by mass spectrometry and 1D and 2D NMR spectroscopy showed complete disappearance of DOX in all cases, excluded any anthracycline species, which are destroyed in the tested conditions, and proved formation of an un-harmful compound-glycerol, while no trace of metal was detected by XRF. Preliminary data also showed decomposition of oxytetracycline in similar conditions. By this study, we bring into attention a less-addressed pollution issue and we propose a mild and effective method for the removal of drug emerging pollutants.