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Iron ions can be used to degrade tetracycline dispersed in nature. Studies of absorption and fluorescence spectra and quantum chemistry calculations showed that iron is more readily released from Fe(III)-citrate than from Fe(III)-EDTA, so Fe(III)-citrate (Fe(III)-Cit) is more suitable for tetracycline (TC) degradation. At 30 °C, a severe degradation of TC by Fe(III)-Cit occurred as early as after 3 days of incubation in the light, and after 5 days in the dark. In contrast, the degradation of TC by Fe(III)-EDTA proceeded very slowly in the dark. By the fifth day of incubation of TC with Fe(III)-Cit in darkness, the concentrations of the former compound dropped by 55% and 75%, at 20 °C and 30 °C, respectively. The decrease in tetracycline concentrations caused by Fe(III)-EDTA in darkness at the same temperatures was only 2% and 6%, respectively. Light increased the degradation rates of TC by Fe(III)-EDTA to 20% and 56% at 20 °C and 30 °C, respectively. The key role of the light in the degradation of tetracycline by Fe(III)-EDTA was thus demonstrated. The TC degradation reaction showed a second-order kinetics. The rate constants of Fe(III)-Cit-induced TC degradation at 20 °C and 30 °C in darkness were k = 4238 M−1day−1 and k = 11,330 M−1day−1, respectively, while for Fe(III)-EDTA were 55 M−1day−1 and 226 M−1day−1. In light, these constants were k = 15,440 M−1day−1 and k = 40,270 M−1day−1 for Fe(III)-Cit and k = 1012 M−1day−1 and 2050 M−1day−1 at 20 °C and 30 °C; respectively. A possible reason for the higher TC degradation rate caused by Fe(III)-Cit can be the result of its lower thermodynamical stability compared with Fe(III)-EDTA, which we confirmed with our quantum chemistry calculations. Two quantum chemistry calculations showed that the iron complex with EDTA is more stable (the free energy of the ensemble is 15.8 kcal/mol lower) than the iron complex with Cit; hence, Fe release from Fe(III)-EDTA is less effective. [ABSTRACT FROM AUTHOR]

Antibiotics represent a novel type of environment pollutants which modify chlorophyll content in plants. Spectroscopic methods were employed to investigate the effect of tetracycline on chlorophyll degradation. Changes in absorbance and fluorescence demonstrated that tetracycline reaction with chlorophyll results in the formation of pheophytin, which was confirmed by new bands typical of pheophytin which appeared in the absorbance spectrum. The rate of pheophytin formation depended on ratio tetracycline to chlorophyll concentration in solution. In solutions with chlorophyll concentration of C = 1 × 10−5 M and tetracycline concentrations of C = 1 × 10−3 M and C = 1 × 10−2 M, pheophytin was formed after 28 h and 25 min, respectively. The obtained lifetime for pheophytin formed during chlorophyll reaction - with tetracycline hydrochloride was τ = 5.71 ± 0.02 ns and its value coincides, within the error limits, with the value obtained for pure pheophytin purchased from ChromaDex. The experiment demonstrated two mechanisms of chlorophyll degradation to pheophytin by tetracycline hydrochloride, i.e. 1) loss of Mg2+ ions from the chlorophyll molecule as a result of the presence of H+ ions in solution (i.e. as a result of medium acidification), and 2) removal of Mg2+ ions directly from chlorophyll by tetracycline which binds Mg2+ ions from the chlorophyll. We demonstrated that magnesium occurring in low concentrations attached to a tetracycline molecule in the BCD ring, and that the second ion of Mg2+ may attach to the A ring of tetracycline at higher Mg2+ concentrations. Two fluorescence bands appeared which indicated such magnesium attachments indeed occurred. • Tetracycline degrades chlorophyll to pheophytin and magnesium knocked out from chlorophyll is attached to tetracycline. • Several chlorophyll degradation processes have been demonstrated in the presence of tetracycline. • Magnesium in low concentrations attaches to a tetracycline in the BCD ring, whereas in higher concentrations to the A ring. [ABSTRACT FROM AUTHOR]

Abstract Tetracycline (TC) is an antibiotic produced on the largest scale in the world and used for the treatment of both humans and animals. Its removal from the circulation chain between the natural environment and animals is still a serious problem. Fe(III) ions can be used to break this chain. Fe(III) ions appear in water in spite of irradiation of Fe(III)-Cit complex and oxidation by oxygen present in water. Fe(III)-Cit was a reservoir of Fe(III) ions from which they were continuously released. Therefore, in this paper we studied an interaction between tetracycline (TC) and Fe(III) ions under fluorescent light at 20 °C and 30 °C in the water environment. This interaction leads to TC + Fe(III) coordinating complex formation. Changes caused by this process were monitored within 1860 min by measuring absorption and fluorescence spectra. The absorption spectra showed a charge-transfer stacking band(s) of oxidized and non-oxidized form of TC above 400 nm; in turn the fluorescence spectra revealed decay of initial bands and formation of the new ones. The initial, main fluorescence band at 16,660 cm−1 associated with the intramolecular proton transfer has gradually disappeared after Fe(III) ions binding to oxygen atoms in the BCD system rings of a TC molecule. Gaussian decomposition of all fluorescence spectra allowed extracting new bands, their evolution in time and calculating the rate of the first reaction step. Temperature rise of 10 °C caused more than a ten-fold increase in the first-order reaction rate. Graphical abstract Unlabelled Image Highlights • Fe(III) and tetracycline (TC) form a molecular complex in BCD ring system of TC. • The resulting complex of TC and Fe (III) does not fluoresce. • Charge-transfer complex of oxidized and unoxidized form of TC is formed. • New fluorescence bands are formed during 2 days of light irradiation. • To analyze the data, Gaussian decomposition of fluorescence spectra was applied. [ABSTRACT FROM AUTHOR]