It is known that some metals (Cu, Zn, Cd, Au) markedly increase the toxic effect of thiocarbamates. It was shown in the present study that hydroxycobalamin (a form of vitamin B12, HOCbl), which incorporates cobalt, significantly enhances the cytotoxicity of diethyldithiocarbamate (DDC), decreasing its IC50 value in tumor cells three to five times. The addition of HOCbl to aqueous DDC solutions accelerated the reduction of oxygen. No hydrogen peroxide accumulation was observed in DDC + HOCbl solutions; however, catalase slowed down the oxygen reduction rate. Catalase as well as the antioxidants N-acetylcysteine (NAC) and glutathione (GSH) partially inhibited the cytotoxic effect of DDC + HOCbl, whereas ascorbate, pyruvate, and tiron, a scavenger of superoxide anion, had no cytoprotective effect. The administration of HOCbl into DDC solutions (> 1 mM) resulted in the formation of a crystalline precipitate, which was inhibited in the presence of GSH. The data of UV and NMR spectroscopy and HPLC and Mass Spectrometry (LC/MS) indicated that the main products of the reaction of DDC with HOCbl are disulfiram (DSF) and its oxidized forms, sulfones and sulfoxides. The increase in the cytotoxicity of DDC combined with HOCbl occurred both in the presence of Cu2+ in culture medium and in nominally Cu-free solutions, as well as in growth medium containing the copper chelator bathocuproine disulfonate (BCS). The results indicate that HOCbl accelerates the oxidation of DDC with the formation of DSF and its oxidized forms. Presumably, the main cause of the synergistic increase in the toxic effect of DDC + HOCbl is the formation of sulfones and sulfoxides of DSF.
The growth in the production of titanium metal and its compounds leads to an increase in the amount of toxic waste. As a result, at the legislative level, emissions of such wastes are limited, which leads to a drop in the production of titanium-containing products and a shortage of titanium in the international market. This paper presents the results of the process of fluorination of rutile concentrate from the Tarsky deposit (Russia, Omsk region) with elemental fluorine using a laboratory setup of a special design. For fluorination, samples of rutile concentrate weighing 0.1–1.0 g were used. The particle size distribution of particles varied from 2 × 10−6 to 2 × 10−5 m. To determine the possibility of carrying out the process, the calculation of the change in the logarithm of the equilibrium constant versus temperature was performed. The influence of the following operating parameters on the fluorination process has been studied: various concentrations of F2 in a fluorinating mixture of fluorine with nitrogen; process time from 0 to 9 min; different ratios of the initial solid phase to fluorine (10 and 50% excess of fluorine and 10 and 50% of its deficiency); fluorination temperature in the range of 300–1800 K. A kinetic equation is selected that most accurately describes the fluorination process. The values of the activation energy and the preexponential factor in the kinetic equation are determined. The obtained results show that with an increase in the fluorine content in the fluorinating gas mixture and the temperature of the process, the fluorination rate increases. Optimal conditions for fluorination: temperature—680 K; time—5 min excess fluorine in the fluorinating mixture—20–25%. The obtained results allow to propose and consider the conditions of process execution on industrial equipment.
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