Degradation of Minocycline by the Adsorption–Catalysis Multifunctional PVDF–PVP–TiO2 Membrane: Degradation Kinetics, Photocatalytic Efficiency, and Toxicity of Products

The photocatalytic degradation of minocycline was studied by using polyvinylidene fluoride–polyvinylpyrrolidone–TiO2 (PVDF–PVP–TiO2) fiber mats prepared by an electrospinning technology. The influences of the TiO2 dosage, minocycline concentrations, inorganic anions, pH values, and dissolved organic matter (DOM) concentrations on the degradation kinetics were investigated. A mass of 97% minocycline was degraded in 45 min at 5% TiO2 dosage. The corresponding decomposition rate constant was 0.069 min−1. The inorganic anions affected the minocycline decomposition in the order of HCO3− > Cl− > SO42− > NO3−, which was confirmed by the results of electron spin resonance (ESR) spectra. The lowest electrical energy per order (EEO) was 6.5 Wh/L. Over five cycles, there was no change in the photocatalytic performance of the degrading minocycline. Those investigations suggested that effective degradation of minocycline could be reached in the PVDF–PVP–TiO2 fiber mats with a low energy consumption, good separation and, good recovery. Three photocatalytic decomposition pathways of minocycline were proposed: (i) hydroxyl substitution of the acylamino group; (ii) hydroxyl substitution of the amide group, and (iii) a cleavage of the methyl groups and further oxidation of the amino group by OH. Potential risks caused by TP159 and TP99 should not be ignored, while the TP90 are nontoxic. Tests indicated that the toxicity of the photocatalytic process may be persistent if minocycline and its products were not mineralized completely.

ELECTRICAL CONDUCTIVITY OF SOLUTIONS OF IONIC LIQUIDS BASED ON 1-ALKYL-2-METHYLPYRIDINIUM SALTS WITH INORGANIC ANIONS IN ACETONITRILE

Авторами работы получены ионные жидкости с катионом 1-алкил-2-метилпиридиния и неорганическими анионами. Проведены исследования электропроводности их растворов в ацетонитриле. Методом Ли-Уитона рассчитаны константы ионной ассоциации K, предельная молярная электрическая проводимости (λ) и энергия Гиббса ассоциации (ΔG) в растворах. The authors of the work obtained ionic liquids with 1-alkyl-2-methylpiridinium cation and inorganic anions. Studies of the electrical conductivity of their solutions in acetonitrile have been carried out. The Li-Wheaton method was used to calculate the ion association constants K, the limiting molar electrical conductivity (λ), and the Gibbs association energy (ΔG) in solutions.

Understanding distortions of inorganic substructures in chloridobismuthates(III)

The molar ratio variations of organic and inorganic reactants of chloridobismuthates(III) with N,N-dimethylethane-1,2-diammonium, [(CH3)2NH(CH2)2NH3]2+, and N,N,N′,N′-tetramethylguanidinium, [NH2C{N(CH3)2}2]+, cations lead to the formation of four different products, namely, tris(N,N-dimethylethane-1,2-diammonium) bis[hexachloridobismuthate(III)], [(CH3)2NH(CH2)2NH3]3[BiCl6]2 (1), catena-poly[N,N-dimethylethane-1,2-diammonium [[tetrachloridobismuthate(III)]-μ-chlorido]], {[(CH3)2NH(CH2)2NH3][BiCl5]} n (2), tris(N,N,N′,N′-tetramethylguanidinium) tri-μ-chlorido-bis[trichloridobismuthate(III)], [NH2C{N(CH3)2}2]3[Bi2Cl9] (3), and catena-poly[N,N,N′,N′-tetramethylguanidinium [[dichloridobismuthate(III)]-di-μ-chlorido]], {[NH2C{N(CH3)2}2][BiCl4]} n (4). The hybrid crystals 1–4, containing relatively large but different organic cations, are composed of four distinct anionic substructures. They are built up from isolated [BiCl6]3− octahedra in 1, from face-sharing bioctahedral [Bi2Cl9]3− units in 3, from polymeric corner-sharing {[BiCl5]2−} n chains in 2 and from edge-sharing {[BiCl4]−} n chains in 4. The distortions shown by the single [BiCl6]3− polyhedra in 1–4 are associated with intrinsic interactions within the anionic substructures and the organic...inorganic substructures interactions, namely, N/C—H...Cl hydrogen bonds. The first factor is the stronger, which is evident in comparison of the experimentally determined geometrical and calculated distortion parameters for the isolated octahedron in 1 to the more complex inorganic substructures in 2–4. The formation of N—H...Cl hydrogen bonds, in terms of their number and strength, is favoured for 1 and 3 containing relatively easily accessed hydrogen-bond acceptors of isolated [BiCl6]3− and [Bi2Cl9]3− units. The studies of the deviations from regularity of the [BiCl6]3− octahedra within inorganic substructures were supported by a survey of the Cambridge Structural Database, which confirmed the role played by different factors in the variations in geometry of the inorganic anions.