Experimental and molecular docking investigation on metal-organic framework MIL-101(Cr) as a sorbent for vortex assisted dispersive micro-solid-phase extraction of trace 5-nitroimidazole residues in environmental water samples prior to UPLC-MS/MS analysis.

In the presented work, metal-organic framework (MOF) material MIL-101(Cr) (MIL, Matérial Institute Lavoisier) was used as a sorbent for vortex assisted dispersive micro-solid-phase extraction (VA-D-µ-SPE) of trace amount of metronidazole (MNZ), ronidazole (RNZ), secnidazole (SNZ), dimetridazole (DMZ), tinidazole (TNZ), and ornidazole (ONZ) in different environmental water samples. Ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UPLC-MS/MS) was used to quantify the target analytes. The extraction conditions, including type of sorbents, amount of MIL-101(Cr), solution pH, extraction method, extraction time, effect of salt, and elution conditions were investigated. Upon the optimal conditions, the developed method showed an excellent extraction performance with the average recovery ranging from 75.2 to 98.8 %. Good sensitivity levels were achieved with the detection limits of 0.03∼0.06 µg/L and the quantitation limits of 0.09∼0.20 µg/L. The linear ranges were varied from 0.1 to 20 for SNZ and ONZ and from 0.2 to 40 µg/L for MNZ, RNZ, DMZ, and TNZ (r 2 > 0.992), and repeatability of the method was satisfactory with the relative standard deviations (RSD) <8 %. Ultimately, the applicability of the method was successfully confirmed by the extraction and determination of 5-nitroimidazoles (5-NDZs) in 12 real water samples, showing the positive findings of MNZ and TNZ ranging from 0.3 to 1.0 µg/L. Furthermore, molecular docking was applied to explain the molecular interactions and free binding energies between MIL-101(Cr) and 5-NDZs, providing a deep insight into the adsorption mechanism. The proposed method exhibited the advantages of simplicity, rapidly, less solvent consumption, ease of operation, higher sensitivity, and lower matrix effect. Graphical abstract Schematic diagram of the extraction process and molecular docking investigation.

Photocatalysis-PMS oxidation system based on CQDs-doped carbon nitride nanosheets for degradation of residual drugs in water.

Graphite-like carbon nitride (g-C3N4) is favored for its excellent physicochemical properties. However, the high complexation rate of photogenerated carriers greatly limits its practical applications. Based on this, a novel CQDs-doped carbon nitride nanosheets composite (CNS/CQDs) was prepared and applied to the visible light-induced activation of peroxymonosulfate (PMS) for meloxicam (Mel) and tetracycline (TC) degradation. The photocatalytic degradation of Mel and TC were remarkably promoted in the CNS/CQDs+PMS+vis system. Mel photodegradation of 99.90% was achieved over 30 min with 20 mg CNS/CQDs and 20 mg PMS at pH11. And TC photodegradation of 95.97% was achieved over 45 min with 20 mg CNS/CQDs and 20 mg PMS at nature pH6.5. The TOC mineralization rates of Mel and TC were 75.49% and 52.00%, respectively. The transient photocurrent response and electrochemical impedance measurements (EIS) results indicated that the doping of CQDs could improve the charge transfer efficiency of pure g-C3N4, and CNS/CQDs had a low charge transfer resistance. Capture experiments and EPR tests explored the effective actives in the CNS/CQDs+PMS+vis system. Possible degradation pathways of Mel were also analyzed. This study provides valid residual drugs degradation under the dual conditions of visible light catalytic oxidation and persulfate oxidation, which will be a novel perspective for advanced oxidation technology to effectively remove organic pollutants from water.

Microwave-assisted synthesis of defective Ca1-xAgxTi1-yCoyO3 with high photoelectrocatalytic activity for organic pollutant removal from water.

CaTiO3 is considered to be one of the most promising catalysts for the degradation of organic pollutants, but its application is limited by the wide band gap and low catalytic activity. Element doping is an effective strategy to solve these problems. Herein, a novel CaTiO3 co-doped with Ag and Co (Ca1-xAgxTi1-yCoyO3) was synthesized by combining co-precipitation and the microwave hydrothermal method for the first time. The crystal structure, microstructure and light absorption of the material were systematically investigated. The results showed that Ca1-xAgxTi1-yCoyO3 had higher light absorption than pure CaTiO3, and the band gap was reduced to 2.78 eV. First-principles calculations indicated that Ag-Ca and Co-Ti tended to form donor-acceptor defect pairs in the doping process. These defect states not only enhanced the adsorption properties, but also could be used as carrier traps to optimize the dielectric properties of CaTiO3. In the photoelectrocatalytic system, with 0.01 g of catalyst, 98% of methylene blue in 100 mL solution (10 mg L-1) was degraded in 150 min. In addition, Ca1-xAgxTi1-yCoyO3 showed strong stability and excellent recyclability. The double ion co-doping technology will provide an effective strategy for improving the catalytic activity of traditional wide-band gap semiconductors.