Enhanced hydrolytic stability and photocatalytic performance of a uranium‐based organic framework by hybrid carbon nanotubes

Enhanced hydrolytic stability and photocatalytic performance of a uranium-based organic framework by hybrid carbon nanotubes

Incorporation of multiwalled carbon nanotubes (CNTs) into a metal–organic framework (TCPP-U1) was able to maintain the crystal structure and morphology of the original TCPP-U1 while enhancing the hydrolytic stability. In addition, CNTs@TCPP-U1 had a photocatalytic effect on the degradation of tetracycline hydrochloride in aqueous solution.


Owing to their highly predictable porous structures, facile synthesis, and the presence of functional open metal sites, metal–organic frameworks (MOFs) are extensively employed in various fields, including energy storage, catalysis, adsorption, and separation. Nevertheless, the limited hydrolytic stability exhibited by numerous MOFs poses a significant challenge to their practical application. In the present study, we present the synthesis and characterization of a uranyl organic framework (TCPP-U1) with a highly porous structure, which is constructed by assembling cobalt, uranyl, and the porphyrin ligand 5,10,15,20-tetra(4-carboxyphenyl)porphyrin (TCPP). However, TCPP-U1 demonstrates poor hydrolytic stability when exposed to water (the structure can be destroyed even after 2 min of exposure to water), greatly impeding its potential applications that would benefit from its high surface area. To address this limitation, we developed a hybrid composite by incorporating acid-treated multi-walled carbon nanotubes (CNTs) into the TCPP-U1 framework via a solvothermal method designated as CNTs@TCPP-U1. Remarkably, the obtained CNTs@TCPP-U1 composite possesses an identical crystal structure and morphology to the original TCPP-U1 yet exhibits significant enhancements in hydrolytic stability (the structure remains stable even after 3 days of immersion in water). Furthermore, CNTs@TCPP-U1 demonstrates a significant photocatalytic effect on the degradation of tetracycline hydrochloride in aqueous solutions. The reaction rate constant (k) for the pseudo-first-order kinetic model is 0.0059 min−1. Our findings present a novel perspective for enhancing the stability and expanding the performance of MOFs materials.

Analyzing the structure of the metal complexes of biologically active azo dye ligand

Analyzing the structure of the metal complexes of biologically active azo dye ligand

A newly synthesized azo dye ligand and its Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), Zn(II), and Cd(II) complexes require a range of techniques, including elemental analyses and spectroscopic studies. Nitrogen of the azo group and one oxygen of the carbonyl group coordinate the azo ligand to the metal ions, acting as a neutral bidentate ligand, according to the inferred IR spectra. The molar conductance data indicated that all the complexes were electrolytes. Octahedral geometry was suggested for the complexes being studied. The proposed structural equations for the complexes were, in general, expressed as [M(L)Cl2(H2O)2]·Cr(III), x = 1, n = 0; Cd(II), x = n = 0; Zn(II), x = 0, n = 1, and [M(L)(Cl)(H2O)3] Clx·nH2O Mn(II), Co(II), Ni(II), and Cu(II), x = 1; Clx [M = Fe(III), x = 2].


A novel azo dye ligand was created by diazotizing 4-aminoantipyrine and then coupling it with 2-aminophenol as part of a methodical investigation of physiologically active compounds, 4-aminoantipyrine. The novel complexes containing Cr(III), Fe(III), Mn(II), Co(II), Ni(II), Zn(II), Cu(II), and Cd(II) were created from the target ligand (L). The structures of the ligand and metal complexes were verified by elemental analyses, thermogravimetric analysis–difference thermogravimetry (TGA-DTG), conductivity measurements, infrared (IR), UV–Vis, 1H-nuclear magnetic resonance (NMR), X-ray diffraction (XRD), and mass spectrometry. Using the Gaussian 09 tool, the density functional theory (DFT)/B3LYP method was utilized to compute the energy gaps and other important theoretical features. Also, the newly synthesized azo dye ligand, in comparison with metal complexes, was screened for its antimicrobial activity. The crystal structures of Staphylococcus aureus and Bacillus subtilis as gram-positive bacteria, Salmonella sp. and Escherichia coli as gram-negative bacteria, and fungal (Aspergillus fumigatus and Candida albicans) species were compared with the produced azo dye and its metal complexes via molecular docking. Most of the complexes exhibited greater antimicrobial activities against these organisms than did the original azo dye ligand.

Gold(I) N‐heterocyclic carbene (NHC) complexes containing 6‐mercaptopurine derivatives and their in vitro anticancer and anti‐inflammatory effects

Gold(I) N-heterocyclic carbene (NHC) complexes containing 6-mercaptopurine derivatives and their in vitro anticancer and anti-inflammatory effects

The gold(I)N-heterocyclic-carbene complexes containing 6-mercaptopurine derivatives revealed promising in vitro cytotoxicity against selected human cancer cells. The effects of the complexes on the production of pro-inflammatory cytokine TNF-α and the activation of NF-κB or PPARγ are negligible. Cellular effects of complexes were evaluated on A2780 cells, including cell cycle modification, induction of cell death, mitochondrial membrane potential, and ROS. The proteomic analysis revealed the effects of the complexes on the proteome of A2780 cells.


A series of eight N-heterocyclic carbenes (NHC) gold(I) complexes, involving 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (iPr) ligand in combination with 6-mercaptopurine derivatives (HL1–8), has been prepared and thoroughly characterized, including elemental analysis, mass spectrometry, infrared and multinuclear NMR spectroscopy, and single crystal X-ray analysis. The complexes, showing general composition of [Au (iPr)(Ln)] 18, were evaluated for their in vitro cytotoxicity against four human cancer cell lines including A2780 (ovarian) and A2780R (ovarian Cisplatin resistant), PC3 (prostate) and MCF-7 (breast), and normal human MRC-5 cells (lung fibroblasts). The complexes revealed significant cytotoxicity, with the best IC50 values ≈ 3.4–6.4 μM against A2780 and reasonable selectivity. Cellular effects of the selected complexes on the A2780 cells were evaluated using various flow cytometry assays. Complexes 1, 3, and 4 showed a strong pro-apoptotic effect and a strong effect on the loss of mitochondrial membrane potential. These findings indicate that their major mechanism of action is based on the collapse of the mitochondrial metabolism and activation of the intrinsic signaling pathway of apoptosis, consequently resulting in cell death. The complexes 18 revealed only negligible effect on the production of inflammatory-related cytokine (TNF-α), as well as the activation of nuclear factor kappa-light-chain-enhancer of activated B cells (NF-κB) or peroxisome proliferator-activated receptor gamma (PPARγ). Moreover, the shotgun proteomic analysis was performed, and the obtained results suggest that the mechanism of action of complexes 1, 3, and 4 differs somewhat from that of Auranofin.

Bulk Heterojunction or Layer‐by‐Layer Structure PM6:L8‐BO Based Polymer Solar Cells Exhibiting an Efficiency of 17.84 % or 18.43 %

Bulk Heterojunction or Layer-by-Layer Structure PM6:L8-BO Based Polymer Solar Cells Exhibiting an Efficiency of 17.84 % or 18.43 %

The PCE of 18.43 % and 17.84 % are achieved in LbL and BHJ PSCs with polymer donor PM6 and small acceptor L8-BO. Over 3 % PCE improvement can be obtained in LbL PSC, benefiting from the enhanced exciton dissociation, charge collection efficiency and charge transport in LbL active layer.


Abstract

Two kinds of polymer solar cells (PSCs) were fabricated with polymer donor PM6 and small molecule non-fullerene acceptor L8-BO as accepted based on bulk heterojunction (BHJ) or layer-by-layer (LbL) structure. The power conversion efficiency (PCE) of 18.43 % and 17.84 % can be achieved from the PSCs based on BHJ and LbL structure, respectively. Two kinds of PSCs exhibit the same open circuit voltage (VOC ) of 0.88 V, which can be well explained from the same donor and acceptor materials and the same electrodes. The LbL based PSCs exhibit a relatively large short circuit current density (JSC ) of 26.97 mA cm−2 and fill factor (FF) of 77.64 % in comparison with JSC of 26.64 mA cm−2 and FF of 76.07 % for BHJ based PSCs. The relatively high PCE of LbL based PSCs should be attributed to the sufficient exciton dissociation and charge collection efficiency, as well as the more balanced charge transport, which can be confirmed from the photogenerated current density dependence on the effective bias. This work demonstrates that layer-by-layer structure may have great potential in preparing highly efficient PSCs.

Construction of a Zero‐gap Flow‐Through Microfluidic Reactor with Porous RuO2‐IrO2@Pt Anode for Electrocatalytic Oxidation of Antibiotics in Water

Construction of a Zero-gap Flow-Through Microfluidic Reactor with Porous RuO2-IrO2@Pt Anode for Electrocatalytic Oxidation of Antibiotics in Water

The FT-MF reactor with porous Ti/RuO2-IrO2@Pt as anode exhibits high degradation efficiency and low energy consumption in antibiotic degradation.


Abstract

In this study, a zero-gap flow-through microfluidic reactor was constructed for the degradation of tetracycline and norfloxacin in water using a porous Ti/RuO2-IrO2@Pt electrode as the anode and porous titanium plate as the cathode. The operation parameters included electrolyte type, electrolyte concentration, current density, initial concentration of pollutants and pH, were investigated. The degradation efficiency and energy consumption were calculated and compared with traditional electrolyzer. In the zero-gap flow-through microfluidic reactor, 100 % of both tetracycline and norfloxacin can be decomposed in 15 min, and high mineralization rate were achieved under the optimized reaction condition. And the reaction was consistent with pseudo-first-order kinetics with k value of 0.492 cm−1 and 1.010 cm−1, for tetracycline and norfloxacin, respectively. In addition, the energy consumption was 28.33 kWh ⋅ kg−1 TC and 8.36 kWh ⋅ kg−1 NOR, for tetracycline and norfloxacin, respectively, which was much lower than that of traditional electrolyzer. The LC–MS results showed that tetracycline underwent a series of demethylation, dehydration and deamination reactions, and the norfloxacin went through ring opening reaction, decarboxylation and hydroxylation reaction, and finally both produced CO2 and H2O.

Wastewater‐based Epidemiology to Investigate Spatio‐Temporal Trends in Alcohol Consumption in Aotearoa, New Zealand

Wastewater-based Epidemiology to Investigate Spatio-Temporal Trends in Alcohol Consumption in Aotearoa, New Zealand

Alcohol consumption in Aotearoa, New Zealand (NZ) was analysed through the use of Wastewater-based Epidemiology (WBE), covering ~40 % of the population over a six-month period in 2021. Factors including geographical (NZ locations, settlement size), temporal (day of the week, public holidays) and COVID-19 restrictions were found to significantly affect alcohol consumption in Aotearoa, NZ.


Abstract

Alcohol is an influential drug that has extensive societal impact. In Aotearoa New Zealand, there are a number of worrying trends related to alcohol consumption including rates of alcohol-related harm and violence and heavy episodic drinking. To understand and address these issues, alcohol consumption rates and related trends need to be understood. A wastewater-based epidemiology study was carried out over the course of six months (April–September 2021), sampling one week per month from ten catchment areas covering ~40 % of the national population. The average alcohol consumption was found to be 12.2 mL/person/day. Temporal and geographical trends in alcohol consumption were found; there was higher alcohol consumption on the weekends compared to weekdays, alcohol consumption was inversely related to settlement size, there was increased alcohol consumption due to public holidays and alcohol consumption was not seen to increase during COVID restrictions, however there was a notable change in the weekly trend during lockdowns. This application of alcohol WBE to Aotearoa New Zealand represents a comprehensive national study to understand alcohol consumption and its influences. The knowledge obtained will allow appropriate services and public policies to be reviewed to best serve communities.

Controllably Modulating Oxygen Vacancies on Nonstoichiometric Nd−Ce−O Binary Oxides for Low‐temperature Oxidative Coupling of Methane

Controllably Modulating Oxygen Vacancies on Nonstoichiometric Nd−Ce−O Binary Oxides for Low-temperature Oxidative Coupling of Methane

As the amount of Nd3+ increases, the oxygen vacancies in Nd−Ce−O composite oxides gradually increase, leading to an amount increasing in the C2-selective O2 species generated by the oxygen vacancies, and the number of surface moderate basic sites, hence improving the OCM reaction performance.


Abstract

Herein, we synthesised a series of nonstoichiometric Nd−Ce−O composite oxides with a fluorite or rare-earth C-type phase structure using the glycine combustion method for the oxidative coupling of methane (OCM) reaction. As the amount of Nd3+ increases, the oxygen vacancies in this series of composite oxides gradually increase, leading to an amount increasing in the C2-selective oxygen species O2 generated by the oxygen vacancies. In addition, with the increase in Nd3+, the number of moderate basic sites on the catalyst surface also improves, another significant factor affecting the OCM reaction performance of the composite oxides. Nd0.9Ce0.1O1.55 possesses optimal low-temperature OCM reaction performance, achieving 8.0 % C2 yield at 450 °C and 14.1 % C2 yield at 700 °C. This can be attributed to the nonstoichiometric rare-earth C-type crystalline phase structure of Nd0.9Ce0.1O1.55, which exhibits the highest abundance of oxygen vacancies, selective oxygen species O2 , and moderate basic sites.

Studying the adsorption of emerging organic contaminants in zeolites with dispersion‐corrected density functional theory calculations: From numbers to recommendations

Studying the adsorption of emerging organic contaminants in zeolites with dispersion-corrected density functional theory calculations: From numbers to recommendations

The performance of 13 dispersion-corrected density functional theory methods is compared systematically for adsorption energy calculations of emerging organic contaminants in all-silica zeolites . While qualitative trends are similar, large differences in absolute values are observed. Among the tested approaches, the rev-vdW-DF2 functional reproduces reference values from high-level wave function calculations most accurately.


Abstract

Adsorption energies obtained from dispersion-corrected density functional theory (DFT) calculations show a considerable dependence on the choice of exchange-correlation functional and dispersion correction. A number of investigations have employed different approaches to compute adsorption energies of small molecules in zeolites, using reference values from high-level calculations and/or experiments. Such comparative studies are lacking for larger functional organic molecules such as pharmaceuticals or personal care products, despite their potential relevance for applications, e. g., in contaminant removal or drug delivery. The present study aims to fill this gap by comparing adsorption energies and, for selected cases, equilibrium structures of emerging organic contaminants adsorbed in MOR- and FAU-type all-silica zeolites. A total of 13 dispersion-corrected DFT approaches are compared, including methods using a pairwise dispersion correction as well as non-local van der Waals density functionals. While absolute values of adsorption energies vary widely, qualitative trends across the set of zeolite-guest combinations are not strongly dependent on the choice of functional. For selected cluster models, DFT adsorption energies are compared to reference values from coupled cluster (DLPNO-CCSD(T)) calculations. Although all DFT approaches deliver systematically more negative adsorption energies than the coupled cluster reference, this tendency is least pronounced for the rev-vdW-DF2 functional.