Application of Functionalized Zn-Based Metal-Organic Frameworks (Zn-MOFs) with CuO in Heterocycle Synthesis via Azide-Alkyne Cycloaddition.

The main goal of this article is to discuss the expansion of click chemistry. A new catalyst composed of CuO nanoparticles embedded in Zn-MOF with the ligand 2,4,6-tris(4-carboxyphenoxy)-1,3,5-triazine (H3L) is presented. The incorporation of CuO nanoparticles into the Zn-MOF structure led to desirable morphology and catalytic properties. The designed catalyst was evaluated for its catalytic role in the multicomponent reaction and copper-catalyzed azide-alkyne cycloaddition (CuAAC) for preparation of triazole rings with 80-91% yield. The catalyst demonstrated an appealing architecture and exhibited robustness, high efficiency, and environmental friendliness. Characterization of the catalyst was performed using various techniques, including Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), transmission electron microscopes (TEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), energy-dispersive X-ray spectroscopy (EDX), elemental mapping, and X-ray diffraction (XRD). The results suggest that this novel catalyst has the potential to be a valuable tool in the development of new synthetic approaches for a wide range of applications.

Application of Metal-Organic Frameworks with Sulfonic Acid Tags in the Synthesis of Pyrazolo[3,4-b]pyridines via a Cooperative Vinylogous Anomeric-Based Oxidation.

Herein, we report the design and synthesis of Co-MOF-71/imidazole/SO3H as a novel porous catalyst with sulfonic acid tags. The structure and morphology of the catalyst were investigated using various techniques such as Fourier transform-infrared spectroscopy (FT-IR), X-ray diffraction, scanning electron microscopy (SEM), SEM elemental mapping, energy-dispersive X-ray spectroscopy, Barret-Joyner-Halenda, and N2 adsorption-desorption isotherms. Co-MOF-71/imidazole/SO3H was studied in the preparation of novel pyrazolo[3,4-b]pyridines under mild and green conditions via a cooperative vinylogous anomeric-based oxidation. A wide range of mono and bis pyrazolo[3,4-b]pyridines were synthesized with good to excellent yields (65-82%). A hot filtration test for the heterogeneous nature of the catalyst indicated the high stability of the prepared catalyst. The recyclability of Co-MOF-71/imidazole/SO3H is another advantage of the present methodology. The structures of the final products were confirmed using FT-IR, 1H-NMR, and 13C-NMR spectroscopic techniques.

One-pot synthesis of graphene hydrogel/M (M: Cu, Co, Ni) nanocomposites as cathodes for electrochemical removal of rifampicin from polluted water.

Nowadays, the removal of pharmaceutical contaminants from water resources and wastewater is of great importance due to environmental and health issues. Over the decades, various methods have been reported to remove pollutants from wastewater. Among the developed methods, advanced oxidation processes (AOPs) have received significant attention from researchers. In this study, we report the one-pot synthesis of graphene hydrogel-metal (GH-M, M: Co, Ni, Cu) nanocomposites via the combination of polyol and hydrothermal methods. The structure of the resulting nanocomposites was examined by transmission electron microscopy (TEM), inductively coupled plasma-mass spectroscopy (ICP-MS), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), and Raman spectroscopy methods. Afterward, as-prepared GH-Cu, GH-Co, and GH-Ni nanocomposites were used to prepare cathodes for the electro-Fenton (EF) process to remove rifampicin (RIF) from polluted water. The effect of operational parameters, including current density (mA/cm2), initial pH, initial RIF concentration (mg/L), and process time (min) was investigated via response surface methodology (RSM). The optimal values for current density, pH, initial RIF concentration, and process time using GH-Ni as cathode were 30 mA/cm2, 5, 30 mg/L, and 90 min, respectively. The results at optimal values showed that the maximum RIF removal efficiency for GH-Cu, GH-Co, and GH-Ni cathodes was 90.47, 92.60, and 93.69%, respectively. Brunauer Emmett Teller (BET), atomic force microscopy (AFM), energy-dispersive X-ray (EDX), and cyclic voltammetry (CV) analyses were performed to investigate the performance of the cathodes for the RIF removal. Finally, total organic carbon (TOC), gas chromatography-mass spectrometry (GC-MS), and atomic absorption spectroscopy (AAS) analyses were performed for further investigation of the RIF removal from polluted water. The results claimed that one-pot synthesized GH-M cathodes can effectively remove RIF from polluted water through EF process.

Electrochemical removal of fluoxetine via three mixed metal oxide anodes and carbonaceous cathodes from contaminated water.

In this work, the fluoxetine (FLX) removal has been studied via the anodic oxidation (AO) process. Anode electrodes were Ti/RuO2, Ti/RuO2-IrO2, and Ti/RuO2-IrO2-SnO2, and cathode electrodes were graphite and carbon nanotubes (CNTs). The performances of electrodes were compared in terms of FLX removal efficiency. As a result, Ti/RuO2-IrO2-SnO2 and CNTs were the optimal anode and cathode, respectively. The properties of the optimal electrodes were investigated using scanning electron microscopy, atomic force microscopy and X-ray diffraction spectroscopy. Cyclic voltammetry analysis was performed to study the electrochemical behavior of electrodes. The effect of current intensity (mA), initial pH, initial FLX concentration (mg/L) and process time (min) on the FLX removal efficiency was investigated and the response surface methodology was applied for the optimization of the AO process. The results showed that at current intensity, pH, initial FLX concentration and process time of 500 mA, 6, 25 mg/L and 160 min, maximum FLX removal efficiency was observed, which was 96.25%. Gas Chromatography-Mass Spectrometry (GC-MS), and total organic carbon (TOC) analysis was determined to evaluate the intermediates, and mineralization efficiency. The TOC removal efficiency was reached 81.51% after 6 h under optimal experimental conditions, indicating the successful removal of the FLX.

Removal of Phenazopyridine from wastewater by merging biological and electrochemical methods via Azolla filiculoides and electro-Fenton process.

In the present study, the potential of Azolla filiculoides (A. filiculoides) was first investigated for degradation of Phenazopyridine (PhP), an analgesic drug. The effects of main variables such as initial pharmaceutical concentration, amount of plant, and pH were studied on the efficiency of the biological process. It was observed that A. filiculoides was able to remove pharmaceuticals from contaminated water up to 85.90% during 48 h. Then, the electro-Fenton (EF) method was applied for further removal of PhP yielding a removal rate of about 98.72% under optimum conditions during 2 h. The effects of variables including the current, amount of catalyst, and pH were also studied in this phase. Also, the probability of adsorption was investigated during this step. Scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis were performed for the used magnetite nanoparticles, total organic carbon (TOC) were performed to investigate PhP removal efficiency during the reaction time and Gas chromatography-mass spectrometry (GC-MS) were performed to analyze degradation byproducts of PhP. Based on the results, it was found that a combination of these bioremediation and electrochemical removal steps were capable of PhP removal from contaminated water. Therefore, this approach may be effective for phytoremediation of pharmaceutical-contaminated aquatic ecosystems.

Synthesis of Nitroolefins and Nitroarenes under Mild Conditions.

1,3-Disulfonic acid imidazolium nitrate {[Dsim]NO3} was prepared and characterized as a new ionic liquid and nitrating agent for the ipso-nitration of various arylboronic acids and nitro-Hunsdiecker reaction of different α,ß-unsaturated acids and benzoic acid derivatives, by in situ generation of NO2 to give various nitroarenes and nitroolefins without using any cocatalysts and solvents under mild conditions.

Synthesis of picolinates via a cooperative vinylogous anomeric-based oxidation using UiO-66(Zr)-N(CH2PO3H2)2 as a catalyst.

The anomeric effect highlights the significant influence of the functional group and reaction conditions on oxidation-reduction. This article successfully investigates the anomeric effect in the synthesis of picolinate and picolinic acid derivatives through a multi-component reaction involving 2-oxopropanoic acid or ethyl 2-oxopropanoate, ammonium acetate, malononitrile, and various aldehydes. To facilitate this process, we employed UiO-66(Zr)-N(CH2PO3H2)2 as a novel nanoporous heterogeneous catalyst. The inclusion of phosphorous acid tags on the UiO-66(Zr)-N(CH2PO3H2)2 offers the potential for synthesizing picolinates at ambient temperature.

Application of Nanomagnetic Metal-Organic Frameworks in the Green Synthesis of Nicotinonitriles via Cooperative Vinylogous Anomeric-Based Oxidation.

In the current study, we synthesized a new nanomagnetic metal-organic framework Fe3O4@MIL-53(Al)-N(CH2PO3)2 and characterized it using various techniques. This nanomagnetic metal-organic framework was used for the synthesis of a wide range of nicotinonitrile derivatives as suitable drug candidates by a four-component reaction of 3-oxo-3-phenylpropanenitrile or 3-(4-chlorophenyl)-3-oxopropanenitrile, ammonium acetate (NH4OAc), acetophenone derivatives, and various aldehydes including those bearing electron-donating, electron-withdrawing, and halogen groups, which afforded desired products (27 samples) via a cooperative vinylogous anomeric-based oxidation (CVABO) mechanism under solvent-free conditions in excellent yields (68-90%) and short reaction times (40-60 min). Increasing the surface-to-volume ratio, easy separation of the catalyst using an external magnet, and high chemical and temperature stability are the advantages of the described nanomagnetic metal-organic frameworks.

Application of Zr-MOFs based copper complex in synthesis of pyrazolo[3, 4-b]pyridine-5-carbonitriles via anomeric-based oxidation.

In this research article, Zr-MOFs based copper complex as a novel heterogeneous and porous catalyst was designed and prepared. The structure of catalyst has verified by various techniques such as FT-IR, XRD, SEM, N2 adsorption-desorption isotherms (BET), EDS, SEM-elemental mapping, TG and DTG analysis. UiO-66-NH2/TCT/2-amino-Py@Cu(OAc)2 was used as an efficient catalyst in the synthesis of pyrazolo[3,4-b]pyridine-5-carbonitrile derivatives. The aromatization of titled molecules is performed via a cooperative vinylogous anomeric-based oxidation both under air and inert atmospheres. The unique properties of the presented method are short reaction time, high yield, reusability of catalyst, synthesis of desired product under mild and green condition.

Catalytic Application of Functionalized Bimetallic-Organic Frameworks with Phosphorous Acid Tags in the Synthesis of Pyrazolo[4,3-e]pyridines.

Combining two different metals for the synthesis of a metal-organic framework (MOF) is a smart strategy for the architecture of new porous materials. Herein, a bimetal-organic framework (bimetal-MOFs) based on Fe and Co metals was synthesized. Then, phosphorous acid tags were decorated on bimetal-MOFs via a postmodification method as a new porous acidic functionalized catalyst. This catalyst was used for the synthesis of pyrazolo[4,3-e]pyridine derivatives as suitable drug candidates. The present study provides new insights into the architecture of novel porous heterogeneous catalysts based on a bimetal-organic framework (bimetal-MOFs). The type of final structures of catalyst and pyrazolo[4,3-e]pyridine derivatives were determined using different techniques such as fourier transform infrared (FT-IR), X-ray diffraction (XRD), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX), SEM-elemental mapping, N2 adsorption-desorption isotherm, Barrett-Joyner-Halenda (BJH), thermogravimetry/differential thermal analysis (TG/DTA), 1H NMR, and 13C NMR.

Carbonaceous CoCr LDH nanocomposite as a light-responsive sonocatalyst for treatment of a plasticizer-containing water.

The carbonous-based nanocomposites of CoCr layered double hydroxide (LDH) with graphene oxide (GO) and reduced graphene oxide (rGO) were prepared. The successful synthesis of the CoCr LDH in hydrotalcite crystalline structure was deduced from the pattern obtained from X-ray diffraction, and the chemical composition of its surface was checked by X-ray photoelectron spectroscopy. The prosperous decorating of LDH on the sheets of rGO and GO was authenticated by the energy dispersive X-ray spectroscopy analysis and micrographs of scanning electron and transmission electron microscopy. The photo-assisted sonocatalytic activity of the prepared nanocomposites was appraised for the decomposition of dimethyl phthalate (DMP) as a plasticizer. The highest decomposition efficiency of 100% was obtained in the existence of CoCr LDH/rGO nanocomposite (0.5 g/L) during 20 min of reaction time via photo-assisted sonocatalysis. The rGO improved the catalytic activity of the CoCr LDH by increasing the specific surface area from 1.2 m2/g to 4.5 m2/g and reducing the band gap from 1.7 eV to 1.3 eV. Moreover, the results of the colony-forming unit method endorsed antibacterial property improvement of the CoCr LDH via hybridizing with rGO. The results of this research provide an optimistic perspective for applying carbonous-based nanocomposites of CoCr LDH as a novel catalyst with antibacterial properties in photo-assisted sonocatalytic processes.

Application of novel metal-organic framework [Zr-UiO-66-PDC-SO3H]FeCl4 in the synthesis of dihydrobenzo[g]pyrimido[4,5-b]quinoline derivatives.

In the current paper, we produce a new metal-organic framework (MOF) based on Zr metal, [Zr-UiO-66-PDC-SO3H]FeCl4, via an anion exchange method, which is fully characterized by FT-IR, SEM with elemental mapping and EDX, FE-SEM and TEM. Furthermore, the use of [Zr-UiO-66-PDC-SO3H]FeCl4 as a porous catalyst was examined for the one-pot synthesis of novel dihydrobenzo[g]pyrimido[4,5-b]quinoline derivatives by reaction of 6-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione, 2-hydroxynaphthalene-1,4-dione and various aldehydes at 100 °C with good to excellent yields.

An effective natural mineral-catalyzed heterogeneous electro-Fenton method for degradation of an antineoplastic drug: Modeling by a neural network.

In this study, the heterogeneous electro-Fenton method was used to remove Paclitaxel as an antineoplastic medicine. The cathode based on three-dimensional graphene (3DG) was applied as a gas diffusion electrode. The potential of five eco-friendly and recyclable iron minerals derived from nature (Magnetite, Siderite, Hematite, Limonite, and Pyrite) was investigated. Among the applied iron minerals, Pyrite showed the best, and Magnetite and Siderite showed good catalytic activity at pH 3.0. The current intensity of 300 mA, pHi 7.0, Paclitaxel concentration of 3 mg L-1, amount of Pyrite 4.5 g L-1, and time of 120 min was the optimum condition of the process with the removal efficiency of 99.13% in the presence of Pyrite. Repeating the experiments eight times revealed the reusability of the prepared 3DG as a cathode. Also, using radical scavengers indicated the principal role of the hydroxyl radicals (OH) in the treatment process. Analysis of total organic carbon reached 77.64% mineralization of 3 mg L-1 Paclitaxel at 360 min. Finally, ten by-products of small molecules were identified by gas chromatography-mass spectrometry device.

A convenient catalytic method for preparation of new tetrahydropyrido[2,3-d]pyrimidines via a cooperative vinylogous anomeric based oxidation.

In this study, a novel functionalized metal-organic frameworks MIL-125(Ti)-N(CH2PO3H2)2 was designed and synthesized via post-modification methodology. Then, MIL-125(Ti)-N(CH2PO3H2)2 as a mesoporous catalyst was applied for the synthesis of a wide range of novel tetrahydropyrido[2,3-d]pyrimidines as bioactive candidate compounds by one-pot condensation reaction of 3-(1-methyl-1H-pyrrol-2-yl)-3-oxopropanenitrile, 6-amino-1,3-dimethylpyrimidine-2,4(1H,3H)-dione and aromatic aldehydes at 100 °C under solvent-free condition. Interestingly, the preparation of tetrahydropyrido[2,3-d]pyrimidine was achieved via vinylogous anomeric based oxidation mechanism with a high yield and short reaction time.

Catalytic synthesis of new pyrazolo [3,4-b] pyridine via a cooperative vinylogous anomeric-based oxidation.

In this study, a novel nano-magnetic metal-organic frameworks based on Fe3O4 namely Fe3O4@MIL-101(Cr)-N(CH2PO3)2 was synthesized and fully characterized. The prepared sample was used as catalyst in the synthesis of pyrazolo [3,4-b] pyridines as convenient medicine by condensation reaction of aldehydes, 5-(1H-Indol-3-yl)- 2H-pyrazol-3-ylamine and 3-(cyanoacetyl)indole via a CVABO. The products were obtained with high yields at 100 °C and under solvent-free conditions.

Phosphonic acid tagged carbon quantum dots encapsulated in SBA-15 as a novel catalyst for the preparation of N-heterocycles with pyrazolo, barbituric acid and indole moieties.

Herein, we have presented a new insight for the synthesis of a hybrid heterogeneous catalyst. For this purpose, phosphonic acid tagged carbon quantum dots of CQDs-N(CH2PO3H2)2 encapsulated and assembled in channels of SBA-15 using a post-modification strategy. The mesoporous catalyst of functionalized carbon quantum dots (CQDs) was characterized by several techniques. CQDs-N(CH2PO3H2)2/SBA-15 as an excellent catalyst was applied for the preparation of novel pyrazolo[4',3':5,6]pyrido[2,3-d]pyrimidine derivatives by using pyrazole, barbituric acid and indole moieties at 100 °C under the solvent-free condition. The present work shows that a significant increase in the catalytic activity can be achieved by a rational design of mesoporous SBA-15 modified with CQDs for the synthesis of biological active candidates. The synthesized compounds did not convert to their corresponding pyridines via an anomeric-based oxidation mechanism.

Efficient electrochemical removal of 5-fluorouracil pharmaceutical from wastewater by mixed metal oxides via anodic oxidation process.

Nowadays, the entry of organic compounds into water resources is one of the leading global concerns due to the lack of water resources and rapid population growth. In this research, anodic oxidation (AO) method was used to remove 5-fluorouracil (5-FU) from aqueous solutions via Ni/RuO2 and Ti/IrO2-TiO2-RuO2 electrodes as cathode and anode, respectively. For this purpose, the characterization analysis of the electrodes, including X-ray diffraction, scanning electron microscopy, energy dispersive X-ray, and atomic force microscopy were performed. The electrochemical performance of the anode was investigated via cyclic voltammetry analysis. Then, the effect of operational variables, including applied current (mA), initial pH of the solution, initial 5-FU concentration (mg/L), and process time (min) on the 5-FU removal efficiency under the AO process was evaluated via artificial neural network (ANN) modeling. The results revealed that the maximum 5-FU removal efficiency was 96.96%. The applied current intensity, pH, initial 5-FU concentration, and process time were 300 mA, 5, 20 mg/L, and 140 min, respectively. Moreover, the investigation of 5-FU removal by-products and mineralization efficiency of the AO process was carried out via gas chromatography-mass spectrometry and total organic carbon analysis, respectively. The total organic carbon mineralization efficiency was 84.80% after 6 h of reaction time. The reusability and stability of the Ti/IrO2-TiO2-RuO2 anode on 5-FU removal efficiency were measured and showed an approximately 5% decay in 5-FU removal efficiency after eight consecutive runs. The overall results and analysis confirmed this method is capable of removing 5-FU through Ti/IrO2-TiO2-RuO2 anode and Ni/RuO2 cathode from aqueous medium.

MOF-Zn-NHC as an efficient N-heterocyclic carbene catalyst for aerobic oxidation of aldehydes to their corresponding carboxylic acids via a cooperative geminal anomeric based oxidation.

As an efficient heterogenous N-heterocyclic carbene (NHC) catalyst, MOF-Zn-NHC was used in the aerobic oxidation of aryl aldehydes to their corresponding carbocyclic acids via an anomeric based oxidation. Features such as mild reaction conditions and no need for a co-catalyst or oxidative reagent can be considered as the major advantages of the presented method in this study.

Preparation of Fe@Fe2O3/3D graphene composite cathode for electrochemical removal of sulfasalazine.

In the present study, heterogeneous electro-Fenton (EF) process was applied to remove the sulfasalazine (SU) pharmaceutical from aqueous solutions. In the first part, 3D graphene loaded with Fe@Fe2O3 core-shell nanowires (Fe@Fe2O3/3D-GO) was used as a cathode electrode in the EF process. Graphene oxide (GO) was synthesized for the synthesis of 3D graphene nanocomposites using the improved Hummers' method and subsequently 3D graphene synthesized by the hydrothermal method using glycine. Finally, Fe@Fe2O3/3D-GO composite was synthesized and its properties were assessed by Scanning electron microscopy, Atomic force microscopy, Brunauer-Emmett-Teller, Fourier-transform infrared spectroscopy and X-ray diffraction methods. Then, the cathode electrode was prepared using the resulting composite and its performance was evaluated using Cyclic Voltammetry analysis. In the final part of this work, the Fe@Fe2O3/3D-GO electrode was used as the cathode electrode in the heterogeneous EF process to remove SU from aqueous solutions. The effect of operating parameters such as applied current (mA), initial pH of solution, initial pharmaceutical concentration (mg L-1) and process time (min) on pharmaceutical removal efficiency under heterogeneous EF process was investigated by response surface methodology. The results showed that the optimum values for applied current, pH, initial pharmaceutical concentration and electrolysis time were respectively 300 mA, 7, 30 mg L-1 and 100 min, resulting 99.60% of SU removal. Finally, the intermediates of SU degradation were determined by Gas chromatography-mass spectrometry analysis and the amount of mineralization was determined by total organic carbon analysis. About 5.2% drop in the SU removal efficiency was observed within 8 operational runs.

Synergy of production of value-added bioplastic, astaxanthin and phycobilin co-products and Direct Green 6 textile dye remediation in Spirulina platensis.

Phyco-remediation of dyestuffs in textile wastewaters is of economic, industrial, and environmental importance. We evaluated the remediation of the textile dye, Direct Green 6 (DG6), by Spirulina platensis, and investigated the novel possibility that DG6 treatment enhances production of the biopolymer, polyhydroxybutyrate (PHB). We showed that both live and dead cells of Spirulina were capable of DG6 remediation, but live cells could be re-used with no loss of remediation efficiency. Furthermore, DG6 remediation by live cells resulted in increased algal biomass and trichome lengths, and stimulated production of valuable metabolites, including PHB, antioxidants, carbohydrates and pigments (phycobilins and astaxanthin). We determined the optimal conditions for DG6 remediation and an artificial neural network (ANN) accurately modeled the experimental data and predicted the concentration of dye as the most and algal turbidity as the least important parameters for DG6 removal efficiency. A DG6 concentration of 60 mg L-1 resulted in the highest simultaneous co-production of PHB (12.7 ± 1.7% DW) and increase of astaxanthin (194%), carotenoids (50%), phenol (51%), carbohydrates (27%) total phycobilin (43%), together with the enhancement of biomass and trichome lengths (95%). Oxidative stress indices and enzyme activities such as peroxidases and laccase (involved in dye removal/antioxidant functions) were also increased by dye dosage. On the basis of our results, we propose that S. platensis may use DG6 dye as a nitrogen/carbon source for co-accumulation of valuable bioplastic and metabolites.