Oxidation of Aromatic Amines to Quinones by Iodic Acid under Microwave Irradiation in the Presence of Montmorillonite K10 and Silica Gel

Summary. A variety of aromatic amines are oxidized to their corresponding quinones in excellent yields by supported iodic acid under microwave irradiation and solvent free conditions.     

NiO nanoparticles prepared via thermal decomposition of the bis(dimethylglyoximato)nickel(II) complex: A novel reusable heterogeneous catalyst for fast and efficient microwave-assisted reduction of nitroarenes with ethanol

NiO nanoparticles with an average size of 12 nm and a high specific surface area of 88.5 m²/g were easily prepared via the thermal decomposition of the complex Ni(dmgH)₂ and were characterized by TGA, XRD, FT-IR, TEM and BET surface area measurement. This nanosized transition metal oxide was used as a new heterogeneous catalyst for the reduction of nitroarenes under microwave irradiation. The efficient and selective reduction of aromatic nitro compounds into their corresponding amines was observed by using ethanol as a hydrogen donor (reducing agent) and KOH as a promoter under microwave irradiation. This highly regio- and chemoselective method is fast, simple, inexpensive, high yielding, clean and compatible with several sensitive functionalities, such as halogens, -OH, -OCH₃, -CHO, -COCH₃, -COOH, -COOEt, -CONH₂, -CN, -CHCH₂ and -NHCOCH₃. This method is suitable for the large scale preparation of different substituted anilines as well as other arylamines. In addition, the catalytic activity of nanosized NiO is higher than that of the bulk sample.     

Fabrication and characterization of low-cost freeze-gelated chitosan/collagen/hydroxyapatite hydrogel nanocomposite scaffold

In the present research, chitosan/collagen and chitosan/collagen/nano-hydroxyapatite (nHAP) hydrogel nanocomposites were prepared using naturally extracted chitosan from Persian Gulf shrimp wastes and rat tail-tendon collagen. Freeze-gelation method was used to prepare highly porous scaffolds. The morphology, chemical structure, water retainability, and thermal properties were characterized using SEM, FTIR, water content experiment, simultaneous thermal analysis (STA), respectively. Atomic force microscopy (AFM) nanoindentation and unconfined compression test were used to assess different feature of the mechanical properties of the hydrogels. The obtained results were so promising that the prepared nanocomposites can be considered as a potential candidate for cartilage tissue engineering.     

The first X-ray crystal structure of a mercury(II) complex with an SP(N)3-based ligand: Synthesis and crystal structure of SP(NC5H10)3 and [Hg{SP(NC5H10)3}Cl2]2

The synthesis, spectral characteristics (IR and NMR), elemental analysis and X-ray crystal structure of phosphorothioic triamide SP(NC₅H₁₀)₃ (1) and its dinuclear mercury(II) complex [Hg₂(μ-Cl)₂(Cl)₂{SP(NC₅H₁₀)₃}₂] (2) were investigated. A survey using the Cambridge Structural Database (CSD, version 5.38, May 2017) shows structures of coordination compounds of Au, Ag, Cd, Cu, Li, Mo, Ni, Pd, Te, Ti, Zn, and Zr with sulfur-donor SP(N)₃-based ligands; the complex 2 is the first example of a mercury complex with the SP(N)₃-based ligand studied by X-ray crystallography. Valence bond calculation was performed for the Hg–S bond in 2 and compared with the Hg–O bond in the only structure with a Cl₂Hg–OP(N)₃ structural motive in the CSD. The calculation confirms a more covalent nature of the Hg–S bond with respect to the Hg–O bond made by the EP(N)₃-based ligands (E?=?S, O). The supramolecular structures based on C–H···S?=?P contacts in 1 and C–H···S═P and C–H···Cl–Hg assemblies in 2 are discussed.     

Analysis and evaluation of the antimicrobial and anticancer activities of the essential oil isolated from Foeniculum vulgare from Hamedan,Iran

In this study, biological properties of the essential oil isolated from seeds of Foeniculum vulgare (F. vulgare) were evaluated. GC-MS analysis revealed Trans-Anethole (80.63%), L-Fenchone (11.57%), Estragole (3.67%) and Limonene (2.68%) were the major compounds of the essential oil. Antibacterial activity of the essential oil against nine Gram-positive and Gram-negative strains was studied using disc diffusion and micro-well dilution assays. Essential oil exhibited the antibacterial activity against three Gram-negative strains of Pseudomonas aeruginosa, Escherichia coli, and Shigella dysenteriae. The preliminary study on toxicity of seed oil was performed using Brine Shrimp lethality test (BSLT). Results indicated the high toxicity effect of essential oil (LC50 = 10 μg/mL). In vitro anticancer activity of seed oil was investigated against human breast cancer (MDA-Mb) and cervical epithelioid carcinoma (Hela) cell lines by MTT assay. Results showed the seed oil behave as a very potent anticancer agent with IC50 of lower than 10 μg/mL in both cases.     

Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X‐Ray Spectroscopy

Manganese oxide (MnO_x) electrocatalysts are examined herein by in situ soft X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L‐edge XAS data with previous mechanistic studies indicates Mn^IV is the highest oxidation state involved in the catalytic mechanism. MnO_x is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn?O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K‐edge provide complementary evidence for such a transition. This step is crucial for the formation of O₂ from water.     

Porous MoO3@SiC hallow nanosphere composite as an efficient oxidative desulfurization catalyst

A novel N‐doped MoO ₃ @SiC hollow nanosphere has been synthesized through two steps. Due to the first step, N‐doped MoO₂@C nanosphere was synthesized using the hydrothermal method and in the second step, Si‐C bonds were formed through the low‐temperature magnesiothermic method and MoO ₃ @SiC hollow nanosphere was produced. The prepared nanostructures were identified by various techniques such as IR, XRD, XPS, BET/BJH, SEM/EDS, and Raman spectroscopy. Results show that converting of C to SiC increase the surface area from 17 to 241 m²/g with remarkably decrease in pore diameter. Also, molybdenum is present in the form of MoO₂ in carbon catalyst while during magnesiothermic process, it transfers to MoO₃ form in the SiC catalyst. The synthesized products were employed as catalysts in oxidative desulfurization of model fuel. The results displayed that MoO ₃ @SiC hollow nanostructure shows a superior catalytic activity (99.9%, 40 min) compared to C support (56%, 60 min). Furthermore, the recycling of MoO₂@C catalyst shows a dramatic decrease even after the first run, while, SiC support exhibit higher stability during the stronger interaction between molybdenum catalyst and SiC support.     

One-pot Synthesis of 3-Aminoimidazo[1,2-a]pyridines Catalyzed by Heteropolyacids

Condensation of aldehydes, isonitriles and 2‐aminopyridines in the presence of H₃PMo₁₂O₄₀ affords different derivatives of 3‐aminoimidazo[1,2‐a]pyridine in good to excellent yields.     

1H NMR Study of Hindered Internal Rotation of Tetramethylthiuram Disulfide in Binary Dimethyl Sulfoxide‐Chloroform Mixtures

Hindered internal rotation about the C‐N single bonds joining the thiuram disulfide was studied by ¹H NMR complete line‐shaped analysis in different dimethyl sulfoxide‐chloroform (DMSO‐CDCl₃) mixtures. From the temperature dependence of methyls proton spectra, activation parameters (E_a, ΔH^≠, ΔS^≠, and ΔG^≠) were obtained. The Arrhenius plots showed a distinct isokinetic temperature at about 35 °C at which the exchange rate is more or less independent of the solvent composition. The resulting ΔH^≠ against TΔS^≠ plot showed a firmly good linear correlation, indicating the existence of an enthalpy‐entropy composition in an exchange process.     

Characterization and determination of fatty acids in fish oil using gas chromatography-mass spectrometry coupled with chemometric resolution techniques

Characterization and determination of a complex mixture of fatty acid methyl esters was performed for commercial fish oil using two-dimensional GC-MS data coupled with resolution techniques. Various principle component analysis methods such as significant factor analysis and fixed size moving window evolving factor analysis were used for the number of factors, zero concentration and selective regions. Then, the convoluted chromatograms were resolved into pure chromatograms and mass spectra using heuristic evolving latent projections (HELP) method. Fatty acids of C16:1omega7, C18:4omega3, C18:1omega11, C18:1omega9, C18:0, C20:2omega6, C20:1omega9, C22:1omega11, C22:1omega9 and C24:1omega9 were resolved an fied by using similarity searches between deconvoluted mass spectra and MS database, in different parts of total ion current chromatogram. Window target testing factor analysis is also applied for confirming the presence or absence of target analytes. The results of the present work show that combination of hyphenated chromatographic methods and resolution techniques provide a complementary method for accurate analysis of real multi-component systems such as fish oil.