FACILE REDUCTION OF AROMATIC NITRO COMPOUNDS WITH HYDROIODIC ACID UNDER MICROWAVE IRRADIATION ON SOLID SUPPORT

Reduction of aromatic nitro compounds to amine with hydroiodic acid was revisited. Under microwave irradiation on solid support the reduction proceeded efficiently and rapidly.     

Synthesis of oxo-Phosphoranylidene Aminobenzoic Acid Derivatives by a Multicomponent Reaction

2-Aminobenzoic acids or 4-aminobenzoic acid react with dimethyl acetylenedicarboxylate/triphenylphosphine in less than 20 min at 15–25°C to produce new organic phosphorus compounds in good to excellent yields. The conversion occurs with selective N- over O-alkylation of the amino group and isolation of the products is accomplished simply by filtration.     

SELECTIVE OXIDATION OF BENZYLIC ALCOHOLS USING CAN SUPPORTED ONTO SILICA GEL UNDER MICROWAVE IRRADIATION

Cerium ammonium nitrate (CAN) adsorbed on HNO ₃ /silica gel is a mild reagent for selective oxidation of benzylic alcohols to the corresponding aldehydes under microwave irradiation in solventless system.     

A simple accurate model for prediction of deflagration temperature of energetic compounds

A novel general method is introduced to predict deflagration temperature of organic energetic compounds containing at least –NNO₂, –ONO₂, or –CNO₂ groups. Deflagration temperature is an important safety parameter in working with dangerous energetic compounds and their environmental problems. It is shown that the contribution of some molecular structure parameters can be used to interpret thermal decomposition of an energetic compound. For 86 energetic materials (corresponding to 102 measured values) with different molecular structures, the new correlation has the root mean square (rms) and the average deviations of 23.8 and 19.0 K, respectively. The new method is also tested for some energetic compounds with complex molecular structures, e.g., two new organic energetic molecules N,N′-bis(1,2,4-triazol-3yl)-4,4′-diamino-2,2′,3,3′,5,5′,6,6′-octanitroazobenzene (BTDAONAB) and 2,4,6-trinitrophloroglucinol.     

Photoelectrocatalytic degradation of 3-nitrophenol at surface of Ti/TiO2 electrode

The widely utilization of phenol and its derivatives such as 3-nitrophenol (3-NP) has led to the worldwide pollution in the environment. In this study, Ti/TiO₂ photoelectrode was prepared with anodic oxidation of Ti foil electrode and then the photoelectrocatalytic (PEC) degradation of 3-NP was performed via this electrode, comparing with photocatalytic (PC), electrooxidation and direct photolysis by ultraviolet light. A significant photoelectrochemical synergetic effect in 3-NP degradation was observed on the Ti/TiO₂ electrode and rate constant for the PEC process of Ti/TiO₂ electrode was about three times as high as its PC degradation process. 3-NP concentration monitoring was carried out with differential pulse voltammetry. Results showed that PEC degradation has highest effect on concentration decreasing of 3-NP at solution and degraded it about 38 %, while other processes degradation efficiencies were about 4, 7, and 12 % for electrooxidation, direct photolysis and photocatalytic degradation, respectively. Finally, effects of solution pH and applied potential on degradation efficiency were studied and results showed that optimum pH for degradation is equal 4.00 and optimum potential is 1.2 V vs. Ag|AgCl|KCl (3M) reference electrode.     

Organically modified montmorillonite and chitosan–phosphotungstic acid complex nanocomposites as high performance membranes for fuel cell applications

Nanocomposite membranes based on polyelectrolyte complex (PEC) of chitosan/phosphotungstic acid (PWA) and different types of montmorillonite (MMT) were prepared as alternative membranes to Nafion for direct methanol fuel cell (DMFC) applications. Fourier transform infrared spectroscopy (FTIR) revealed an electrostatically fixed PWA within the PEC membranes, which avoids a decrease in proton conductivity at practical condition. Various amounts of pristine as well as organically modified MMT (OMMT) (MMT: Cloisite Na, OMMT: Cloisite 15A, and Cloisite 30B) were introduced to the PEC membranes to decrease in methanol permeability and, thus, enhance efficiency and power density of the cells. X-ray diffraction patterns of the nanocomposite membranes proved that MMT (or OMMT) layers were exfoliated in the membranes at loading weights of lower than 3 wt.%. Moreover, the proton conductivity and the methanol permeability as well as the water uptake behavior of the manufactured nanocomposite membranes were studied. According to the selectivity parameter, ratio of proton conductivity to methanol permeability, the PEC/2 wt.% MMT 30B was identified as the optimum composition. The DMFC performance tests were carried out at 70 °C and 5 M methanol feed and the optimum membrane showed higher maximum power density as well as acceptable durability compared to Nafion 117. The obtained results indicated that owing to the relatively high selectivity and power density, the optimum nanocomposite membrane could be considered as a promising polyelectrolyte membrane (PEM) for DMFC applications.     

The electrochemical behaviors of methylene blue on the surface of nanostructured NiWO4 prepared by coprecipitation method

A simple coprecipitation method was used for preparation of monoclinic nanostructured NiWO₄ from an aqueous solution at a fixed pH and temperature of 7.0 and 80 °C, respectively. The prepared material was characterized by X-ray diffraction, scanning electron microscopy, photoluminescence spectroscopy, and electrochemical measurements. Nano-NiWO₄ was incorporated into a carbon paste electrode and by means of cyclic voltammetry; the electrochemical behavior of methylene blue on the surface of nano-NiWO₄ was investigated. A mechanism on terms of obtained cyclic voltammograms showing one reduction peak and two sequential oxidation peaks was suggested by emphasizing on the stabilizing role of nano-NiWO₄ for semi-methylene blue. A diffusion coefficient of 5.30?×?10^?6 cm²/s was gained for methylene blue.     

Theoretical studies on tautomerism of imidazole-2-selenone

The tautomerism of all possible forms of imidazole selenone (ISe1–ISe6), induced by proton transfer was studied theoretically in different environments including gas phase, continuum solvent, and microhydrated environment with one explicit water molecule. The calculations were performed at the MP2 and CAM-B3LYP levels of theory, separately. It was found that the imidazole selenone, in the form of ISe3, is the most stable isomer in both gas phase and solvent. The activation energy for conversion of ISe3 to imidazole selenol (ISe6), as the second stable form, is 41.72 and 43.0 kcal/mol in the gas phase and water, respectively. The infrared spectral frequencies as well as the vibrational frequency shifts were reported and assigned to their corresponding vibrational modes. In addition, the variation of dipole moments and charges on the atoms with change of solvent was studied. The energies of HOMO, LUMO, and HOMO–LUMO gap were calculated in both gas phase and solvent. Specific solvent effects with addition of water molecule near the electrophilic centers of tautomers and the transition states of proton transfer, assisted by water molecule, were investigated. It was found that the water molecule can form different hydrogen bonds with the molecule. Aggregation of the isomers with water molecule does not change the order of stability of isomers, but proton transfer reaction assisted by a water molecule needs less energy than when the proton shifts through the intramolecular process.     

Effect of axial strain on structural and electronic properties of zig-zag type of boron nitride nanotube (BNNT): a quantum chemical study

The influence of strain on structural and electronic properties of zig-zag type of boron nitride nanotubes (BNNTs) has been studied by density functional theory calculations. The variations of HOMO–LUMO gaps, geometrical parameters, cohesive energy, radial buckling, isodensity surfaces of the HOMOs and LUMOs, electrophilicity index, chemical potential, and chemical hardness and softness have been investigated for BNNTs at different strains. Our results show that the effect of axial strain on the electronic and structural properties of zig-zag BNNTs depends on the diameter as well as the length of the nanotube.