An Efficient Method for Chemoselective Reduction of Nitro Compounds Using Bimetallic Fe‐Ni NPs/H3PW12O40.×H2O System

The selective reduction of nitro compounds by treatment with bimetallic Fe‐Ni nanoparticles (NPs) and tungestophosphoric acid hydrate (H₃PW₁₂O₄₀.×H₂O) in H₂O is reported. The method has been applied to a broad range of nitro compounds with different sensitive functionalities, including halides, carbonyl, hydroxyl, aldehyde, methyl, acetyl, nitrile, and ester substituents with excellent yields. The reaction yielded single product in all cases with very high yield. The simple experimental procedure and easy purification make the protocol advantageous.     

Synthesis and comparative study of catalytic activity between Pd-metallodendrimer and Pd/Cu-bimetallodendrimer nanoparticle-based on triazine

Triazine-based heterogeneous Pd/Cu-bimetallodendrimer Nanoparticle (Pd/Cu-BMDNP) has been synthesized by sequential loading method from palladium containing metallodendrimer (Pd-MD) which was prepared by the reaction of 2,4,6-Triamine-1,3,5-triazine (melamine) with substituted benzoyl chloride using (Ph₃P)₂PdCl₂ in DMSO at 90 °C. SEM and EDX of Pd/Cu-BMDNP showed the nanosized aggregated spherical surface morphology and the presence of Palladium and copper of the NP. Also, the phase was detected as Face Centered Cubic (FCC) structure by XRD analysis. In addition, the average particle size of Pd/Cu bimetallic catalyst was identified as 12–13 nm by TEM investigation. Greater thermal stability of Pd/Cu-BMDNP than Pd-MD was detected from TG and DSC experiments. The Pd-metallodendrimer has been also characterized by IR, ¹H NMR, ¹³C NMR, SEM, EDX, Mass, TG and DSC techniques. The simple recoverability, high reusability, low amount of catalyst loading, negligible amount of catalyst leaching of the heterogeneous Pd/Cu-BMDNP have made more effective catalyst than homogeneous Pd-metallodendrimer for the C–C cross-coupling reaction such as Heck, Glaser, Sonogashira and Suzuki-Miyaura in excellent yields.     

Significantly enhanced electromagnetic interference shielding effectiveness of montmorillonite nanoclay and copper oxide nanoparticles based polyvinylchloride nanocomposites

In the present study, montmorillonite (MMT) nanoclay and copper oxide (CuO) nanoparticles (NPs) reinforced polyvinylchloride (PVC) based flexible nanocomposite films were prepared via solvent casting technique. Using Fourier-transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), Scanning electron microscopy (SEM) and thermo-gravimetric analysis (TGA), the structural, morphological and thermal properties of PVC/MMT/CuO nanocomposite films with various loadings of CuO NPs and MMT were investigated. These studies suggested that by the addition of dual nanofillers in the polymer matrix some structural modifications occurred owing to the homogenous dispersion of MMT and CuO NPs within the PVC matrix. The TGA results reveal that the addition of CuO NPs and MMT considerably improved the thermal stability of the nanocomposites. The EMI shielding effectiveness (SE) of nanocomposites was examined in the X-band (8–12 GHz) and Ku-band (12–18 GHz) frequency regions. The EMI SE values were found to be −30 dB (X-band) and −35 dB (Ku-band) for nanocomposites containing 0.3 wt% of CuO NPs and 4.7 wt% of MMT respectively while the shielding was found to be absorption dominant. These results emphasize that PVC/MMT/CuO nanocomposite films can be used as a potential EMI shielding material.     

A highly efficient and versatile microchip capillary electrophoresis method for DNA separation using gold nanoparticle as a tag

A highly efficient and versatile method for DNA separation using Au nanoparticles (Au NPs) as a tag based on microchip capillary electrophoresis (MCE) was developed. The thiol-modified DNA-binding Au NPs were utilized as a tag. Target DNA was sandwiched between Au NPs and probe DNA labeled with horseradish peroxidase (HRP). In electrophoresis separation, the difference in electrophoretic mobility between free probe and probe-target complex was magnified by Au NPs, which enabled the resulting mixture to be separated with high efficiency by microchip capillary electrophoresis. Horseradish peroxidase was used as a catalytic label to achieve sensitive electrochemical DNA detection via fast catalytic reactions. With this protocol, 27-mer DNA fragments with different sequences were separated with high speed and high resolution. The proposed method was critical to achieve improved DNA separations in hybridization analyses.     

Fabrication of Au‐Nanoparticle/TiO2‐Nanotubes Electrodes Using Electrochemical Methods and Their Application for Electrocatalytic Oxidation of Hydroquinone

Gold nanoparticle (Au‐NPs)‐Titanium oxide nanotube (TiO₂‐NTs) electrodes are prepared by using galvanic deposition of gold nanoparticles on TiO₂‐NTs electrodes as support. Scanning electron microscopy and energy‐dispersive X‐ray spectroscopy results indicate that nanotubular TiO₂ layers consist of individual tubes of about 60–90 nm diameters and gold nanoparticles are well‐dispersed on the surface of TiO₂‐NTs support. The electrooxidation of hydroquinone of Au‐NPs/TiO₂‐NTs electrodes is investigated by different electrochemical methods. Au‐NPs/TiO₂‐NTs electrode can be used repeatedly and exhibits stable electrocatalytic activity for the hydroquinone oxidation. Also, determination of hydroquinone in skin cream using this electrode was evaluated. Results were found to be satisfactory and no matrix effects are observed during the determination of hydroquinone content of the “skin cream” samples.     

Nanostructured thin films as surface‐enhanced Raman scattering substrates

Nanoporous thin films with silver nanoparticles were synthesized with a bottom–up approach, and its potential as effective surface‐enhanced Raman scattering (SERS) substrates was demonstrated. The use of mesoporous titania films as substrates allowed to control the growth of nanoparticles on the film surface. Atomic force microscopy measurements, Ultraviolet‐visible and X‐ray diffraction analysis confirmed the photoreduction of Ag⁺ to Ag⁰ with the formation of nanoparticles with crystallite dimensions of 32 to 36 nm. The new substrates allowed the detection of two analytes (rhodamine B isothiocyanate and cytochrome c), present in solutions at very low concentrations, highlighting their potential in SERS sensing. Reproducibility, homogeneity, enhancement factor of the substrate, consistency of results and detection limits were also assessed. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and Structural Characterizations of Ternary Iron(Ⅱ) Mixed Ligand Complex: Low Cost Materialsas a Precursor for Preparation of Nanometric Fe_2O_3 Oxide

The reaction of the ligands, ethylenediaminetetraacetic acid terasodium salt (Na₄EDTA) and N-N heterocyclic diamines like2,2’-bipyridine (bipy) with iron(Ⅱ) sulfate with 1∶2∶2 stoichiometric ratios form the mononuclear ternary complex of formulae, [Fe₂(EDTA)(bipy)₂] at pH~7. The FTIR and Raman laser spectra of the iron(Ⅱ) complex show that 2,2’-bipyridine is present asa bidentate ligand and the ethylenediaminetetraacetic acid terasodium salt as monodentate carboxylate anion. The electronic spectra and magnetic moments data suggest the six coordination number. It has two iron(Ⅱ) centers in octahedral environments, which are interlinked by carboxylato-O atoms of ethylenediaminetetraacetate and by nitrogen atoms of the two 2,2-bipyridine ligands in a chelating mode. Thermal analysis study show thatiron(Ⅱ) complex containing EDTA and 2,2’-bipyridine on its thermalde composition form the corresponding Fe₂O₃ oxide in nano size at the temperature range ~475 ℃. The iron(Ⅱ) complex was performed as a convenient low cost precursor for the preparation of Fe₂O₃ nanoparticles by the the thermal decomposition method. The iron(Ⅲ) oxide composition has been discussedusing FTIR, X-ray diffraction (XRD), transmission electron microscopy (TEM) and energy-dispersive X-ray spectroscopy (EDX).     

The influence of ultrasonic irradiation on catalytic performance of ZnO nanoparticles toward the synthesis of chiral 1-substituted-1H-tetrazolederivatives from α-amino acid ethyl esters

In this work, a simple and greener protocol for the synthesis of 1-substituted 1H-tetrazole derived from α-amino acid ethyl esters was demonstrated in the presence of zinc oxide nanoparticles (ZnO NPs) under conventional conditions, with heating (at 60 and 80°C and under reflux) compared with ultrasonic. The effect of solvent was investigated to reveal that the solvent system CH₃CN/H₂O was optimum to obtain 1-substituted 1H-tetrazole in high yield. In addition, the effect of irradiation power was studied, which showed that the yield of the reaction was improved at 200 W and the reaction time was shortened to be 30 min. Also, an improvement in the rate of the reaction and the yield of the products was observed when reactions were carried out under sonication conditions in the presence of ZnO NPs compared with conventional methods using various zinc salts as catalysts. The yields of tetrazole compounds 2a–i under sonication were determined (88–96%). Furthermore, the investigated heterogeneous catalytic system was recycled and reused for five runs with significant production of tetrazole 2a as a model target compound in excellent yields at each reaction cycle. In general, the investigated synthetic strategy for the heterocyclization of α-amino acid ethyl ester derivatives to 1-substituted 1H-tetrazoles was in agreement with the green chemistry point of view.     

Copper immobilized on aminated ferrite nanoparticles by 2‐aminoethyl dihydrogen phosphate (Fe3O4@AEPH2‐CuII) catalyses the conversion of aldoximes to nitriles

Cu^II immobilized on aminated ferrite nanoparticles by 2‐aminoethyl dihydrogen phosphate (Fe₃O₄@AEPH₂‐Cu^II) was prepared and characterized using FT‐IR, TGA, TEM, EDX, VSM, XRD, CHN and ICP techniques. The easily prepared heterogeneous nanocatalyst demonstrated a significant catalytic performance for the transformation of aldoximes to nitriles that is far superior to previously reported methods. The reaction allows for the conversion of a wide variety of aldoximes including aromatic, aliphatic and heterocyclic aldoximes in good to excellent yields (50–98%). High efficiency, mild reaction conditions, easy work‐up, operational simplicity, simple purification of products and safe handling of the catalyst are important advantages of this method. In addition, the environmentally benign heterogeneous nanocatalyst can be easily recovered from reaction mixtures using an external magnet and reused several times without any loss of activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Synthesis,characterization, DNA binding/cleavage,and anticancer and antimicrobial activities: Nano-sized Co(II) and Cd(II) complexes and their use as a precursor for CoO and CdO nanoparticles

In the search of effective bioactive compounds, Co(II) ( C1 ) and Cd(II) ( C2 ) complexes of the type [M(FMAPIMP)(H₂O)Cl].nH₂O (where M = Co(II); n = 2, Cd(II); n = 3, and FMAPIMP = ligand[2-((E)-((2-(((E)-furan-2-ylmethylene)amino)phenyl)imino)methyl)phenol]) were synthesized and characterized using elemental analysis, UV–Vis., cyclic voltammetry, Fourier-transform infrared (FT-IR), nuclear magnetic resonance, and mass spectral studies. The thermal stability of nano-sized Co(II) and Cd(II) complexes was studied using thermogravimetric analysis (TGA). Cobalt and cadmium oxides were synthesized using cobalt and cadmium nanoparticle (NP) structure Schiff base complexes as the raw material after calcination for 5 h at 600 °C. According to the results, Co(II) and Cd(II) complexes with mole ratio 1:1 of metal: H-FMAPIMP which octahedral are the most probable geometry for it. On the contrary, synthesized C1 and C2 NPs were used as suitable precursors for the preparation of CoO and CdO NPs. The obtained NPs were characterized using FT-IR, UV–Vis., TGA, powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and atomic force microscopy techniques. PXRD analysis revealed that the obtained oxides were crystalline and corresponded to CoO and CdO phases. Crystal size, shape, and morphology were determined using SEM and TEM. H-FMAPIMP and its two complexes ( C1 and C2 ) were tested against human ovarian cancer cell line (PA-1). The synthesized Co(II) and Cd(II) complexes exhibited enhanced activity against the tested bacterial (Staphylococcus aureus and Escherichia Coli) and fungal strains (Candida albicans and Aspergillus fumigatus) as compared to H-FMAPIMP. The results of the DNA-cleavage activity indicated that the ligand and its two complexes can cleave calf thymus-DNA at different degrees. Further, antituberculosis activity was performed using microplate alamarBlue assay. Among all these synthesized compounds, C1 exhibited good cleaving ability compared to the newly synthesized C2 . Finally, the geometry of H-FMAPIMP and its Co(II) and Cd(II) complexes was optimized using molecular modeling.