Synthesis of Cu–Cr diketo,sublimable, eutectic composite complex,rod crystals from LDH as suitable MOCVD precursor of CuCr2O4 catalysts upon ceramic preforms for N2O decomposition

Metal-acteylacetonates are important sublimable metal-organic precursors for metal-oxide thin film formation over solid preforms by MOCVD (Metal Organic Chemical Vapour Deposition) technique. Mixed-metal-acetylacetonates (MMAA) are suitable starting materials for mixed metal nano-oxidic thin film formation through such facile routes. Layered Double Hydroxides (LDH) of suitable metal ion combination can perform as appropriate starting base for neutralisation by enol form of 2,4-pentanedione or acteylacetonate tautomer ligands to obtain such MMAA. In this paper synthesis of composite crystals of Cu(II)/Cr(III) acetylacetonates (CCAA) is reported by the reaction of Cu–Cr-LDH with acetylacetone. The products were characterized by various different techniques. The surface area and pore volume analysis of the crystals showed the formation of nanopores in the compound. TEM analysis confirmed that the inner core of the nanoporous crystals of Cu(acac)₂ was covered by coating of poorly crystallised Cr(acac)₃ and they together form the composite crystals, and they together form the composite crystals. Due to eutectic mixture formation the melting point of CCAA lies in between the melting points of individual components Cu(acac)₂ and Cr(acac)₃ and shows sublimability, a property important for the formation of MOCVD films. The composite was used for CuCr₂O₄ spinel mixed oxide films formation over solid ceramic honeycomb monolithic substrates. Application prospects of the route in the field of catalysis is high as it can directly combine the benefits of mixed metal oxide catalysis and structured supports without the involvement of a third component. In this work the performance of such a catalytic device has been tested for low temperature decomposition of high Global Warming Potential (GWP) gas N₂O to N₂ and O₂.     

Phytochemical Mediated Sol–Gel Synthesis,Crystallographic Structure,Morphology and Optical Investigations on ZnO Nanoparticles

Journal of Cluster Science - Zinc oxide nanoparticles were synthesized through sol–gel technique using Azadirachta indica leaves extract. The formation of structure, crystallite parameters,...     

Encapsulation of cobalt phthalocyanine in zeolite-y: evidence for nonplanar geometry

Cobalt (II) phthalocyanine (CoPc) molecules have been encapsulated within the supercage of zeolite-Y. The square-planar complex, being larger than the almost spherical cage, is forced to adopt a distorted geometry on encapsulation. A comparative spectroscopic and magnetic investigation of CoPc encapsulated in zeolite-Y and in the unencapsulated state is reported. These results supported by molecular modeling have been used to understand the nature and extent of the loss of planarity of CoPc on encapsulation. The encapsulated molecule is shown to be the trans-diprotonated species in which the center of inversion is lost due to distortions required to accommodate the square complex within the zeolite. Encapsulation also leads to an enhancement of the magnetic moment of the CoPc. This is shown to be a consequence of the nonplanar geometry of the encapsulated molecule resulting in an excited high-spin state being thermally accessible.     

Influence Of Zro2 on The Physicochemical Properties of Phosphate-Based Glasses and Glass Ceramics

Abstract

Phosphate-based bioactive glasses and their glass ceramics for 47P₂O₅– (30.5)CaO–(22.5 ? x)Na₂O–xZrO₂ for different ZrO₂ contents (x = 0, 1.5, 3.0, 4.5, and 6.0 mol%) were prepared through melt quenching and controlled heat treatment procedures. The amorphous nature of glasses and the presence of crystalline phases in glass ceramics were studied by means of X-ray diffraction (XRD) studies. The density, molar volume, ultrasonic velocities, attenuation, elastic constants, and microhardness of glass and glass ceramics were used to study the structural changes. The formation of hydroxyapatite layer on the surface of glasses and glass ceramics after immersion in simulated body fluid (SBF) was explored through XRD, Fourier transform infrared (FTIR), and scanning electron microscopy (SEM) analyses. The results indicate that the added ZrO₂ increases the crosslink density of glasses, resulting in network stability, and also induces the formation of an apatite layer on the surface of glasses.

Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file.     

Crystal structure and DFT analyses of a pentacoordinated PCP pincer nickel(II) complex

The reaction of NiCl₂ with 1,3‐bis[(diphenylphosphanyl)methyl]hexahydropyrimidine in the presence of 2,6‐dimethylphenyl isocyanide and KPF₆ afforded a new pentacoordinated PCP pincer Ni^II complex, namely {1,3‐bis[(diphenylphosphanyl)methyl]hexahydropyrimidin‐2‐yl‐κN²}(2,6‐dimethylphenyl isocyanide‐κC)nickel(II) hexafluoridophosphate 0.70‐hydrate, [Ni(C₉H₉N)(C₃₀H₃₀ClN₂P₂)]PF₆·0.7H₂O or [NiCl{C(NCH₂PPh₂)₂(CH₂)₃‐κ³P,C,P′}(Xylyl‐NC)]PF₆·0.7H₂O, in very good yield. Its X‐ray structure showed a distorted square‐pyramidal geometry and the compound does not undergo dissociation in solution, as shown by variable‐temperature NMR and UV–Vis studies. Density functional theory (DFT) calculations provided an insight into the bonding; the nickel dsp²‐hybridized orbitals form the basal plane and the nearly pure p orbital forms the axial bond. This is consistent with the NBO (natural bond orbital) analysis of analogous nickel(II) complexes.     

Dications of benzylidenefluorene and diphenylmethylidene fluorene: the relationship between magnetic and energetic measures of antiaromaticity

Oxidation of m- and p-substituted benzylidene fluorenes to antiaromatic dications was attempted by electrochemical and chemical means. Electrochemical oxidation to dications was successful for benzylidene fluorenes with p-methoxy, p-methyl, p-fluoro, and unsubstituted phenyl rings in the 3-position; attempts to oxidize the m-substituted derivatives via electrochemistry were unsuccessful. Chemical oxidation with SbF(5)/SO(2)ClF gave the dication of 9-[(4-methoxyphenyl)methylene]-9H-fluorene cleanly; oxidation of all other substituted benzylidene fluorenes resulted in mixtures of products. The excellent linear relationship between the chemical shifts calculated by the GIAO method and the experimental shifts for the p-methoxy-substituted benzylidene fluorene dication suggests that the calculations satisfactorily reflect the magnetic properties of this dication and potentially those of the other dications studied. The redox potentials from electrochemical oxidation, a measure of the stability of the dications, showed a good linear relationship with another measure of stability, the calculated difference in energy between each dication and its neutral precursor. The dications of benzylidene fluorenes were less stable than the dications of diphenylmethylidene fluorenes; within each type of compound, dications with p-substituted phenyl rings were more stable than dications with m-substituted phenyl rings and dications with phenyl rings substituted with electron-donating groups were more stable than dications with phenyl rings substituted with electron-withdrawing groups. The antiaromaticity of the fluorenyl system was assessed through the nucleus-independent chemical shift (NICS) that was also calculated by the GIAO method. The plot of the NICS values per square area versus the calculated energy difference for the dications showed a moderate degree of linearity; the plot of NICS values per square area versus the oxidation potentials was less linear. Thus, a suggestive, but not conclusive, relationship between magnetic and energetic measures of antiaromaticity was observed.     

Immobilized Carboxypeptidase A for Sequential Analysis

The use of carboxypeptidase for sequence determination is attractive because of its technical simplicity. In chemical methods all molecules of a peptide are made to go through a degradation cycle before a new cycle is started. In the enzymatic degradation of a protein, the order of the amino acid residues is not necessarily determined in a stepwise fashion but rather from the rate at which the amino acids appear in the digest, i.e., an amino acid appearing faster than another presumably precedes it in the sequence. Under favorable circumstances the rate of appearance of the amino acids released during digestion give sufficient evidence for the C-terminal sequence to be deduced. The present work pertains to a study on the use of immobilized carboxypeptidase A columns for sequential analyses.     

Polyfunctional Lithium,Magnesium, and Zinc Alkenyl Reagents as Building Blocks for the Synthesis of Complex Heterocycles

New conjunctive β‐silylated organometallic reagents of Li, Mg, and Zn have been prepared and used for an expeditive construction of various polyfunctionalized 5‐, 6‐, and 7‐membered heterocycles, such as furans, pyrroles, quinolines, benzo[b]thieno‐[2,3‐b]pyridine, naphthyridines, fused pyrazoles, and 2,3‐dihydro‐benzo[c]azepines. The latent silyl group has been converted into various carbon–carbon bonds in most heterocycle types.     

Protective Effect of <Emphasis Type="Italic">Zingiber officinale</Emphasis> Against Dalton’s Lymphoma Ascites Tumour by Regulating Inflammatory Mediator and Cytokines

The aim of the present investigation was to evaluate Zingiber officinale paste against Dalton’s lymphoma ascites (DLA)-induced tumours in Swiss albino mice. Experimental animals received Z. officinale paste (low dose 100 mg/kg bw and high dose 500 mg/kg bw) orally for eight alternative days. Treatment with Z. officinale paste showed significant increase in haemoglobin level and decrease in aspartate amino transferase (AST), alanine aminotransferase (ALT), alkaline phosphatase (ALP) and gamma glutamyl transferase (γ-GT) level. Z. officinale paste reduced the inflammatory mediators and cytokine levels, such as inducible nitric oxide (iNOS), tumour necrosis factor level (TNF-α) and interleukin-1β (IL-1β). Treatment with Z. officinale paste also significantly increased the antioxidant enzyme level, such as superoxide dismutase (SOD), catalase (CAT), reduced glutathione (GSH) and glutathione transferase (GST), and decreased the lipid peroxidation. Treatment also increased the vitamin C and E levels in treated animals compared with the DLA-bearing host. Histopathological studies also confirmed the protective influence of Z. officinale paste against DLA. The present study suggested that Z. officinale paste could be used as natural spice and a potent antitumour agent.     

Synthesis and characterization of LiCo<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Mn<Subscript>2−<Emphasis Type="Italic">x</Emphasis></Subscript>O<Subscript>4</Subscript> powder by a novel CAM microwave-assisted sol–gel method for Li ion battery

LiMn₂O₄-based spinels are of great interest as positive electrode materials for lithium ion batteries. LiCo _x Mn_2−x O₄ (x = 0.0, 0.1, 0.2, 0.3, and 0.4) spinel phases have been synthesized by novel citric acid-modified microwave-assisted sol–gel method. The structural properties of the synthesized products have been investigated by X-ray powder diffraction and scanning electron microscopy. To improve the recharge capacity of Li/LiCo _x Mn_2−x O₄ cells, the electrochemical features of LiCo _x Mn_2−x O₄ compounds have been evaluated as positive electrode materials. The structural properties of Co-doped oxides are very similar to LiMn₂O₄ electrode. Techniques like cyclic voltammetry, charge–discharge and cycle life are also used to characterize the LiCo _x Mn_2−x O₄ (x = 0.0, 0.1, 0.2, 0.3, and 0.4) electrodes.