Characterization of the citrate precursor, used for synthesis of nanosized Mg-Zn ferrites

The citrate precursor has been used to synthesize nanocrystalline Mg-Zn-ferrites. The nature of the prepared precursor is characterized and compared with those of the precursors studied earlier, prepared by the same process. The study has been performed by inorganic and organic elemental analyses, Fourier Transformed Infrared Spectroscopy (FTIR), Mössbauer spectroscopy, X-ray Photoelectron Spectroscopy (XPS), Electron Paramagnetic Resonance (EPR), Electronic absorption spectrometry in the UV-VIS region, Differential Thermal analysis/ Thermogravimetry (DTA-TG) analyses, and X-ray diffraction (XRD) analysis. The collected results determined the precursor as a coordination polymer with monomer unit (NH₄)₄{M [Fe(C₆H₅O₇)₂]₂}, where M=Zn or Mg.      

Copper-cobalt ferrites as catalysts for methanol decomposition

Copper-cobalt ferrites with composition Cu_1?xCo_xFe₂O₄, where x= 0.2 and 0.8 were prepared by thermal treatment of co-precipitated precursor. The obtained materials were characterized by TG-DSC, XRD, Transmission and Conversion Electron Mössbauer spectroscopy and temperature programmed reduction with hydrogen. The catalytic properties of ferrites were tested in methanol decomposition to CO and hydrogen.      

Comparative studies of Pd, Ru, Ni, Cu/ZnAl2O4 catalysts for the water gas shift reaction

The activity of monometallic Pd, Ru, Ni and Cu catalysts supported on spinel ZnAl₂O₄ for water gas shift reaction (WGS) was investigated. The physicochemical properties of each catalyst was studied by XRD, TPR, BET and chemisorption methods. The highest activity was obtained for Cu/ZnAl₂O₄ among the catalysts tested. The activation process carried out in a reducing atmosphere 5%H₂-95%Ar in the case of Cu/ZnAl₂O₄ system lead to the catalytic activity improvement. In the case of copper catalysts, the water gas shift reaction proceeded by the redox surface mechanism between Cu⁰/Cu⁺. The PdZn alloy formation after reduction at 350°C was shown.      

Transport properties of ZrV2O7-V2O5 composites with liquid-channel grain boundary structure

Transport properties (conductivity, transport numbers of oxygen ions, oxygen permeability) are studied for new composites of ZrV₂O₇-25, 30, 35, 40 mol % of V₂O₅ with a liquid-channel grain boundary structure (LGBS) at 680–740°C. It is shown that the composite of ZrV₂O₇-40 mol % of V₂O₅ with LGBS has high selective oxygen permeability of 1.1 × 10^?8 mol cm^?2 s^?1 (T = 740°C, $P'_{O_2 } $ = 0.21 atm, $P''_{O_2 } $ = 0.003 atm, L = 2 mm) and can be used as an ion-transport membrane for separation of oxygen from air.     

Synthesis and spectral characterization of stannocanes of the type [O(CH2CH2S)2SnR2](R=Me1,Bun2,Ph3)

The stannocanes of the type [O(CH₂CH₂S)₂SnR₂](R=Me1,Buⁿ 2,Ph3) have been synthesized in an improved method by the reaction of R₂SnCl₂ with 2, 2′-oxydiethanethiol O(CH₂CH₂SH)₂ in molar ratio of 1:1 at the presence of sodium ethoxide in anhydrous ethanol. The reactions are carried out under inert atmosphere. These compounds have been extensively characterized by FT-IR, UV-Vis spectrophotometry, multi-nuclear (¹H, ¹³C, ¹¹⁹Sn) NMR, elemental analysis and mass spectrometry. The obtained data clearly indicates that, there is a strong interaction between oxygen atom of the ligand as a donor and Sn atom of the organotin species as a Lewis acid acceptor. Therefore, the resulted dithiostannocanes possess a transannular secondary bonding and hypervalency at the central Sn atom which leads to an increase in the coordination number of tin from four to five-coordinated tin.      

Experimental and theoretical studies on the photodegradation of 2-ethylhexyl 4-methoxycinnamate in the presence of reactive oxygen and chlorine species

2-Ethylhexyl 4-methoxycinnamate (EHMC) is one of the most commonly used sunscreen ingredient. In this study we investigated photodegradation of EHMC in the presence of such common oxidizing and chlorinating systems as H₂O₂, H₂O₂/HCl, H₂O₂/UV, and H₂O₂/HCl/UV. Reaction products were detected by gas chromatography with a mass spectrometric detector (GC-MS). As a result of experimental studies chloro-substituted 4-methoxycinnamic acid (4-MCA), 4-methoxybenzaldehyde (4-MBA) and 4-methoxyphenol (4-MP) were identified. Experimental studies were enriched with DFT and MP2 calculations. We found that reactions of 4-MCA, 4-MBA and 4-MP with Cl₂ and HOCl were in all cases thermodynamically favorable. However, reactivity indices provide a better explanation of the formation of particular chloroorganic compounds. Generally, those isomeric forms of mono- and dichlorinated compounds which exhibits the highest hardness were identified. Nucleophilicity of the chloroorganic compounds precursors were examined by means of the Fukui function.      

Preparation and conductivities of polyacrylic acid/polyvinylimidazole grafted and ungrafted iron oxide nanocomposite polymer electrolytes

Nanocomposites of Polyacrylic acid/polyvinylimidazole (PAA/PVI) with grafted and ungrafted iron oxide nanoparticles were prepared by a Reflux method. The Fe₃O₄ nanoparticles with 10 nm average diameter were synthesized by controlled co-precipitation and silanization of Si-PVI on Fe₃O₄ was used to obtain the grafted ones. Grafting becomes important at composites of less PVI that cause drastic decreases in AC conductivity. The content of PVI has important effects on the conductivity mechanism of these composites. The effect of grafting and Polyacrylic acid/polyvinylimidazole molar ratio on the conduction mechanism were studied. The conduction mechanism of iron oxide nanocomposites can be adjusted by changing molar ratio of Polyacrylic acid/polyvinylimidazole and grafting of Fe₃O₄ NPs.      

The phase diagrams of the systems MgCl2 + MgB6O10 + H2O and MgSO4 + MgB6O10 + H2O at 323.15 K and Pitzer model

The solubilities and the relevant physicochemical properties of the systems MgCl₂ + MgB₆O₁₀ + H₂O and MgSO₄ + MgB₆O₁₀ + H₂O at 323.15 K were determined by the method of isothermal dissolution, and the phase diagrams and the diagrams of physicochemical properties versus composition were plotted. Both of the systems belong to a simple eutectic type, and neither double salts nor solid solution were found. Based on the extended Harvie-Weare (HW) model and its temperature-dependent equations, the value of the singlesalt Pitzer parameters ??⁽⁰⁾, ??⁽¹⁾, ??⁽²⁾, and C ^? for MgCl₂, MgSO₄, and Mg(B₆O₇)(OH)₆, the mixed ion-interaction parameters $\theta _{Cl, B_6 O_{10} }$ , $\theta _{SO_4 , B_6 O_{10} }$ , $\Psi _{Mg, Cl, B_6 O_{10} }$ , $\Psi _{Mg, SO_4 , B_6 O_{10} }$ , the average equilibrium constants (lnK _aver) of solids in the systems and the Debye-Hückel parameter A ^? were fitted. Using the Pitzer parameters and the average equilibrium constants of solids at equilibrium, the solubilities of the two systems at 323.15 K have been calculated. Comparisons between the calculated and experimental results show that the predicted solubilities agree well with experimental data.     

Polymer conjugates with potential biological activity based on new derivatives of 2-mercaptobenzoxazole-synthesis and characterization

New potentially biologically active compounds derived from 2-mercapto-benzoxazole were synthesized and coupled on polymeric support of poly (maleic anhydride-alt-vinyl acetate) for the preparation of polymer-drug conjugates with controlled drug release. All compounds were characterized by elemental and spectroscopy (FT-IR, ¹H-NMR) analysis. The toxicological tests recommend the products for further laboratory screening.      

Promoted ternary CuO-ZrO2-Al2O3 catalysts for methanol synthesis

Ternary CuO-ZrO₂-Al₂O₃ catalysts promoted by palladium or gold were prepared and tested in CO hydrogenation reaction at 260°C under elevated pressure (4.8 MPa). The promotion effect of palladium or gold addition on the physicochemical and catalytical properties of CuO-ZrO₂-Al₂O₃ catalysts in methanol synthesis (MS) was studied. The catalysts were characterized by BET, XRD, TPR-H₂, TPD-NH₃ methods. The BET results showed that the ternary system CuO-ZrO₂-Al₂O₃ had the largest specific surface area, cumulative pore volume and average pore size in comparison with the promoted catalysts. The yield of methanol can be given through the following sequence: 5%Pd/CuO-ZrO₂-Al₂O₃ > CuO-ZrO₂-Al₂O₃ > 2%Au/CuO-ZrO₂-Al₂O₃. We also found that the presence of gold or palladium on catalyst surface has strong influence on the reaction selectivity. The high selectivity of gold doped ternary catalyst is explained by the gold-oxide interface sites created on the catalyst surface and the acidity of those systems. The higher selectivity to methanol in the case of the palladium catalyst is explained by the spillover effect between Pd and CuO.      

P-Triazinylphosphonium chlorides as a new group of coupling reagents

Tertiary phosphines in reaction with 2-chloro-4,6-dialkoxy-1,3,5-triazines gave unstable quaternary P-triazinylphosphonium chlorides, which readily decomposed with a departure of the alkyl group of the triazine ring substituent. Stable quaternary P-triazinylphosphonium chlorides were obtained only in reaction of 2-chloro-4,6-diphenoxy-1,3,5-triazine. Both, stable quaternary P-triazinylphosphonium chlorides as well unstable analogues prepared in situ activated carboxylic acid yielding “superactive” triazine esters, useful as highly efficient reagents in peptide bond synthesis.      

Morpho-structural and luminescence investigations on yttrium silicate based phosphors prepared with different precipitating agents

Yttrium silicate doped with cerium (Y₂SiO₅:Ce) was obtained from Y-Ce-Si based precursors prepared by the simultaneous addition of reagents (SimAdd) technique. The synthesis of the precursors was done in well controlled conditions using ammonium oxalate, ammonium carbonate or urea as precipitating agents. Results regarding the influence of precipitating agents on the morpho structural and photoluminescent characteristics of Y₂SiO₅:Ce are reported. The TG analysis in correlation with EGA, FT-IR and XRD investigations reveals the formation of oxalate, hydroxy-carbonate or hydroxy-nitrate based compounds, the same as the conversion of the precursors to well crystallized yttrium silicate. XRD patterns show that the precursors are amorphous except for the sample prepared with ammonium oxalate. Depending on the precipitation conditions, the phosphors phase composition varies from single phase (X2-Y₂SiO₅) to a mixture of phases (X2-Y₂SiO₅, X1-Y₂SiO₅, Y₂O₃). Under UV excitation, phosphors exhibit the specific blue emission of cerium with an intensity that varies from 175.8% (urea) to 96.0% (ammonium carbonate) and to 78.5% (ammonium oxalate). The emission intensity depends on the phase purity and order degree of the phosphors. PACS Classification codes:78.55 Hx, 81.20Fw      

Application of Box-Behnken design with response surface methodology for modeling and optimizing ultrasonic oxidation of arsenite with H2O2

A combined ultrasound (US)/H₂O₂ process was used to oxidize arsenite to arsenate, yielding a synergistic effect value of 1.26. This showed that the combined process could be an effective method of oxidizing arsenite, instead of using either ultrasonic or H₂O₂ oxidation processes. This combined process was successfully modeled and optimized using a Box-Behnken design with response surface methodology (RSM). The effects of the US power density, the initial concentration of arsenite, and the H₂O₂ concentration on the sonochemical oxidation efficiency of arsenite were investigated. Analysis of variance indicated that the proposed quadratic model successfully interpreted the experimental data with coefficients of determination of R ² = 0.95 and adjusted R ² = 0.91. Through this model, we can predict and control the oxidation efficiency under different conditions. Furthermore, the optimal conditions for the oxidation of arsenite were found to be a US power density of 233.26 W L^?1, an initial arsenite concentration of 0.5 mg L^?1, and an H₂O₂ concentration of 74.29 mg L^?1. The predicted oxidation efficiency obtained from the RSM under the optimal conditions was 88.95%. A confirmation test of the optimal conditions verified the validity of the model, yielding an oxidation efficiency of 90.1%.      

Agglomeration of ZnS nanoparticles without capping additives at different temperatures

ZnS nanoparticles were precipitated in diluted aqueous solutions of zinc and sulphide ions without capping additives at a temperature interval of 0.5–20°C. ZnS nanoparticles were arranged in large flocs that were disaggregated into smaller agglomerates with hydrodynamic sizes of 70–150 nm depending on temperature. A linear relationship between hydrodynamic radius (R _a ) and temperature (T) was theoretically derived as R _a =652 - 2.11 T. The radii of 1.9–2.2 nm of individual ZnS nanoparticles were calculated on the basis of gap energies estimated from their UV absorption spectra. Low zeta potentials of these dispersions of ?5.0 mV to ?6.3 mV did not depend on temperature. Interactions between individual ZnS nanoparticles were modelled in the Material Studio environment. Water molecules were found to stabilize ZnS nanoparticles via electrostatic interactions.      

Characterisation of the surface structure and bioactivity of glass and glass ceramics using surface topography

The present paper reports the results of the relationship between the surface topography, microstructure and the in vitro bioactivity of samples with and without fluorapatite content in simulated body fluid. Glasses and glass ceramics belonging to the Li₂O-SiO₂-CaO-P₂O₅-CaF₂ system were prepared by using conventional melting technique following by heat treatment to obtain glass ceramics. This current study demonstrates the benefits of combining two microscopic methods for better investigation of the surface structure. The formation of apatite layer on the surface and the increase in surface roughness proved that the glasses and glass ceramics with bioactive fluorapatite content could satisfy to the requirements for biomaterial applications. The results also showed that the roughness of apatite layer formed after immersion in body fluid on the surface of glasses with fluorapatite was more pronounced than that of equivalent glass ceramic samples cured under the same conditions.      

Investigation of electrical properties of PANI/chalcogenide junctions

Pure Polyaniline (EB) and Polyaniline doped with different protonic acids (ESs) were chemically synthesized using ammonium peroxydisulphate (APS) as an oxidant. Junctions have been prepared by evaporating chalcogenide materials (ZnSe, CdSe) on conducting polyaniline (EB & ESs) pellets using a vacuum evaporation technique. I–V characteristics of junctions have been studied at room temperature using the Keithley electrometer 6517A. I–V measurements show the rectification effect. A junction of ES[PO₄ ^3?] may be preferred over the other junctions due to its low ideality factor and maximum rectification ratio.      

Optimization of synthesis procedure and structure characterization of manganese tungstate nanoplates

A simple and fast chemical method was used for synthesis of manganese tungstate nanoplates in flower-like clusters; while Taguchi robust design was employed as statistical method for optimization of the experimental parameters for the procedure. Ultrafine manganese tungstate plates in flower-like clusters were synthesized via a direct precipitation method involving addition of manganese ion solution to the aqueous tungstate reagent. Effects of various reaction conditions such as manganese and tungstate concentrations, flow rate of reagent addition and reactor temperature on the thickness of the synthesized manganese tungstate plates were investigated experimentally. Analysis of variance (ANOVA) showed that manganese tungstate nanoplates could be effectively synthesized by tuning significant parameters of precipitation procedure. Meanwhile, optimum conditions for synthesis of MnWO4 nanoplates via this simple, fast, and cost effective method were proposed. The structure and composition of the prepared nanoplates under optimum conditions were characterized by EDX, X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), FT-IR spectroscopy, and photoluminescence techniques.      

Salutaridine and its derivatives as thebaine-equivalents in the synthesis of aporphines

Here we report the transformation of tetracyclic morphinan salutaridine (1) into 2,3,10,11-tetrasubstituted (R)-aporphines. This method serves as another chemical proof of the previously verified biosynthetic connection with pentacyclic morphinan-6,8-diene-type thebaine. In the presence of nucleophiles, this procedure could lead to pharmacologically interesting new tetrasubstituted aporphinoids. The enantioselective synthesis of 7S-salutaridinol (2) has been also achieved in order to investigate the acid-catalyzed reactions of this natural morphinan.