Structural characterization and dielectric properties of the solid solutions AgPb(Sb,Bi)S3

The new solid solutions AgPbSb_1 − x Bi _x S₃ were prepared by solid state reactions. The phases were characterized by powder X-ray diffractions (XRD), scanning electron microscopy, and thermal analysis. The XRD patterns of different members (x = 0.5, 0.7, 0.8, and 1.0) are consistent with pure phases crystallizing in the cubic PbS-type structure. The electrical characterization was carried out using ac impedance spectroscopy and dc methods. The temperature dependence of the dc conductivity shows typical semiconductor Arrhenius behavior. The impedance measurements were performed in the frequency range of 0.1 Hz to 10 MHz and at the temperature range of 15 °C to 350 °C. The ac conductivity conforms to Jonscher’s universal power law. The frequency dependence of the dielectric permittivity follows the normal dielectric material behavior, and the relaxation is thermally activated. The frequency and temperature dependences of the electrical data are found to follow Summerfield scaling formalism.     

Photodegradation of 2-nitrophenol catalyzed by CoO, CoS and CoO/CoS nanoparticles

The nanoparticles of CoO, CoS and CoO/CoS composite are synthesized using precipitation method. The X-ray diffraction, UV–Vis absorption spectroscopy, energy dispersive X-ray spectroscopy, scanning electron microscopy and FT-IR spectroscopy are used to characterize the prepared nanoparticles. The EDX analysis shows the formation of CoO_0.67S_0.33 composite. The XRD pattern indicates the hexagonal structure for nanocomposite. The formation of Co–O and Co–S bonds is confirmed by FT-IR spectra. The band-gap energies of 2.97, 3.06 and 2.91 eV are obtained from UV–Vis spectra of CoO, CoS and CoO/CoS nanoparticles, respectively. The results of photodegradation of 2-nitrophenol show that the photoreactivity order of nanocatalysts is CoO/CoS > CoO > CoS. The pseudo first-order kinetic rate constants of 6.4 × 10^?3, 4.3 × 10^?3 and 12.2 × 10^?3 min^?1 are obtained for CoO, CoS and CoO/CoS nanoparticles, respectively, at photodegradation reaction conditions of pH 10, 30 mg/L of 2-NP and 1.3 g/L of the catalyst. The proposed nanocomposite shows an acceptable reusability and stability against photocorrosion in four-cycle photodegradation experiments.     

Thermal behaviour,surface properties and vibrational spectroscopic studies of the synthesized Co3xNi3−3x(PO4)2·8H2O (0 ≤ x ≤ 1)

Co_3xNi_3−3x(PO₄)₂·8H₂O (x = 1, 0.8, 0.6, 0.4, 0.2, and 0) were synthesized via simple wet chemical reaction and energy saving route method. The final decomposition products of hydrates are corresponding anhydrous tri(cobalt nickel) diphosphates. The metal and water contents of the synthesized hydrates were confirmed by AAS and TG/DTG/DTA techniques, respectively. The observed metal and water contents agree well with the formula of the title compounds. The crystal structures and lattice parameters as well as crystallite sizes of the studied compounds were determined using XRD data. The results from XRD and TG/DTG/DTA techniques confirmed that Co_3xNi_3−3x(PO₄)₂·8H₂O at all ratios were the single phase. The FTIR spectra of studied compounds were recorded and assigned. The thermal behaviours of single and binary tri(cobalt nickel) diphosphate octahydrates were studied for the first time. The morphologies of the studied compounds were investigated by using the SEM technique. The micrographs of all studied compounds exhibited the thin plated morphology. The surface area and the pore size data of anhydrous forms were measured by N₂ adsorption at −190 °C according to the BET method. The anhydrous forms of binary metal phosphate at x = 0.8, Co_2.4Ni_0.6(PO₄)₂, exhibits the highest surface area and expects to improve the catalytic activity.     

Structural,mechanical, electronic,optical properties and effective masses of CuMO2 (M = Sc,Y, La) compounds: First-principles calculations

The structural, elastic, mechanical, electronic, optical properties and effective masses of CuM_IIIBO₂ (M_IIIB = Sc, Y, La) compounds have been investigated by the plane-wave ultrasoft pseudopotential technique based on the first-principles density-functional theory under local density approximation. The equilibrium structural parameters are in good agreement with previous experimental and theoretical data. To our knowledge, there are no available data of elastic constants for comparison. The bulk, shear and Young's modulus, ratio of B/G, Poisson's ratio and Lamé's constants of CuM_IIIBO₂ have been studied. The electronic structures of CuM_IIIBO₂ are consistent with other calculations. The population analysis, charge densities and effective masses have been shown and analyzed. The imaginary and real parts of the dielectric function, refractive index and extinction coefficient of CuM_IIIBO₂ are calculated. The interband transitions to absorption of CuM_IIIBO₂ have been analyzed.     

Determination of cyromazine and melamine in chicken eggs using quick,easy, cheap,effective, rugged and safe (QuEChERS) extraction coupled with liquid chromatography–tandem mass spectrometry

A rapid and sensitive method has been developed for the simultaneous detection of cyromazine and melamine in chicken eggs using the quick, easy, cheap, effective, rugged and safe (QuEChERS) method coupled with liquid chromatography–tandem mass spectrometry (LC–MS/MS). The optimal extraction solvent for the liquid–liquid extraction was 5 mL of acetonitrile with a 0.1 M hydrochloric acid aqueous solution (99.5:0.5, v/v). The extract was cleaned with 0.5 g of anhydrous magnesium sulfate and 10 mg of graphitized carbon black. The analysis of cyromazine and melamine was accomplished by combining the use of an anion exchange LC column with tandem mass spectrometry in the positive electrospray ionization mode with selected reaction monitoring mode (SRM). The detection limits were 1.6 ng g⁻¹ for cyromazine and 8 ng g⁻¹ for melamine, and the quantitation limits were 5.5 ng g⁻¹ for cyromazine and 25 ng g⁻¹ for melamine. The recoveries of cyromazine and melamine in the spiked egg samples were 83.2% and 104.6%, respectively, with an relative standard deviation (RSD) of less than 18.1%. The intra-day and inter-day precisions, represented by the RSD, ranged from 1.5% to 8.8% and 6.8% to 14.3%, respectively. The proposed method was tested by analyzing chicken eggs from the markets and from the veterinary medicine laboratory. The concentrations of cyromazine and melamine detected in these samples were in the range of 20–94 ng g⁻¹. The results demonstrated that the QuEChERS method combined with LC–MS/MS is a simple, rapid and inexpensive method for the analysis of cyromazine and melamine in eggs.     

Potentiality of partial least-squares multivariate calibration in the spectrophotometric analysis of binary mixtures of purine bases

Abstract  

A partial least-squares (PLS) modeling was developed for the simultaneous spectrophotometric determination of adenine (AD) and guanine (GU). The determination of these analytes is pharmacologically necessary. Multivariate calibration is used because of spectral overlapping. The calibration set contained AD and GU in the concentration range of 1.4–20.3 and 1.5–25.7 μg cm⁻³, respectively. The absorption spectra were recorded from 200 to 300 nm. The predicted residual error sum-of-squares for AD and GU was 0.0500 and 0.4000 for number of principal components 3 and 2, respectively. The root mean square error of prediction for AD and GU was 0.0913 and 0.2582, respectively. The limits of detection were 0.02 and 0.03 μg cm⁻³ for AD and GU, respectively. The proposed method allows the simultaneous determination of AD and GU in spiked real matrixes of human urine, serum, and plasma.     

Study of a fluorescence quenching mechanism of enoxacin and its determination in human serum and urine samples

The maximum emission wavelength of dopamine is 317 nm with excitation at 290 nm. The relative fluorescence intensity of dopamine decreased in the presence of enoxacin, which showed that fluorescence quenching occurred. The Stern-Volmer (S-V) plot showed a nonlinear relationship between the relative fluorescence intensity of dopamine and the concentration of enoxain. The quenching mechanism was studied and the results suggested that both dynamic and static quenching processes were responsible for the observed positive deviation in the S-V plot. When the S-V plot was modified by logarithm, the linear relationship was obtained between logF ₀/F and C in the range of 0.10 to 13.0 μg/mL (where F ₀ is the relative fluorescence intensity of dopamine, F is the relative fluorescence intensity of dopamine in the presence of enoxacin, and C is the concentration of enoxacin). The fluorescence quenching method for the determination of enoxacin was developed. The linear regression equation of the calibration graph of enoxacin was C = 13.70 (logF ₀/F) − 0.5836, with the correlation coefficient 0.9984. The detection limit was 2.0 ng/mL and the relative standard deviation was 2.52%. The effects of pH, the stability of dopamine in the presence of enoxacin, and foreign ions on the determination of enoxacin have been examined. The recovery of enoxacin was from 94.9 to 103.0% in a human serum sample and from 94.9 to 108.0% in a urine sample. The method is simple, rapid, and can be used for the determination of enoxacin in human serum and urine samples with satisfactory results. The text was submitted by the authors in English.     

Effect of chemical condition of technetium-99m sodium pertechnetate on the active kit components and radiolabeling yield of Tru-Scint® ADTM monoclonal antibody kit

The chemical condition of^99mTc eluate obtained from a⁹⁹Mo-^99mTc generator is a function of the source, time elapsed after elution and age of the eluate. The radiochemical purity and stability of^99mTc labeled MAb-170 (Tru-Scint^®AD^TM, photoactivated monoclonal antibody kit) preparations was evaluated comparing pertechnetate source of known age and elution history. The effect of H₂O₂, a radiolytic impurity in^99mTc eluates, on the active kit components stannous ion and photoactivated MAb and radiolabeling, yield has been investigated. The lyophilized Tru-Scint^® AD^TM kit has been labeled with 20 to 80 mCi in 0.5 to 4.0 ml of Sodium Pertechnetate^99mTc Injection, USP. The eluates were obtained from three brands of generators and used up to six hours after elution. The kits were reconstituted either with Sodium Pertechnetate^99mTc Injection, USP or Sodium Chloride Injection, USP, 0.9% containing known amounts of H₂O₂. The reconstituted kits were analyzed for radiolabeling yield and radiochemical impurities, stannous ion and protein sulfhydryl group. The results indicated that the radiolabeling yield is a function of both the chemical condition of^99mTc eluate, generator brand and the radiolabeling parameters like reconstitution volume and activity. The observed radiolabeling yield differences did not depend on the amount of chemical technetium in the eluate. The major radiochemical impurities at 15-minute post labeling have been identified as the^99mTc-buffer complex and column adsorbed reduced^99mTc (^99mTc-Ad) species and not the unreduced^99mTcO ₄ ^– .     

Development and validation of a high-throughput high-performance liquid chromatographic assay for the determination of caffeine in food samples using a monolithic column

The present study reports the development and validation of a high-throughput high-performance liquid chromatographic (HPLC) assay for the determination of caffeine in food samples. The analyte was separated rapidly from sample matrix using a short monolithic column (50 mm × 4.6 mm i.d.). The flow rate was 3.0 mL min⁻¹, while the mobile phase consisted of ACN/water (10:90, v/v). Caffeine was detected directly at 274 nm. Under the optimal HPLC conditions, the sampling rate was 60 h⁻¹. The assay was validated for linearity, LOD and LOQ, precision, selectivity and ruggedness. The case of external calibration versus standard addition for the analysis of real samples was also examined. The proposed assay was applied to the analysis of beverages and coffee samples.     

Characterization of a few Mexican clays

The characterization of a few Mexican clays with chemical treatmentfor possible application as catalysers is shown. The natural clays are treatedwith H₂ SO₄ , HF, F₃ CSO₃ H, ClSO₃ H, HClO₄ and their behavior in reactions with some alcoholswas recorded. The analysis were made before and after using the clays as catalysers.The clays were characterized by Mössbauer spectroscopy, X-ray diffraction,X-ray fluorescence analysis, and differential thermo analysis. The predominantmineral species are: montmorillonite, christobalite and quartz. The main elementsare: Si, Al, Fe, Ca, K, etc. The Mössbauer results show mainly a paramagneticdoublet of Fe₃₊ . The clays behave similarly as described in theliterature.     

Oxidation of naphthalene and phenanthrene by pyridinium fluorochromate (PFC)—a kinetic and mechanistic study

The kinetics of the oxidation of naphthalene and phenanthrene by pyridinium fluorochromate, C₅H₅NHCrO₃F, PFC, has been studied. The main product of the oxidation is the corresponding quinone. While each oxidation, studied in aqueous acetic acid (80–95%, v/v) medium, is first order with respect to the oxidant, the rate is almost independent of the substrate concentration. The reactions are catalyzed by acid, the acid-catalyzed reactions being very fast, which precluded determination of their order in acid medium. The kinetic isotope effect, k_H/k_D is 5.50 at 303 K for naphthalene. The reaction does not induce polymerization of acrylonitrile. The effects of temperature and solvent compositions were studied and activation parameters evaluated. Probable mechanisms are discussed.     

The application of the perrin–agishev model for calculation of the translational diffusion coefficients of liquid dichloroalkanes

The article presents the translational diffusion coefficients calculated for dichloroalkanes series C _n H_{2 n} Cl₂ (where n =?6, 8, 10, 12) in the liquid state, with the use of the Perrin and Agishev model. It has been shown that the molecules of dichloroalkanes assume a mutually parallel arrangement in three possible coordinations. The model of arrangement, orientations and packing of the molecules has been presented. The activation parameters of the compounds studied have been discussed. The physical and structural properties of the liquids studied (macroscopic density, electron density and molecular weight) are correctly described within the van der Waals model predicting their orientations and packing. The formulae linking the diffusion, viscosity and temperature for the liquids have been presented. The assumption that each molecule can be approximated by an ellipsoid of the semiaxes lengths a, b and c has been justified. The translations become slower with increasing volume and weight of the molecule. The diffusion coefficients decrease with increasing molecular weight.     

Use of cetyltrimethylammonium bromide as surfactant for the determination of copper and chromium in gasoline emulsions by electrothermal atomic absorption spectrometry

In this work, the use of cetyltrimethylammonium bromide as surfactant for the preparation of oil-in-water emulsions for the determination of Cu and Cr in gasoline by electrothermal atomic absorption spectrometry (ET AAS) was evaluated. The surfactant amount was tested in the range of 25 to 300 mg, added to 2 ml of gasoline, and completed to 10 mL with 0.1% (v/v) nitric acid solution. 150 mg of surfactant was found optimum, and a sonication time of 10 min sufficient to form an oil-in-water emulsion that was stable for several hours. The ET AAS temperature program was established based on pyrolysis and atomization curves. The pyrolysis temperatures were set at 700 and 1300 °C for Cu and Cr, respectively and the selected atomization temperatures were 2400 and 2500 °C. The time and temperature of the drying stage and the atomization time were experimentally tested to provide optimum conditions. The limits of detection were found to be 5 μg L^− 1 and 1.5 μg L^− 1 for Cu and Cr, respectively in the original gasoline samples. The relative standard deviation (RSD) ranged from 4 to 9% in oil-in-water emulsions spiked with 5 μg L^− 1 and 15 μg L^− 1 of each metal, respectively. Recoveries varied from 90 to 98%. The accuracy of the proposed method was tested by an alternate procedure using complete evaporation of the gasoline sample. The method was adequate for the determination of Cu and Cr in gasoline samples collected from different gas stations in Salvador, BA, Brazil.     

Electrochemical activity of rhodium complexes supported on fibrous-carbon material

The redox properties of heterogenized Rh^I, Rh^II, and Rh^III complexes with different, particularly organophosphorus, ligands were studied by cyclic voltammetry (CVA). The support is a carbon-paste electrode based on a fibrous-carbon material and activated carbon. The electrochemical reduction of Rh^III produces Rh metal, which further catalyzes hydrogen evolution. After the reduction of water-soluble binuclear Rh^II complexes, the CVA curves exhibit peaks of electrocatalytic hydrogen evolution and irreversible Rh^I→Rh^II oxidation. The Rh^II complexes with organophosphorus ligands are characterized only by the peak of Rh^I→Rh^II oxidation. After reduction, the Rh^I complexes behave as a pseudo-reverse Rh⁰/Rh^I pair. The electron-donating properties of the ligand determine the reversibility of the system. The degree of structurization of the carbon matrix and the presence of phosphorus(v) atoms in it affect the electrochemical activity of the Rh^II and Rh^I complexes. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 908–914, May, 1999.     

Viscosity of Aqueous Solutions of Lithium,Sodium, Potassium,Rubidium and Caesium Cyclohexylsulfamates from 293.15 to 323.15 K

The viscosities of aqueous solutions of lithium, sodium, potassium, rubidium and caesium cyclohexylsulfamates were measured at 293.15, 298.15, 303.15, 313.15 and 323.15 K. The relative viscosity data were analyzed and interpreted in terms of the Kaminsky equation, η _r=1+Ac ^1/2+Bc+Dc ². The viscosity A-coefficient was calculated from the Falkenhagen-Dole theory. The viscosity B-coefficients are positive and relatively large. Their temperature coefficient ∂ B/∂ T is negative or near zero for lithium and sodium salts whereas for potassium, rubidium and caesium salts it is positive. The viscosity D-coefficient is positive. This was explained by the size of the ions, structural solute–solute interactions, hydrodynamic effect, and by higher terms of the long-range Debye-Hückel type of forces. From the viscosity B-coefficients the thermodynamic functions of activation of viscous flow were calculated. The limiting partial molar Gibbs energy of activation of viscous flow of the solute was divided into contributions due to solvent molecules and the solute in the transition state. The activation energy of the solvent molecules was calculated using the limiting Gibbs energy of activation for the conductance of the solute ions. The activation energy of the solvent molecules was then discussed in terms of the nature of the alkali-metal ions and their influence on the structure of water. The limiting activation entropy and enthalpy of the solute for activation of viscous flow were interpreted by ion-solvent bond formation or breaking in the transition state of the solvent. The hydration numbers of the investigated electrolytes were calculated from the specific viscosity of the solutions.     

Determination of ferruginol in rat plasma via high‐performance liquid chromatography and its application in pharmacokinetics study

Ferruginol, a diterpene phenol, has recently received attention for its extensive pharmacological properties, including anti‐tumor, antibacterial, cardio‐protective and gastroprotective effects. In the present study, a high‐performance liquid chromatographic (HPLC) method was developed for determination of ferruginol in rat plasma and applied for the pharmacokinetics study. The HPLC assay was performed with a VP ODS‐C₁₈ column. The mobile phaseconsisted of methanol and 1% acetic acid solution (90:10, v/v). The flow rate was 1.0 mL/min, and the wavelength was set at 270 nm. This method was linear over the studied range of 0.1–10.0 µg/mL for ferruginol. The correlation coefficient was 0.9998. The intra‐day and inter‐day precisions were better than 4 and 5%, respectively. The extraction recovery and accuracy were greater than 97 and 96%, respectively. The detection limit was 30 ng/mL. The mean maximum concentration of ferruginol in rat plasma was 3.14 µg/mL at 40 min after oral administration at a dose of 20 mg/kg. Ferruginol was absorbed quickly p.o. with t_1/2ka = 14.86 min and had a high rate of elimination with t_1/2 = 41.73 min. The pharmacokinetic process of ferruginol in rat was well described with a one‐compartment model. Copyright © 2009 John Wiley & Sons, Ltd.     

Ruthenium(III)-catalyzed and uncatalyzed kinetic studies on the oxidation of sulfanilic acid by chloramine-T in perchloric acid medium: a mechanistic approach

The kinetics of the oxidation of sulfanilic acid (SAA) by sodium N-chloro-p-toluenesulfonamide (CAT) in the presence and absence of ruthenium(III) chloride have been investigated at 303 K in perchloric acid medium. The reaction shows a first-order dependence on [CAT]_o and a non-linear dependence on both [SAA]_o and [HClO₄] for both the ruthenium(III)-catalyzed and uncatalyzed reactions. The order with respect to [Ru^III] is unity. The effects of added p-toluenesulfonamide, halide, ionic strength, and dielectric constant have been studied. Activation parameters have been evaluated. The rate of the reaction increases in the D₂O medium. The stoichiometry of the reaction was found to be 1:1 and the oxidation product of SAA was identified as N-hydroxyaminobenzene-4-sulfonic acid. The ruthenium(III)-catalyzed reactions are about four-fold faster than the uncatalyzed reactions. The protonated conjugate acid (CH₃C₆H₄SO₂NH₂Cl⁺) is postulated as the reactive oxidizing species in both the cases.     

Optical and other physical characteristics of amorphous Ge15Te85−xCux alloys

Composition dependencies of the optical properties of as- deposited amorphous Ge₁₅Te_85−xCu_x (x = 2, 3, 4, 5 and 6 at %) prepared by thermal evaporation have been studied. The optical transmission and reflection spectra are measured in the wavelength range (200–1200 nm). The optical absorption coefficient are studied for as- deposited samples. The optical absorption edge shift to higher energy range, as the copper content, x, increases in the film. Tauc's relation for the allowed direct transition is successfully describing the mechanism of the optical absorption. The refractive index, n has been determined from the transmission spectra measured at normal incidence. The absorption coefficient, α, therefore extinction coefficient, k, have been determined from the transmission spectra at the strong absorption region. The dispersion of refractive index is discussed in terms of the Single-oscillator Wimple–DiDomenico model. The optical dielectric constant is also estimated. The average heat of atomization and related parameters such as the average coordination number were also calculated from the heat of atomization and coordination number of the used elements. These obtained results were discussed in terms of chemically ordered network model and constraints theory.     

CO2预处理操作条件对Ni-Co双金属催化剂性能与结构的影响

与传统H₂预处理方法相比,新型H₂+CO₂预处理方法（HCD）能显著提升Ni-Co双金属催化剂的沼气重整活性及抗积碳性能. 考察了HCD预处理操作条件对催化剂性能与结构的影响. 较好的HCD预处理操作条件是在催化剂经H₂处理之后,再用175-200 mL·min^-1的原料气CH₄/CO₂（比例为0：10）在780-800 ℃下还原0.5-1h. 在优化预处理操作条件下对催化剂进行了511 h的耐久性考察,并运用X射线衍射（XRD）、热重-差示扫描量热（TG-DSC）、透射电子显微镜（TEM）等手段对耐久性测试后的催化剂进行了表征. 在511 h 的稳定性实验内,CH₄、CO₂转化率,H₂、CO选择性及H₂/CO体积比分别高达96%、97%,98%、99%及0.98. 催化剂在测试期间的平均积碳速率仅为0.2 mg·g^-1·h^-1. 在该预处理操作参数下,催化剂拥有最好的综合性能和良好的耐久性.     

Synthesis,characterization, speciation and biological studies on metal chelates of 1-benzoyl(1,2,4-triazol-3-yl)thiourea

Proton-ligand association constants of 1-benzoyl(1,2,4-triazol-3-yl)thiourea (BTTU) and its complex formation constants with some bivalent metal ions Ni(II), Co(II), Mn(II), Zn(II), and Cu(II), have been determined potentiometrically in 50% EtOH–H₂O and 0.1 M NaNO₃. The complexes formed in solution have a stoichiometry of 1:1 and 1:2 [M:L], where M represents the metal ion and L the BTTU ligand. The corresponding thermodynamic parameters are derived and discussed. The complexes are stabilized by enthalpy changes and the results suggest that complexation is an enthalpy-driven process. The effects of metal ion, ionic radius, electronegativity, and nature of ligand on the formation constants are discussed. The formation constants of the complexes with 3d transition metals follow the order Mn²⁺ < Co²⁺ < Ni²⁺ < Cu²⁺ > Zn²⁺. The metal complexes were synthesized and characterized by elemental analyses, conductance, IR, ¹H NMR, and magnetic measurements. The low magnetic moment of 0.11 BM for the Cu(II) complex is suggestive of dimerization through Cu–Cu interaction. The concentration distribution diagrams of the complexes were evaluated. The ligands and their metal complexes have been screened in vitro against some bacteria and fungi.