On-line preconcentration and determination of Au(III) in various environmental/industrial samples by flame atomic absorption spectrometry

A rapid and simple on-line method is described for the determination of Au(III) in various samples. The method is based on the sorption of gold(III) on Lewatit MonoPlus TP207 chelating resin including the iminodiacetate group, which is used as sorbent material and packed in a minicolumn. The chemical variables such as the pH of the sample solution, eluent type, interfering ions and concentrations of reagents, and instrumental variables such as sample loading volume, reagents flow rates, and tubing length, which affect the efficiency of the method were studied and optimised. Au(III) was sorbed on the chelating resin, from which it could be eluted with 3 mol L^?1 HCl, and then introduced directly to the nebuliser-burner system of FAAS. The limit of detection of the method was 0.2 µg L^?1 while the relative standard deviation was <4.0% for 20 µg L^?1 Au(III) concentration. The preconcentration factor was found to be 106 while the optimised sample volume was 15.3 mL. The accuracy of the method was verified by analysing the certified reference material. The developed method was applied successfully for the determination of gold in different samples with satisfactory results.     

Purification of transferrin by magnetic immunoaffinity beads

Immunoaffinity adsorbent for transferrin (Tf) purification was prepared by immobilizing anti‐transferrin (Anti‐Tf) antibody on magnetic monosizepoly(glycidyl methacrylate) beads, which were synthesized by dispersion polymerization technique in the presence of Fe₃O₄nanopowder and obtained with an average size of 2.0 μm. The magnetic poly(glycidyl methacrylate) (mPGMA) beads were characterized by Fourier transform infrared spectroscopy, swelling tests, scanning electron microscopy, electron spin resonance spectroscopy, thermogravimetric analysis and zeta sizing analysis. The density and swelling ratio of the beads were 1.08 g/cm³ and 52%, respectively. Anti‐Tf molecules were covalently coupled through epoxy groups of mPGMA. Optimum binding of anti‐Tf was 2.0 mg/g. Optimum Tf binding from aqueous Tf solutions was determined as 1.65 mg/g at pH 6.0 and initial Tf concentration of 1.0 mg/mL. There was no remarkable loss in the Tf adsorption capacity of immunoaffinity beads after five adsorption–desorption cycles. Tf adsorption from artificial plasma was also investigated and the purity of the Tf molecules was shown with gel electrophoresis studies.     

Stereoselective synthesis of optically active cyclopenta[c]pyrans and cyclopenta[c]furans by the intramolecular Pauson–Khand reaction

An intramolecular Pauson–Khand reaction of enynes derived from homoallyl, homopropargyl, and allyl alcohols is described. 2-Heteroaryl-substituted homoallyl, homopropargyl, and allyl alcohols are easily and efficiently resolved through enzymatic resolution in high ee (91–99%) and with a known stereochemistry. Each enantiomerically enriched enyne derived from homoallyl and homopropargyl alcohols affords the conformationally most stable diastereomeric cyclopenta[c]pyran ring system as the sole product, whereas enantiomerically enriched enynes derived from allyl alcohols give a diastereomeric cis:trans mixture of the cyclopenta[c]furan ring system.     

Synthesis,crystal structure and catalytic activity for H2O2 disproportionation of the manganese(II) coordination polymer {[Mn(O2C(CF2)8CO2)(phen)2]H2O}n (phen = 1,10-phenanthroline)

The title polymeric complex {[Mn(O₂C(CF₂)₈CO₂)(phen)₂]H₂O}_n was synthesized through the reaction of 1,10-phenanthroline, perfluorosebacic acid and MnCO₃ · H₂O. The molecular structure was characterized by X-ray diffraction, elemental analysis, thermal gravimetry, IR and UV–Vis spectroscopy and its catalytic activity has been studied. X-ray structure analysis shows that each Mn(II) ion is octahedrally coordinated by two bidentate phenanthroline ligands and the carboxylate oxygen atoms from two symmetry related perfluorosebacate ligands, which are coordinated in cisoid positions. The structure consists of polymeric chains, with the perfluorosebacato ligand bridging the Mn(II) ions in a monodentate fashion. Crystallographic characterization shows a supramolecular structure involving hydrogen bonds, π–π and π-ring interactions. The catalytic results indicated that the complex has reasonably good activity towards the disproportionation of hydrogen peroxide into water and dioxygen in methanol and it does not exhibit saturation kinetics with the substrate. The initial reaction rates and their temperature and base dependencies were investigated by monitoring the dioxygen evolution. Kinetic studies revealed a first-order dependence on the catalyst concentration. Activation parameters have been calculated at 301 K.     

FT-IR spectra, vibrational assignments, and density functional calculations of imidazo[1,2-a]pyridine molecule and its Zn(II) halide complexes

The geometry, frequency, and intensity of the vibrational bands of imidazo[1,2-a]pyridine (which is abbreviated as impy) were obtained by the density functional theory (DFT) calculations with BLYP, B3LYP, and B3PW91 functionals and 6-31G(d) basis set. The optimized geometric bond lengths and bond angles are in good agreement with the available X-ray data. The infrared spectrum of imidazo[1,2-a]pyridine was computed by the DFT method in order to reproduce the vibrational wavenumbers and intensities with an accuracy, which allows reliable vibrational assignments. Total energy distribution and isotopic shifts have been calculated in order to help for the perfect assignment of the vibrational modes. The zinc halide complexes Zn(impy)₂X₂ [X = Cl, Br, and I] have also been synthesized. The compounds were characterized using the elemental analysis, FT-IR spectra, and quantum chemical calculations. The geometry optimization of Zn(impy)₂X₂ yields distorted tetrahedral environment around Zn ion.     

Novel phthalocyanines with naphthalenic substituents

Phthalocyanines with four naphthyl-malonic ester groups on the periphery were synthesized by cyclotetramerization of 4-(1,1-dicarbethoxy-2-(1-naphthyl)-ethyl)-phthalonitrile. The new compounds were characterized by spectroscopic methods. The electronic spectra exhibit intense π–π* transitions from the naphthyl moiety together with the characteristic Q and B bands of the phthalocyanine core. The electrochemical properties of the 2,9,17,23-tetra-(1,1-(dicarbethoxy)-2-(1-naphthyl)-ethyl) phthalocyaninato copper(II) complex were studied by cyclic voltammetry.     

Style goods pricing with demand learning

For many industries (e.g., apparel retailing) managing demand through price adjustments is often the only tool left to companies once the replenishment decisions are made. A significant amount of uncertainty about the magnitude and price sensitivity of demand can be resolved using the early sales information. In this study, a Bayesian model is developed to summarize sales information and pricing history in an efficient way. This model is incorporated into a periodic pricing model to optimize revenues for a given stock of items over a finite horizon. A computational study is carried out in order to find out the circumstances under which learning is most beneficial. The model is extended to allow for replenishments within the season, in order to understand global sourcing decisions made by apparel retailers. Some of the findings are empirically validated using data from U.S. apparel industry.     

On Riesz spaces with b-property and strongly order bounded operators

A Riesz space E is said to have the b-property if each subset that is order bounded in the bidual remains to be order bounded in E. Properties of a Riesz space with the b-property, the relationship between the b-property and various classes of operators are studied.     

Comparison of pre-irradiation and mutual grafting of 2-chloroacrylonitrile on cellulose by gamma-irradiation

Radiation-induced graft polymerization is one of the best methods for obtaining materials with new properties. In this work, radiation grafting of 2-chloroacrylonitrile to cellulose by mutual and pre-irradiation grafting methods was investigated. The grafting yield was enhanced by applying the emulsion grafting method. The grafting yield determined in the above systems was observed as 27% at highest and 6% at lowest. The effects of concentration of monomer, reaction time and reaction temperature on grafting yield were studied. Evidence of grafting has been based on the comparative studies of cellulose and grafted cellulose by infrared spectroscopy, thermal analysis and contact angle measurement. Grafting enhances thermal stability of cellulose backbone.     

Asymptotic properties of a new Sturm–Liouville problem with retarded argument

In this work, we study the asymptotic properties of a new Sturm–Liouville problem with retarded argument. Contrary to previous works, differential equation includes eigenparameter as a quadratic function. In the considered problem arise new difficulties. Copyright © 2013 John Wiley & Sons, Ltd.