K2M(H2P2O7)2·2H2O (M = Ni,Cu, Zn): ortho­rhom­bic forms and Raman spectra

The crystal structures of three isotypic ortho­rhom­bic dihydrogendiphosphates, namely dipotassium copper(II)/nickel(II)/zinc(II) bis­(dihydrogendiphosphate) dihydrate, K₂M(H₂P₂O₇)₂·2H₂O (M = Cu, Ni and Zn), have been refined from single‐crystal data. The M²⁺ and K⁺ cations are located at sites of m symmetry, and the P atoms occupy general positions. These compounds also exist in triclinic forms with very similar structural features. The structures of both forms are compared, as well as the geometry of the MO₆ octa­hedron, which is considerably elongated towards the water mol­ecules for M = Ni and Cu. Such elongation has not been observed among the other representatives of the family. A Raman study of the whole series K₂M(H₂P₂O₇)₂·2H₂O (M = Mn, Co, Ni, Cu, Zn and Mg) is reported.     

Development of carbon paste electrode modified with cadmium ion-imprinted polymer for selective voltammetric determination of Cd2+

A simple and fast voltammetric method based on a new electrode composed of carbon paste electrode/bifunctional hybrid ion imprinted polymer (CPE/IIP) was developed for the quantification of Cd²⁺ in water samples. The voltammetric measurements by Differential Pulse Voltammetry were performed by using CPE containing 11.0 mg of IIP under phosphate buffer solution at concentration 0.1 mol L^?1 and pH 6.5. The electrochemical method was carried out by Cd²⁺ preconcentration at ?1.2 V during 210 s, followed by anodic stripping. The performance of IIP towards Cd²⁺ determination was evaluated by comparison to non-imprinted polymer, whose detectability of IIP was much higher (45%). The sensitivity of the sensor was found to be 0.0105 µA/µg L^?1. The limits of detection and limits of quantification were found to be 4.95 μg L^?1 and 16.4 μg L^?1, respectively. The developed method was successfully applied to Cd²⁺ determination in mineral, tap and lake water samples, whose results are in agreement with thermospray flame furnace atomic absorption spectrometry (TS-FF-AAS) used as reference analytical technique. According to achieved results, the developed method can be used for routine analysis of quality control of water samples from different sources.     

Fast Algorithms for Centro-Symmetric and Centro-Skewsymmetric Toeplitz-Plus-Hankel Matrices

Subject of the paper are centro-symmetric and centro-skewsymmetric Toeplitz-plus-Hankel matrices with the property that all central submatrices are nonsingular. Fast algorithms are presented that solve an n×n system of equations with O(n ²) operations in sequential and O(n) operations in parallel processing and compute the ZW-factorization with the same computational complexity. These algorithms are more efficient than existing algorithms because they fully exploit the symmetry properties of the matrices.     

New Method for Determining the Degree of Cellulose I Crystallinity by Means of FT Raman Spectroscopy

A Raman crystallinity index – Xc_Raman – characterizing the degree of crystallinity of partially crystalline cellulose I samples was created, utilizing the crystallinity dependence of CH₂ bending modes. For calibration, physical mixtures containing different mass fractions of crystalline cellulose I and its amorphous form were prepared. Crystallinities from 0 to 60% were generated. Relative intensity ratios of the Raman lines I and I characterizing crystalline and amorphous parts of cellulose I correlated linearly with the mass fraction of crystalline cellulose I of the mixtures. Xc_Raman values of microcrystalline celluloses of different origins and varying degree of crystallinity correlated reasonably with results obtained from NMR spectroscopy (Xc_NMR values).     

Terpolymerization of acrylonitrile,styrene, and 2,3-dibromopropyl acrylate

The terpolymerization of acrylonitrile with styrene and 2,3-dibromopropyl acrylate in emulsion and dimethyl formamide solution was investigated. Polymerizations, when stopped at low conversions, yielded terpolymers that showed good agreement between experimental and theoretical copolymerization composition data, calculated from the Alfrey-Goldfinger equation. The relationship between monomer feed and terpolymer compositions is displayed on triangular coordinate graphs proposed by Slocombe. By using a computer program the lines of unique composition and binary azeotropic composition for both systems were established. In the case of emulsion polymerization the azeotropic ternary point was determined at a molar ratio for acrylonitrile/styrene/2,3-dibromopropyl acrylate of 0.27/0.61/0.12. The experimental results of emulsion terpolymerization fit the calculated curves satisfactorily over a wide range of monomer compositions up to high conversions. The influence of 2,3-dibromopropyl acrylate on the thermal and flammability characteristics of the terpolymers is described.     

Rational design,synthesis, and pharmacological evaluation of 2-azanorbornane-3-exo,5-endo-dicarboxylic acid: a novel conformationally restricted glutamic acid analogue

The design and synthesis of conformationally restricted analogues of alpha-amino acids is an often used strategy in medicinal chemistry research. Here we present the rational design, synthesis, and pharmacological evaluation of 2-azanorbornane-3-exo,5-endo-dicarboxylic acid (1), a novel conformationally restricted (S)-glutamic acid (Glu) analogue intended as a mimic of the folded Glu conformation. The synthesis of 1 was completed in its racemic form in eight steps from commercially available starting materials. As a key step, the first facially selective hydroboration of a 5-methylidene[2.2.1]bicyclic intermediate was investigated. In this transformation, the catalytic methodology of Wilkinson's/catechol borane proved superior to stoichiometric borane or dialkyl borane reagents, in terms of higher diastereomeric excess and chemical yield. To our surprise (+/-)-1 did not show affinity in binding studies on native 2-amino-3-(3-hydroxy-5-methyl-4-isoxazolyl)propionic acid (AMPA) (IC(50) > 300 microM, [(3)H]AMPA) or kainic acid (IC(50) > 160 microM, [(3)H]kainic acid) receptors nor in binding studies on the cloned iGluR5,6 subtypes (IC(50) > 300 microM, [(3)H]kainic acid).     

Ultrasound enhanced synthesis of 1,5-benzodiazepinic heterocyclic rings

1,5-Benzodiazepines are synthesized by a reaction of o-phenylenediamines with a diketone or ketones series by ultrasound irradiation in presence of APTS. The condensation occurred in a mild condition with good to excellent yields.     

Terpolymerization of acrylonitrile,styrene, and 2,4,6-tribromophenyl acrylate

Acrylonitrile was terpolymerized with styrene and 2,4,6-tribromophenyl acrylate in aqueous emulsion and dimethylformamide solution. Experimental terpolymerization data agreed well with calculations based on the Alfrey–Goldfinger equation. Triangular coordinate graphs show the feed/terpolymer relationships; the lines of unique and binary azeotropic compositions were identified. No points of true azeotropic composition were found but a “pseudo-azeotropic” region was recognized. The experimental data of the emulsion terpolymerization experiment agreed well with the theoretical curves over a wide range of monomer compositions up to high conversions. Incorporation of 2,4,6-tribromophenyl acrylate in the terpolymer decreased the thermal stability but improved the flame retardancy of the terpolymers.