Microdetermination of Xanthates

Summary A rapid, convenient and accurate method for the determination of xanthates has been developed. N-bromosuccinimide has been used to displace iodine from potassium iodide which in turn oxidizes xanthate to dixanthogen. The p_H 4 is optimum for the determination. The maximum relative standard deviation is 6% in the case of ethyl potassium xanthate when a 0.5 mg sample was taken.

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Zusammenfassung Ein genaues Verfahren zur raschen Bestimmung von Xanthat wurde entwickelt. N-Bromsuccinimid dient zur Freisetzung von Jod aus KJ; Jod oxydiert Xanthat zu Dixanthogen. Das optimale p_H für die Bestimmung ist 4. Die größte relative Standardabweichung ist 6% bei einer Einwaage von 0,5 mg Kaliumäthylxanthat.

     

Mononuclear complexes of manganese(II), iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), with 4-amino-3,5-bis(pyridin-2-yl)-1,2,4 triazole and tris(2-aminoethyl) amine: crystal structure of [Ni(tren)(abpt)](NO3)2(H2O)2.25

Complexes of the type [M(tren)(abpt)](NO₃)₂(H₂O)_n (1–6) [M = Mn^II, Fe^II, Co^II, Cu^II, Zn^II (n = 2), Ni^II (n = 2.25), tren = tris(2-aminoethyl)amine, and abpt = 4-amino-3,5-bis(pyridin-2yl)-1,2,4 triazole] have been prepared. The bonding mode and overall geometry of the complexes have been deduced by elemental analyses, molar conductance values, spectral studies (obtained from FT-IR), ¹H-n.m.r., electronic spectral analyses and magnetic susceptibility measurements. A detailed molecular structure of complex (4) has been determined by single X-ray crystallography.     

Synthesis of new dinuclear dicopper(II) and dinickel(II) complexes. The kinetics of catechol oxidase and electrochemistry of a dicopper(II) complex

A new dinuclear ligand L, ethylene[OO-bis-salicylidene--diketone] bearing two symmetrical coordination sites was synthesized by the condensation of salicylaldehyde and acetylacetone, L, with 1,2-dibromoethane under reflux. The ligand L in a 1:1 ratio was treated with CuCl₂ and NiCl₂ to yield the complexes, tetrachloro bis[OO-bis- salicylidene--diketone copper(II)] and bis[OO-bis-salicylidene--diketone nickel(II)] chloride. The complexes were subsequently characterized by spectroscopic techniques, elemental analysis, i.r., ¹H-n.m.r., ¹³C-n.m.r., u.v.–vis., e.p.r. spectroscopy, and conductance measurements. The conductance measurements in DMF reveal that the Cu^II complex is covalent while the Ni^II complex is ionic and the spectral data support the Cu^II complex to be distorted octahedral whereas the Ni^II complex has square-planar geometry. The dioxygen binding was studied spectrophotometrically by the oxidation of tetrachloro bis[OO-bis-salicylidene--diketone copper(II)] with pyrocatechol in the presence of oxygen. The kinetic experiments were performed with the copper complex in DMF by monitoring the increase in absorbance over time at pH 8.0 in the presence of pyrocatechol at 25 °C. The kinetic parameters V_max and K_M were determined on the Michaelis–Menten Approach. Redox behavior of the dinuclear copper(II) complex was investigated by cyclic voltammetry in the presence of O₂ with the pyrocatechol (substrate) and also without the substrate. The large difference in potentials E⁰ is indicative of reversible oxygen binding of the complex and distinct catalytic activity.     

Microbial transformation of dehydroepiandrosterone

Transformation of dehydroepiandrosterone (DHEA) (1) was carried out by a plant pathogen Rhizopus stolonifer, which resulted in the production of seven metabolites. These metabolites were identified as 3beta,17beta-dihydroxyanandrost-5-ene (2), 3beta,17beta-dihydroxyandrost-4ene (3), 17beta-hydroxyandrost-4-ene-3-one (4), 3beta,11-dihydroxyandrost-4-ene-17-one (5), 3beta,7alpha-dihydroandrost-5-ene-17-one (6), 3A,7alpha,17beta-trihydroxyandrost-5-ene (7) and 11beta-hydroxyandrost-4,6-diene-3,17-dione (8). The structures of the transformed products were determined by the spectroscopic techniques.     

Derivatives of 4‐(2‐hydro­xy­lphenyl)‐2‐phenyl‐2,3‐di­hydro‐1,5‐benzothiazepine

In the structures of 2‐(4‐chloro­phenyl)‐4‐(2‐hydroxyphenyl)‐2,3‐di­hydro‐1,5‐benzo­thia­zepine, C₂₁H₁₆ClNOS, 4‐(2‐hy­droxy­phenyl)‐2‐(4‐tolyl)‐2,3‐di­hydro‐1,5‐ben­zo­thia­zepine, C₂₂H₁₉NOS, and 4‐(2‐hydroxyphenyl)‐2‐(3‐methoxy­phenyl)‐2,3‐di­hydro‐1,5‐benzo­thia­zepine, C₂₂H₁₉NO₂S, the central seven‐membered heterocyclic rings adopt twist‐boat conformations in which the N atoms are involved in strong intramolecular hydrogen bonds with the hydroxyl H atoms, resulting in six‐membered rings.     

Interaction of manganese(II), iron(II), cobalt(II), nickel(II), copper(II) and zinc(II) with acetylhydrazine, formed in situ; first crystal structure of tris(acetylhydrazine) nickel(II) perchlorate

A series of transition metal complexes of the type [M(ah)₃](ClO₄)₂ (1–6) [M = Mn^II, Fe^II, Co^II, Ni^II, Cu^II and Zn^II, ah = acetylhydrazine] have been prepared by the reaction of M(ClO₄)₂ · 6H₂O with acetylhydrazine formed in situ by the reaction of hydrazine hydrate and acetylsalicylic acid methyl ester. The chelating behaviour of acetylhydrazine and overall geometry of these complexes have been spectroscopically investigated by means of FT-IR, ¹H-n.m.r. and electronic spectral techniques, as well as by elemental analysis data, molar conductance values and magnetic susceptibility measurements. Single X-ray structure determination of complex (4) revealed three acetylhydrazine ligands coordinated to nickel ion in a bidentate manner maintaining an octahedral environment. In all other complexes too, an octahedral geometry has been proposed on the basis of results obtained by various physico-chemical studies.     

On the geometry of null congruences in general relativity

Some theorems for the null conguences within the framework of general theory of relativity are given. These theorems are important in themselves as they illustrate the geometric meaning of the spin coefficients. The newly developed Geroch-Held-Penrose (GHP) formalism has been used throughout the investigations. The salient features of GHP formalism that are necessary for the present work are given, and these techniques are applied to a pair of null congruences C (l) and C(n).     

Synthesis,characterization, AC conductivity,and diode properties of polyaniline–CaTiO3 composites

Polyaniline–CaTiO₃ composites of different weight percentages were prepared by in situ polymerization. The prepared composites were characterized by Fourier transform infrared spectroscopy for structural studies, and a morphology analysis was carried out by scanning electron microscopy studies. Real and imaginary parts of the complex impedance were determined for given samples as a function of frequency. Current–voltage and capacitance–voltage measurements were also carried out. The carrier mobility μ values of neat polyaniline and polyaniline–CaTiO₃ composites were found to be 5.37 × 10^?3 and 2.73 × 10^?2, respectively, and a significant enhancement, as compared with the reported data, was observed. Therefore, this study may provide a better route for technological applications in all fields in the near future and can also be represented by a pure electronic model. Copyright © 2013 John Wiley & Sons, Ltd.     

An Efficient and Convenient Synthesis of Imidazolines and Benzimidazoles via Oxidation of Carbon‐Nitrogen Bond in Water Media

The metal coordination complex K₄[Fe(CN)₆] is an efficient and environmentally benign catalyst for the synthesis of imidazolines and benzimidazoles from various aldehydes and 1,2‐diamines in aqueous medium at room temperature. This protocol gives excellent yield of product with desired purity.     

Lesion edge preserved direct average strain estimation for ultrasound elasticity imaging

Elasticity imaging techniques with built-in or regularization-based smoothing feature for ensuring strain continuity are not intelligent enough to prevent distortion or lesion edge blurring while smoothing. This paper proposes a novel approach with built-in lesion edge preservation technique for high quality direct average strain imaging. An edge detection scheme, typically used in diffusion filtering is modified here for lesion edge detection. Based on the extracted edge information, lesion edges are preserved by modifying the strain determining cost function in the direct-average-strain-estimation (DASE) method. The proposed algorithm demonstrates approximately 3.42–4.25 dB improvement in terms of edge-mean-square-error (EMSE) than the other reported regularized or average strain estimation techniques in finite-element-modeling (FEM) simulation with almost no sacrifice in elastographic-signal-to-noise-ratio (SNRe) and elastographic-contrast-to-noise-ratio (CNRe) metrics. The efficacy of the proposed algorithm is also tested for the experimental phantom data and in vivo breast data. The results reveal that the proposed method can generate a high quality strain image delineating the lesion edge more clearly than the other reported strain estimation techniques that have been designed to ensure strain continuity. The computational cost, however, is little higher for the proposed method than the simpler DASE and considerably higher than that of the 2D analytic minimization (AM2D) method.