Thermal Analysis of Hexachloroplumbate and Chlorides Containing Complex Divalent Lead 2,2'-bipyridine Cations

Lead(II) 2,2'-bipyridine hexachloroplumba tetetrahydrate was synthesized and investigated by DTA, TG and DTG. IR spectroscopy and other methods enabled the identification of some of the decomposition products. Comparative studies on the corresponding chlorides: [Pb(bipy)]Cl₂ and [Pb(bipy)₃]Cl₂, which can be considered as precursors of the hexachloroplumbate, were also undertaken. X-ray measurements enabled the tentative determination of the crystal structure of [Pb(bipy)]Cl₂. Hexachloroplumbate decomposes with the liberation of chlorine, water and organic ligands, and the process is accompanied by the simultaneous transition of Pb(IV)→Pb(II). Chlorides release only ligands upon heating. Residues comprised always PbCl₂. This revised version was published online in August 2006 with corrections to the Cover Date.     

Sr and stable strontium in bones of wild, herbivorous animals from Poland

Activity concentration of ⁹⁰ Sr and stable strontium concentration was analysed in 42 samples of animal (deer, roe-deer, elk and boar) bones, which mostly originated from north-eastern Poland. Strontium separation was performed by extraction chromatography. Determination of chemical yield was controlled by means of stable Sr determination using atomic spectrometry at the beginning and at the end of the separation procedure. Equilibrated ⁹⁰ Sr and ⁹⁰ Y activity was measured using a liquid scintillator spectrometer. Stable strontium range was from 55.4±1.7 ppm to 91.8±4.5 ppm, the mean was 71.84 ppm with a standard deviation (SD) of 9.31 ppm. The mean recovery of strontium was 26.7% with SD = 16.1%. The maximum activity of ⁹⁰ Sr, equal to 629±13 Bq/kg (ash) was found for a deer sample from Augustów Primeval Forest. In average, deer show the highest radiostrontium level, followed by roe-deer, elk and the lowest level were observed for boar. Differences between boar and deer or roe-deer are significant in terms of Kruskal-Wallis statistical test. Animal bones from north-eastern Poland showed about twice the mean concentration of ⁹⁰ Sr, compared to those of south-central Poland, but the difference was found not significant. Activities observed in roe-deer bones suggest the deposition of a concentration of 1.9 to 3.5 kBq/m² in the average of Chernobyl-origin ⁹⁰ Sr in 1986 in north-eastern Poland.     

Monodisperse magnetic poly(glycidyl methacrylate) microspheres for isolation of autoantibodies with affinity for the 46 kDa form of unconventional Myo1C present in autoimmune patients

Monodisperse nonmagnetic macroporous poly(glycidyl methacrylate) (PGMA) microspheres were synthesized by multistep swelling polymerization of glycidyl methacrylate, ethylene dimethacrylate and 2-[(methoxycarbonyl)methoxy]ethyl methacrylate (MCMEMA). This was followed (a) by ammonolysis to modify the microspheres with amino groups, and (b) by incorporation of iron oxide (γ-Fe₂O₃) into the pores to render the particles magnetic. The resulting porous and magnetic microspheres were characterized by scanning and transmission electron microscopy (SEM and TEM), atomic absorption and Fourier transform infrared spectroscopy (AAS and FTIR), elemental analysis, vibrating magnetometry, mercury porosimetry and Brunauer-Emmett-Teller adsorption/desorption isotherms. The microspheres are meso- and macroporous, typically 5 μm in diameter, contain 0.9 mM · g^?1 of amino groups and 14 wt.% of iron according to elemental analysis and AAS, respectively. The particles were conjugated to p46/Myo1C protein, a potential biomarker of autoimmune diseases, to isolate specific autoantibodies in the blood of patients suffering from multiple sclerosis (MS). The p46/Myo1C loaded microspheres are shown to enable the preconcentration of minute quantities of specific immunoglobulins prior to their quantification via SDS-PAGE. The immunoglobulin M (IgM) with affinity to Myo1C was detected in MS patients.

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Graphical abstract Monodisperse magnetic poly(glycidyl methacrylate) microspheres were synthesized, conjugated with 46 kDa form of unconventional Myo1C protein (p46/Myo1C) via carbodiimide (DIC) chemistry, and specific autoantibodies isolated from blood of multiple sclerosis (MS) patients; immunoglobulin M (IgM) level increased in MS patients.

     

Effect of Re addition on the crystallization,heat treatment and structure of the Cu–Ni–Si-Cr alloy

Differential scanning calorimetry (DSC) was used to investigate the thermal behavior and non-isothermal crystallization kinetics of the Fe₆₇Nb₅B₂₈ metallic glasses prepared by melt-spinning method. DSC traces exhibit that the crystallization takes place through a single exothermic reaction, and it processes a good thermal stability in thermodynamics. The activation energies for nucleation and grain growth processes were calculated to be 536 ± 22 and 559 ± 20 kJ mol^?1 by Kissinger equation, respectively, and 551 ± 24 and 574 ± 20 kJ mol^?1 by Ozawa equation, respectively. It means that the grain growth process is more difficult than the nucleation process. The variation of local Avrami exponent n(x) with crystallized fraction x demonstrates that the crystallization mechanism varies at different stages. The n(x) is larger than 2.5 at the initial stage of 0 < x < 0.3, implying a mechanism of diffusion-controlled three-dimensional growth with increasing nucleation rate. The n(x) decreases from 2.5 to 1.5 in the range of 0.3 < x < 0.65, suggesting that the crystallization belongs to three-dimensional nucleation and grain growth with decreasing nucleation rate. And n(x) lies between 1.0 and 1.5 in the range of 0.65 < x < 0.95, indicating that the crystallization corresponds to the growth of particles with an appreciable initial volume. Low-temperature annealing corresponds to the precipitation of α-Fe, Fe₂B, and Fe₂₃B₆ phases, and further annealing leads to the formation of α-Fe, Fe₂B, and FeNbB phases. The magnetic properties in relation to microstructure change of the Fe₆₇Nb₅B₂₈ metallic glasses are discussed.     

Thermodynamic properties of the NdBr3–MBr binary systems (M = Na,K)

Thixoforming involves heating different types of alloys to the semisolid state at high heating rates and forming in die-casting machines or conventional presses. At temperatures higher than the solidus and lower than the liquidus, the mush metal behaves like a high-viscosity thixotropic material. Therefore, determining the thermodynamic behavior of the solid-to-liquid transition is paramount to control thixoforming processes. This article describes a simple, novel experimental setup based on differential thermal analysis (DTA) for analyzing the phase transitions in an alloy heated using high heating rates typical of industrial applications. A365 alloy was chosen to demonstrate the effectiveness of the method as the phase transformations for this alloy in semisolid materials (SSM) processing are well understood. Samples were heated to 750 °C using constant linear heating rates of 5, 10, 15, 20, 25, 50, 75, 100 and 125 °C min in a Norax 25 kW 8 kHz induction furnace with an Omron E5CK temperature controller. AISI 316 austenitic stainless steel was used as the inert reference. Comparison of the results of DTA using the proposed method and the results of simulation with Thermo-Calc^® indicates that the proposed in situ DTA device and its method is suitable for analyzing phase transitions when high heating rates are used.     

Influence of constant magnetic field on electrodeposition of metals,alloys, conductive polymers,and organic reactions

The paper presents and summarizes some research on constant magnetic field effects in chemistry. Metals and alloys electrodeposited under constant magnetic field have greater thickness and smoother surface with finest grains. Metallic materials deposited under the influence of uniform magnetic field may have stronger corrosion resistance, than those obtained without the presence of magnetic field. Constant magnetic field also causes an increase of the electropolymerization rate and yield of some organic reactions. Our research also shows that the presence of constant magnetic field affects the electrodeposition process of alloys and their morphology to a great extent. The effects of magnetic field on metals, alloys, composites, polymers and other materials are due to the Lorentz force and the magnetohydrodynamic effect. It is possible that the further development of magnetoelectrodeposition will allow for using the constant magnetic field to improve the properties of metal coatings, alloys, polymers, and other materials in the industry.     

Stereoselective synthesis of isoindolinones and tert-butyl sulfoxides

A reaction of Grignard reagents with an optically pure N-sulfinylimine derived from methyl 2-formylbenzoate yields enantioenriched isoindolinones and tert-butyl sulfoxides. The products are formed by the addition of the nucleophile to N-sulfinylimine followed by cyclization to form N-tert-butylsulfinylisoindolinone, which readily undergoes substitution with a second equivalent of Grignard reagent. The reaction can be carried out in dichloromethane at room temperature or at elevated temperatures without any loss of stereoselectivity. The use of nucleophiles other than Grignard reagents has also been investigated.     

Conformational search and spectroscopic analysis of bis-β-d-glucopyranosyl azacrown derivative

1,10-N,N′-bis-(β-d-ureidoglucopyranosyl)-4,7,13-trioxa-1,10-diazacyclopentadecane is a new, recently synthesized compound, which exhibits complexation ability towards drugs. In the present study various theoretical methods, including molecular mechanics, computer simulations, semiempirical and DFT calculations, are applied to find the lowest energy conformers of this molecule in vacuo and in aqueous solution. For the most stable structures the vibrational frequencies as well as the C and H chemical shifts were computed. Along with the theoretical investigation the IR in the KBr discs and the NMR spectra in water and in pyridine were experimentally recorded. It is shown that in the lowest energy structures the two glucosyl units are placed on the same side of the diazacrown ring with their mutual orientations favoring formation of hydrogen bonds. The “open” structure, in which no such hydrogen bonds can be formed, is found to have much higher energy. The computed and measured IR spectra and NMR chemical shifts are compared and discussed in detail. The most stable structures are analyzed with respect to the possible mechanism of complexation of drugs.     

Another Unprecedented Wieland Mechanism Confirmed: Hydrogen Formation from Hydrogen Peroxide,Formaldehyde, and Sodium Hydroxide

In 1923, Wieland and Wingler reported that in the molecular hydrogen producing reaction of hydrogen peroxide with formaldehyde in basic solution, free hydrogen atoms (H^.) are not involved. They postulated that bis(hydroxymethyl)peroxide, HOCH₂OOCH₂OH, is the intermediate, which decomposes to yield H₂ and formate, proposing a mechanism that would nowadays be considered as a “concerted process”. Since then, several other (conflicting) “mechanisms” have been suggested. Our NMR and Raman spectroscopic and kinetic studies, particularly the determination of the deuterium kinetic isotope effect (DKIE), now confirm that in this base‐dependent reaction, both H atoms of H₂ derive from the CH₂ hydrogen atoms of formaldehyde, and not from the OH groups of HOCH₂OOCH₂OH or from water. Quantum‐chemical CBS‐QB3 and W1BD computations show that H₂ release proceeds through a concerted process, which is strongly accelerated by double deprotonation of HOCH₂OOCH₂OH, thereby ruling out a free radical pathway.