Anodic stripping coulometry with collection for absolute trace analysis of lead, using flow-through electrochemical cells with porous working electrodes

Summary Flow-through electrochemical cells with porous working electrodes made of crushed reticulated vitreous carbon and plated with mercury were used for absolute analysis of trace amounts of lead by anodic stripping coulometry with collection (ASCWC) in a flow system. The role of mercury coating, flow rate and pH were investigated. The coulombic content of the collection peak corresponded to the theoretical values calculated by Faraday's law in a concentration range from about 10^–9 to 10^–6 mol/l. The relative error and the relative standard deviation was +0.15% and 0.8%, respectively for 2×10^–6 mol/l analyte concentration. The absolute detection limit (3 s) was 0.1 ng of Pb, the linear response range 7×10⁴. One leave from: Department of Analytical Chemistry, Slovak Technical University, CS-812 37 Bratislava, Czechoslovakia     

Left, right, and inner socles of associative systems

We investigate the basic properties of the different socles that can be considered in not necessarily semiprime associative systems. Among other things, we show that the socle defined as the sum of minimal (or minimal and trivial) inner ideals is always an ideal. When trivial inner ideals are included, this inner socle contains the socles defined in terms of minimal left or right ideals. This revised version was published online in June 2006 with corrections to the Cover Date.     

Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007     

Synthesis of polysiltrimethylenes with trimethylsilyl groups in the branch of the main chain

The thermally initiated and platinum-catalyzed polymerization of 1-silacyclobutanes with substitutents containing a trimethylsilyl group was carried out. Soluble, high-molecular-weight, heterochain siltrimethylene polymers were obtained, containing trimethylsilyl groups removed from the main chain by various bridges.A. V. Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 117912 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 1, pp. 223–225, January, 1992.     

On the ordering in [(C2H5)4N]2CuCl4 crystal: an X-ray study and theoretical considerations

The crystal structure [(C₂H₅)₄N]₂CuCl₄ has been determined by X-ray diffraction at 243K. The room temperature phase (phase I) belongs to the space group P4₂/nm [1] whereas the low temperature phase (phase II) is orthorhombic and belongs to the space group Pnna. The phase transition at T_c=258K is of improper ferroelastic type and it is associated with the ordering of the CuCl₄ ^2? and a partial ordering of the [(C₂H₅)₄N]⁺ ions which are disordered in the high temperature tetragonal phase. At lower temperature, there occurs another instability which could correspond to a complete ordering in the crystal.     

Corner spontaneous magnetization

Details are given of a new method allowing an exact calculation of the spontaneous magnetization in the corner as well as along the edge at an arbitrary distance of the corner for a rectangular planar Ising ferromagnet.     

Contributions to the synthesis of some ferrocene-containing antibiotics

This Review discusses the synthesis and characterization by our Group of new antibiotics belonging to the class of penicillins, cephalosporins and rifamycins with ferrocenyl and 1, 1′-ferrocenilene residues in the molecule. As reactants for 6-aminopenicillanic acid (6-APA) and 7-aminocephalosporanic acid (7-ACA) the following were used: 1, 1-bis(chlorocarbonyl)ferrocene, ferrocenyl sulfochloride, 1, 1′-ferrocenylenedisulfochloride and thioglycolic acids S-modified with ferrocene. In the synthesis of rifamycins, the hydrazides of the thioglycolic acids, S-modified with ferrocene, were employed as nucleophilic agents. The synthesized intermediates were characterized by elemental analysis, TLC, IR, UV and ¹H NMR spectra. The characterization of new antibiotics was made by TLC, IR and UV spectral analysis. Biological activity was tested on Gram-negative and Gram-positive bacteria. Good activity is reported towards Gram-positive bacteria in the case of derivatives containing residues of thioglycolic acid S-modified with ferrocene, the antibacterial activity being similar to that of amoxicillin, carbenicillin and cephalothin. All compounds are inactive towards Gram-negative bacteria.     

Rotational temperature and density measurements in a hypersonic flow by dual-line CARS

Rotational temperature and nitrogen number density are measured in the shock wave/boundary layer interaction region in the vicinity of a two-dimensional compression corner disposed in a low pressure, 55 K, Mach 10 hypersonic air flow. Spatially-resolved data are recorded using a nonlinear optical technique named dual-line coherent anti-Stokes Raman scattering (DLCARS). Averaged temperature and density profiles are compared with those predicted by a Navier-Stokes solver. Good agreement is found.     

Cems characterization of SnO2 films obtained by sputtering and sol-gel route

Conversion electron Mössbauer spectroscopy (CEMS) has been used to study tin oxide films prepared by sol-gel dipping and sputtering. The spectra of films prepared by sol-gel route result close to that of crystalline SnO₂ after heat treatment at a temperature as low as 150°C. The Mössbauer parameters of as sputter deposited films indicate that the structure of the deposited stannic oxide has an amorphous character more pronounced for thinner samples. The structure becomes predominantly that of crystalline SnO₂ by heating at 550°C for 30 min provided the film thickness is higher than 10 nm.     

Riccati-based preconditioner for computing invariant subspaces of large matrices

Summary. This paper introduces and analyzes the convergence properties of a method that computes an approximation to the invariant subspace associated with a group of eigenvalues of a large not necessarily diagonalizable matrix. The method belongs to the family of projection type methods. At each step, it refines the approximate invariant subspace using a linearized Riccati's equation which turns out to be the block analogue of the correction used in the Jacobi-Davidson method. The analysis conducted in this paper shows that the method converges at a rate quasi-quadratic provided that the approximate invariant subspace is close to the exact one. The implementation of the method based on multigrid techniques is also discussed and numerical experiments are reported. Received June 15, 2000 / Revised version received January 22, 2001 / Published online October 17, 2001