Quantification of trace elements in human serum fractions by liquid chromatography and inductively coupled plasma mass spectrometry

On‐line coupling of LC and ICP‐MS has been used for fractionation and detection of species of Cu, Fe, I, Se and Zn in human serum. It has been shown that anion exchange chromatography provided better separation capability (both intra‐ and inter‐element) than size‐exclusion chromatography. The mobile phases for ion exchange chromatography consisted of Tris–HNO₃ buffer and ammonium salt (nitrate, acetate or formate). Formate was found to be the best mobile phase counter ion, enabling good chromatographic separation, and is acceptable for mass spectrometry too. The quantitative evaluation of element concentrations adhering to individual fractions was performed by the peak area normalization method. The repeatability of results ranged from 3 to 15% (depending on the element concentration level) and represented the main part of the result uncertainty. The accuracy of Cu and Zn fraction determinations was confirmed by comparison with the isotope dilution technique. Copyright © 2006 John Wiley & Sons, Ltd.     

Structure of norbornene-fused 3,1-oxazine double cycloadducts

Pentacyclic isoxazolines were obtained by the cycloaddition of benzonitrile oxide to norbornene-azetidinone-fused 3,1-oxazines. The constitutions of two of the isomers obtained, and the configurations and conformations of all products, were determined by means of ¹H and ¹³C NMR spectroscopy and DNOE experiments.     

Hydrophilic and hydrophobic copolymer systems based on acrylic derivatives of pyrrolidone and pyrrolidine

This article deals with the synthesis of hydrophilic methacrylic monomers derived from ethyl pyrrolidone [2‐ethyl‐(2‐pyrrolidone) methacrylate (EPM)] and ethyl pyrrolidine [2‐ethyl‐(2‐pyrrolidine) methacrylate (EPyM)] and their respective homopolymers. For the determination of their reactivity in radical copolymerization reactions, both monomers were copolymerized with methyl methacrylate (MMA), the reactivity ratios being calculated by the application of linear and nonlinear mathematical methods. EPM and MMA had ratios of r_EPM = 1.11 and r_MMA = 0.76, and this indicated that EPM with MMA had a higher reactivity in radical copolymerization processes than vinyl pyrrolidone (VP; r_VP = 0.005 and r_MMA = 4.7). EPyM and MMA had reactivity ratios of r_EPyM = 1.31 and r_MMA = 0.92, and this implied, as for the EPM–MMA copolymers, a tendency to form random or Bernoullian copolymers. The glass‐transition temperatures of the prepared copolymers were determined by differential scanning calorimetry (DSC) and were found to adjust to the Fox equation. Total‐conversion copolymers were prepared, and their behavior in aqueous media was found to be dependent on the copolymer composition. The swelling kinetics of the copolymers followed water transport mechanism case II, which is the most desirable kinetic behavior for a swelling controlled‐release material. Finally, the different states of water in the hydrogels—nonfreezing water, freezing bound water, and unbound freezing water—were determined by DSC and found to be dependent on the hydrophilic and hydrophobic units of the copolymers. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 395–407, 2003     

The effect of olefinic terminal chains on the mesomorphic properties of 4,4'-disubstituted diphenyldiacetylenes

New diphenyldiacetylenes of the type with A, B = H and/or F; m = 0, 1; n = 1-4; and X = C n H 2n + 1 , F, CF 3 or CN were synthesized and their mesomorphic properties determined by hot stage polarizing microscopy and DSC. When m = 0, all of these compounds showed only a nematic phase except when X = CF 3 when both nematic and smectic A phases were seen. Both clearing and melting temperatures were higher than those reported for substitution with the corresponding alkyl chains but the much larger increase in clearing temperatures produced considerably wider nematic phases. Eutectic mixtures of a few of these olefins yielded nematic materials also having much wider temperature ranges and higher clearing temperatures than the eutectic mixtures of the alkyl compounds, while retaining their high birefringence and low viscosities. Such materials are of interest for beam-steering devices.

Four of the diacetylenes with m = 1 ( A, B = H) were also prepared ( X = C 6 H 13 , F, n = 2, 3). When X was C 6 H 13 ( n = 2), the nematic range was smaller in the 2- than in the 1-olefin but wider than in the alkyl series. When X = F, either no nematic phase or a monotropic one was observed, whereas the 1-olefins gave a much wider nematic phase. Both transition temperatures were lower than those for the corresponding 1-olefin and alkyl analogues. The compound with X = C 6 H 13 and n = 2 had a melting temperature below room temperature.     

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     

Some remarks on Zienkiewicz-Zhu estimator

In this article, Zienkiewicz-Zhu estimator is analyzed for the piecewise linear finite element approximate solution of an elliptic problem. The estimator is proved to be equivalent to the error for the Poisson equation with a homogeneous Dirichlet boundary condition for any triangular regular mesh. No assumptions are needed about the regularity of the solution (i.e., solutions with corner singularities are not excluded). The estimator is also proved to be asymptotically exact on subdomains where the solution is smooth when parallel meshes are used. Therefore, its behavior is similar to that of other well-known estimators. © 1994 John Wiley & Sons, Inc.     

Synthesis and thermal crosslinking of oxazolidine‐functionalized polyurethanes

A new oxazolidine derivative was obtained from phenol, 2‐amino‐2‐methylpropane‐1,3‐diol and paraformaldehyde. The reaction of this novel oxazolidine diol with phenylisocyanate lead to a urethane model compound which can be polymerized thermally by oxazolidine ring opening to give a Mannich bridge structure. Linear segmented polyurethanes were prepared by reaction of different ratios of oxazolidine diol and commercial polyethylenglycol (M_w ～ 400) with 4,4′‐methylenbis (cyclohexylisocyanate) (HMDI, 90% isomers mixture). The polyurethanes were thermally characterized and crosslinked by oxazolidine ring opening to obtain materials which showed improved thermal stability. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4965–4973, 2007     

Extraction of strontium using an irradiated extraction agent of crown structure

The partition coefficient of strontium upon its extraction from the aqueous solutions of picric acid into chloroform containing DC-18-crown-6, B-15-crown-5 after their exposition to gamma radiation has been studied. A significant decrease of the partition coefficient in the studied range of doses 10–70 kGy was observed. This effect can be attributed to the radiolytic products of chloroform. The radiation destruction as well as dehydrogenation of crown ethers were not observed.     

Observation of hydrogen induced intermediate borides in PrFeB based alloys by Mössbauer effect spectroscopy

In the present work, a quantitative analysis of the phase compositions by Mössbauer effect spectroscopy of solid and conventional hydrogen disproportionated Pr_13.7Fe_80.3B_6.0 and Pr_13.7Fe_63.5Co_16.7Zr_0.1B_6.0 alloys was carried out. Significant amounts of intermediate borides t-Fe₃B and Pr(Fe, Co)₁₂B₆ were detected after solid hydrogen disproportionation treatment in Pr_13.7Fe_80.3B_6.0 and Pr_13.7Fe_63.5Co_16.7Zr_0.1B_6.0 alloys, respectively. After conventional hydrogenation–disproportionation–desorption–recombination treatment these phases were not detected and in no case residual Pr₂Fe₁₄B-phase was found. It was observed that the amount of intermediate borides after disproportionation can be correlated with the degree of texture after recombination at various temperatures.     

Dynamics of a pair of coupled nonlinear oscillators

A pair of coupled classical oscillators with a general potential and general form of coupling is investigated. For general potentials, the single-frequency solution is shown to be stable for small excitations. For special potentials, such system remains stable for an arbitrary excitation. In both cases, the stability does not depend on the form of coupling. Transition to the instability regime follows from the way how nonlinear potential entrains the energy transfer between the oscillators. Relation between the existence of multi-frequency quasi-periodic or periodic solutions and the instability of single-frequency ones is discussed.