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     

Substitution of calcium by strontium within selected calcium phosphates

Sr incorporation in the molecules of amorphous calcium phosphate, apatitic tricalcium phosphate, hydroxyapatite, octacalcium phosphate and dicalcium phosphate dihydrate was investigated. The concentration of Sr ranged from 225 to 1010 μ g / g, i.e. it overlapped with the physiological range of Sr concentrations in human bone. The leading experimental technique was extended X-ray absorption fine structure (EXAFS) at the Sr K edge. Results of these studies demonstrated the following: (1) Sr incorporation in the calcium phosphates is compound-dependent, (2) the coordination of incorporated Sr atoms in the Ca-P molecules is similar to that of Ca atoms, but interatomic distances are ≈0.015 nm larger, (3) in apatitic tricalcium phosphate, hydroxyapatite and octacalcium phosphate lattices Sr atoms may occupy selected Ca sites, which was not the case for dicalcium phosphate dihydrate, (4) in the apatite lattice Sr atoms are coordinated by 6 PO₄ tetrahedrals and (5) EXAFS spectra at the K edge of the incorporated Sr may be used to distinguish the structures of amorphous calcium phosphate, dicalcium phosphate dihydrate as well as apatite and its derivatives (apatitic tricalcium phosphate, octacalcium phosphate).     

X-ray induced fluorescence spectrometry at grazing incidence for quantitative surface and layer analysis

Summary Single layers and layer systems on diverse substrates were measured by Total Reflection X-Ray Fluorescence (TXRF) spectrometry. The angular dependence of the fluorescence intensities at grazing incidence allows the elemental composition, density and thickness of the layers to be evaluated using model calculations.     

Theoretical and experimental investigation of the linear optical response of YBa2Cu4O8 The relevance of LDA calculations

We report results of ellipsometric measurements of the dielectric tensor of YBa₂Cu₄O₈ as well as calculations employing density functional theory in the local density approximation (LDA). For the computation of the one-electron eigenvalues and states the linear-muffin-tin-orbital method (LMTO) was used. Measured and calculated results show good agreement. In particular, the calculation predicts different band structures for YBa₂Cu₃O₇ and YBa₂Cu₄O₈ in the vicinity of the Fermi energy which lead to significant differences in the optical spectra. One such difference is a region of small ε₂ in the near infrared which is a fingerprint of the high (relative to the top of the highest fully occupied band) Fermi energy as compared to the situation in YBa₂Cu₃O₇. Our experimental results confirm the theoretical findings.     

Input control in nonnegative matrix equations

In this paper we consider the nonnegative matrix system c_iA+u_iB=c_i+1 where the nonnegative matrix A is allowed to vary, within bounds. The cone control problem is to find a nonnegative matrix B such that if C_i is a nonnegative vector in a specified cone, then there is a nonnegative vector u_i such that c_i+1 is in that cone. We extend this problem to input control by finding a B such that the cone, generated by the rows of B, is as small as possible. Thus, the percent distribution of ∣u_iB∣ through the states of the sustem by u_iB is either constant or varies little.     

Flow and reactive transport in porous media induced by well injection: Similarity solution

The authors study concentration profiles of solutes undergoingequilibrium absorption in the vicinity of a water well. Forthe case of a contamination event, the limit problem of vanishingwell radius, which is of self-similar nature, is analysed indetail. Existence, uniqueness, and qualitative properties ofsolutions of the corresponding ordinary differential equationsare shown. Some numerical examples are also presented.     

Matrix effects in the determination of butyltin compounds in environmental samples by GC AA after hydride generation

Experiments for the determination of mono-, di and tri-butyltin (MBT, DBT and TBT) by hydride generation/gas chromatography/atomic absorption spectrometry in various matrices (sediment, suspended matter, mussel, algae and water) have revealed that poor butyltin recoveries are obtained in sediments displaying high sulphur and hydrocarbon contents; very poor recoveries were also observed for TBT in sediments with high chlorophyll pigment contents as well as in algal samples. It was however not clear whether the hydride generatin was inhibited by these infering compounds, as was previously assumed in the case of hydrocarbons, or whether interferences affected the atomization rate. Further studies were performed to solve this problem in order to validate this method in the case of analyses of, for example, oil-contaminated sediment and algae. This paper presents the results obtained. It is concluded here that the poor recoveries were due to an inhibition of hydride generation rather than to interference at the atomization stage.     

X-ray diffraction study of 'side-on fixed' homopolysiloxanes from nematic to smectic C phases

The X-ray patterns for the nematic phase in a series of side-on fixed polysiloxanes show different kinds of diffuse elements which imply complex short range ordering. A systematic structural study of the evolution of the patterns versus two molecular parameters, namely the spacer length and the length of the terminal aliphatic tails, suggests the possible occurrence of a smectic C phase for certain values of these parameters. Taking into account these tendencies, new synthesis led to a nematic-smectic C polymorphism observed for the first time in side-on fixed polysiloxanes.