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     

Semi-implicit complementary volume scheme for solving level set like equations in image processing and curve evolution

Summary. We introduce linear semi-implicit complementary volume numerical scheme for solving level set like nonlinear degenerate diffusion equations arising in image processing and curve evolution problems. We study discretization of image selective smoothing equation of mean curvature flow type given by Alvarez, Lions and Morel ([3]). Solution of the level set equation of Osher and Sethian ([26], \[30]) is also included in the study. We prove and estimates for the proposed scheme and give existence of its (generalized) solution in every discrete time-scale step. Efficiency of the scheme is given by its linearity and stability. Preconditioned iterative solvers are used for computing arising linear systems. We present computational results related to image processing and plane curve evolution. Received April 25, 2000 / Revised version received June 11, 2001 / Published online November 15, 2001     

Derivation of the k–ε model for locally homogeneous turbulence by homogenization techniques

We derive the incompressible and compressible k–ε model for locally homogeneous turbulence. The model is rigorously derived on formal mathematical grounds using the MPP modelling technique. This lets us calculate by either analytical or numerical means the closure constants of the model. To cite this article: T. Chacón Rebollo, D. Franco Coronil, C. R. Acad. Sci. Paris, Ser. I 337 (2003).     

Spinors, Inflation, and Non-Singular Cyclic Cosmologies

We consider toy cosmological models in which a classical, homogeneous, spinor field provides a dominant or sub-dominant contribution to the energy-momentum tensor of a flat Friedmann-Robertson-Walker universe. We find that, if such a field were to exist, appropriate choices of the spinor self-interaction would generate a rich variety of behaviors, quite different from their widely studied scalar field counterparts. We first discuss solutions that incorporate a stage of cosmic inflation and estimate the primordial spectrum of density perturbations seeded during such a stage. Inflation driven by a spinor field turns out to be unappealing as it leads to a blue spectrum of perturbations and requires considerable fine-tuning of parameters. We next find that, for simple, quartic spinor self-interactions, non-singular cyclic cosmologies exist with reasonable parameter choices. These solutions might eventually be incorporated into a successful past- and future-eternal cosmological model free of singularities. In an Appendix, we discuss the classical treatment of spinors and argue that certain quantum systems might be approximated in terms of such fields.     

Confidence regions in a multivariate regression model with constraints II

The multivariate model, where not only parameters of the mean value of the observation matrix, but also some other parameters occur in constraints, is considered in the paper. Some basic inference is presented under the condition that the covariance matrix is either unknown, or partially unknown, or known. Supported by the grant of the Council of Czech Republic MSM 6 198 959 214.     

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     

Compact coaxial driver for small-size Z-pinch

The presented one-capacitor pinch driver, designed as a compact coaxial structure (including spark-gap and discharge section) consistent with the capacitor output, generates a current of 200 kA with 700 ns quarter-period, suitable for studying the optimization of Z-pinch radiative characteristics. The driver is described, measurements of its parameters summarized, and relations to our previous and future activities briefly reviewed.This work was supported in part by the Grant Agency of the Czech Republic under contract No. 202/93/1023.     

1H and13C nuclear magnetic relaxation and local dynamics of lysozyme and synthetic polypeptides

The combined analysis of¹H and¹³C NMR relaxation data in solid lysozyme and some typical homopolypeptides was carried out by using “model-free” approach. Three types of relaxation transitions (γ’, γ and β) were revealed in the temperature range investigated. The microdynamical parameters of these motions were determined. From the comparison of these parameters with those of selected synthetic polymers it follows that the molecular motions in proteins and synthetic polymers are of the same nature. All these motions show pronounced anisotropic character. In the investigated temperature range no molecular motions corresponding to α-relaxation (liquid-like) transition were revealed. The hydration effects on parameters of the motions in proteins were considered. The most pronounced effect takes place for β-transition. The effect of Brownian rotation of protein molecule in solution on measured correlation function of local motions was also discussed.     

Energy transfer between the flavin chromophores of electron-transferring flavoprotein fromMegasphaera elsdenii as inferred from time-resolved red-edge and blue-edge fluorescence spectroscopy

Both a mode-locked argon-ion laser and synchrotron radiation were used as excitation sources to obtain time-resolved polarized fluorescence of the two FAD cofactors in electron transferring flavoprotein fromMegasphaera elsdenii. Red-edge excited and blue-edge detected fluorescence anisotropy decay curves did not contain a fast relaxation process which was observed upon mainband excitation and detection. This relaxation was assigned to homo-energy transfer between the two FAD cofactors. Failure of energy transfer as observed with edge spectroscopy on this protein excludes restricted reorientational motion of the flavins as a possible mechanism of depolarization. From the global analysis of the fluorescence anisotropy decay surface obtained at multiple excitation and detection wavelengths, the distance between and the relative orientation of the flavins could be estimated. The methodology described has general applicability in other multichromophoric biopolymers and has the potential to acquire accurate geometrical parameters in these systems.     

Multiple-scattering-theory analysis of XANES spectra of SO2 adsorbed on Cu(100)

The sulphur K-edge x-ray absorption spectra of SO₂ multilayer and of SO₂ submonolayer adsorbed on Cu(100) are analysed. It is found that the dominant spectral features are of a molecular origin. The results support earlier findings that the SO₂ molecule stands perpendicular to the surface. Use of non-selfconsistent potentials does not lead to a good quantitative agreement between theory and experiment.