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     

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.     

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     

Giant dipole resonance in55Mn* studied with the BGO detector

High-energy gamma-rays emitted in the decay of the giant dipole resonance built on excited states of⁵⁵Mn nucleus were measured with a bismuth germanate detector. Resonance parameters were extracted from the fits to the experimental spectra. Two new high-energy calibration points originating from slow-neutron capture in germanium isotopes of bismuth germanate crystal are proposed for large-volume BGO detectors.     

Lifetime study of high-spin states in 104,105In

In the neutron deficient isotopes _104,105In lifetimes of high spin states in the range from 0.5 ps to 600 ps have been measured in a coincidence recoil distance Doppler shift (RDDS) experiment. By combining the Doppler shift attenuation (DSA) and RDDS methods at few μm flight distances, the problem of delayed feeding has been avoided and very short lifetimes in the range 0.5–0.8 ps have been determined. Shell model calculations with strong restrictions for the neutron orbitals reveal good agreement with experimental level energies and still fair agreement for most measured B(M1) and B(E2) values. Received: 30 June 1998     

Book Reviews

Unsigned book reviews are by the Book Review Editor.     

Radiation heterogeneous processes of14C-acetic acid adsorbed in Na-Montmorillonite

This research addresses itself to the study of the mechanism of the acetic acid decarboxylation in Na-Montmorillonite exposed to ionizing radiation. The results obtained indicated that the decarboxylation reaction is enhanced several times by the irradiation. This behavior is probably due to an oxidation reaction at the edges of the clay. Also it is by energy transfer from the clay to adsorbed molecules by an interaction of non-equilibrium charge carriers with the adsorbed molecules.     

An improved process of separation of R- and S-timolol

Diastereomeric timolol tartrates 4 are obtained in a one-pot synthesis from the racemic base 2 and optically active O,O-diacetyl- or O,O-dibenzoyltartaric anhydrides 3 , as only one of the diastereomers precipitates from acetone solution. Acidic hydrolysis as the corresponding 4 leads to timolol in high yield and optical purity.     

On the possibility of designing interacting semiconductor quantum wells with zero perturbation coupling

The paper describes the possibility of designing matched interacting semiconductor quantum wells. It is shown that for a given eigenstate of a quantum well (QW), it is always possible to find another QW in such a way that the coupling leaves the original eigenstate of the host QW unperturbed irrespective of the strength of interaction. For rectangular QWs, the condition is met with whenever the second QW has appropriate width and depth so that phase travelled by an electron wave through it is an integral multiple of π.