Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Some non-local problems for the parabolic-hyperbolic type equation with non-characteristic line of changing type

In this work two non-local problems for the parabolic-hyperbolic type equation with non-characteristic line of changing type are considered. Unique solvability of these problems is proven. The uniqueness of the solution is proven by the method of energy integrals and the existence is proven by the method of integral equations.     

Conditions d'optimalité du second ordre nécessaires ou suffisantes pour les problèmes de commande optimale avec une contrainte sur l'état et une commande scalaires

This Note deals with optimal control problems with only one control variable and one state constraint, of arbitrary order. We consider the case of finitely many boundary arcs and touch times. We obtain a no-gap theory of second-order conditions, allowing us to characterize second-order quadratic growth. To cite this article: J.F. Bonnans, A. Hermant, C. R. Acad. Sci. Paris, Ser. I 343 (2006).     

Generation of 0.2-TW 5.5-fs optical pulses at 1 kHz using a differentially pumped hollow-fiber chirped-mirror compressor

Optical pulses with 1.1-mJ energy and 5.5-fs duration have been generated at 1-kHz repetition rate from a chirped pulse amplification Ti:Sapphire laser incorporating a differentially pumped hollow-fiber chirped-mirror compressor. The effects of self-focusing and multi-photon ionization during the beam propagation were minimized by differentially pumping the hollow fiber filled with neon. The spectral broadening at the hollow-fiber compressor was optimized by adjusting gas pressure, laser intensity, and laser chirp, covering from 540 nm to 950 nm. PACS 42.65.Jx; 42.65.Re     

Nano-electrochemical detection of hydrogen or protons using palladium nanoparticles: distinguishing surface and bulk hydrogen.

The benefits of using nanoparticle-modified electrodes are exemplified through the electrochemical detection of protons and/or hydrogen. It is shown that a palladium-nanoparticle-modified boron-doped diamond allows voltammetric information relating to the relative roles played by the surface and the bulk metal to be obtained for the proton-hydrogen system at palladium surfaces which is not accessible using palladium macroelectrodes or microelectrodes.     

The effect of gamma irradiation and shelf aging in air on the oxidation of ultra-high molecular weight polyethylene

This study has investigated the effect of shelf aging, for up to one year in air, on the properties of gamma-irradiated ultra-high molecular weight polyethylene (UHMWPE). A variety of techniques were used to characterize the properties of treated samples. Differential scanning calorimetery (DSC) was used to characterize the morphology. The extent of cross-linking in a polymer network was detected by swelling measurements. The durometer hardness test was used to measure the relative hardness of this material, and changes in density were also measured. Results from all these measurements were combined to explain the changes in the microstructure of the aged, irradiated UHMWPE. This study shows that crystallinity is increased with radiation dose and with aging due to chain scission, which leads to a reduction in the molecular weight of the material. This allows the chains to rearrange to form crystalline regions. Positron annihilation lifetime spectroscopy confirms these conclusions. Fractional free volumes have been deduced from lifetime parameters, which correlate with the data obtained by the other techniques.     

Influence of octupole interactions on the behavior of negative-parity states at low spins

The energies of negative-parity levels based on two-particle states exhibit a nonlinear behavior at low spins versus the core-rotation energy because the alignment process has not yet been completed for them. This behavior of negative-parity levels in the low-spin region is satisfactorily described upon the inclusion of octupole-octupole interactions. This is demonstrated within the rotational model involving the Coriolis mixing of states for the even-even isotopes ^162–168Hf.     

Propagation of a focused light beam in a circuital system of tunnel-coupled waveguides

The propagation of a pencil beam in a circuital system of tunnel-coupled waveguides is considered. It is shown that the beam periodically focuses into a point when moving along the trajectory. A maximal number of waveguides supporting the propagation of the beam can be estimated in simple terms. The cross-sectional area of the waveguides can be subdivided into three zone with the beam pulsing only in the central one.     

Electrochemical formation and composition analysis of Zn x Cd1-x Se solid solutions

The direct growth of ZnSe–CdSe solid solution onto metallic cathodes by electrodeposition from acidic aqueous sulphate solutions is described. The plating process is studied by simple voltammetry, while the structure and composition of the electrolytic deposits are investigated by X-ray diffraction. The experimental d-spacing values of the as-grown mixed lattice are compared to data from reference Zn _x Cd_1-x Se pellets of standard composition, produced by a sintering method. The findings are supplemented with energy-dispersive X-ray (EDX) elemental analysis. Thereupon, the variation of the mole fraction x in Zn _x Cd_1-x Se, and the solid phase constitution of the electrodeposits are determined and correlated to the electrochemical conditions of growth. The resulting films contain admixtures of CdSe compound and metallic Cd.