Activation processes and polyethylene formation on a phillips model catalyst studied by laser ablation, laser desorption, and static secondary ion mass spectrometry

Since the discovery of the Phillips catalysts, there still is much uncertainty concerning their activation, their molecular structure, the nature of the active chromium sites, and the polymerization mechanisms. Surface techniques are not easy to be used for such study according to the nonconductive behavior of the support. Therefore, model Phillips catalyst is elaborated by spin coating a trivalent chromium precursor on a silicon wafer. The surface characterization of this model catalyst is conducted by laser ablation mass spectrometry (LA-MS), laser desorption/ionization mass spectrometry (LDI-MS), and static secondary ion mass spectrometry (s-SIMS), at different steps of its preparation. To validate our approach, a comparison is also made between the model and the real Philips catalyst. Moreover, the model catalyst efficiency for polyethylene synthesis is evaluated and allows us to discuss the validity of the mechanisms previously proposed to explain the catalytic process. The characterization of Phillips model catalyst by mass spectrometry allows us to better understand the activation processes of such catalyst. Depending on the activation temperature, chromium oxide species are formed and anchored at the support surface. They consist mainly in mono-chromium sites at high temperature. The chromium valence is hexavalent. This model catalyst is active for the polymerization of ethylene. A pseudo-oligomer molecular weight distribution is observed by LA-MS, whereas s-SIMS allows us to elucidate the anchorage of the polymer at activate chromium surface sites.     

The oxime bond formation as an efficient tool for the conjugation of ruthenium complexes to oligonucleotides and peptides

A convenient method for the conjugation of ruthenium complex on oligonucleotides and peptides through chemoselective oxime linkage is reported. Novel Ru(II) complexes sustaining an aminooxy containing ligand were prepared and efficiently coupled with the oligonucleotides and peptides functionalized with the complementary reactive aldehyde group. The method described herein could be a useful tool for preparing a broad range of metal complex-oligonucleotide and peptide conjugates.     

Dipolar relaxations in an epoxy-amine system

Dipolar relaxations in a reactive epoxy-amine system based on diglycidyl ether of bisphenol A with 4,4^′-diaminodiphenylsulfone were studied with the Havriliak-Negami function. The system was cured isothermally at 140 °C using simultaneous kinetic and microdielectric studies.The relaxation time was calculated from the frequency f_max of the peak of the loss factor ε^′′ versus frequency f. A linear relation exists between the logarithm of the relaxation time τ and the glass transition temperature T_g. Then, logτ follows the Di Benedetto equation revisited by Pascault and Williams allowing the prediction of the relaxation time τ during cure.The unrelaxed permittivity at high frequency ε_u, the relaxed or static permittivity ε_s and the skewness parameter β were found independent on the conversion or the curing time. The distribution parameter α decreases as curing time t increases. The difficulty of orientation of dipoles in the electric field due to vitrification is responsible of these behaviours.     

Synthesis, X-ray, and electronic structures of a new nickel dibromide complex. Activity in the regioselective catalyzed dimerization of ethylene into 1-butene

Reaction of the bis-(3,4)-dimethylphosphole-Xanthene 1b with [NiBr2(DME)] afforded a new nickel(II) dibromide complex, 2. Both its color and its NMR behavior change with temperature and solvent due to changes in the spin state of the complex. This led us to study the complex spin states using DFT calculations. Furthermore, the activity of 2 in catalyzed ethylene dimerization was studied, revealing both high activity and selectivity toward the production of 1-butene.     

C-H bond activation of arenes by a transient eta2-cyclopropene niobium complex

The intermolecular C-H bond activation of benzene occurs under very mild conditions (room temperature) via a rare stereospecific 1,3-H addition on an unsaturated eta2-cyclopropene intermediate generated by a beta-H abstraction of CH4 from TpMe2NbMe(c-C3H5)(MeCCMe) to give TpMe2NbPh(c-C3H5)(MeCCMe).     

Jules Horowitz Reactor: a high performance material testing reactor

The physical modelling of materials' behaviour under severe conditions is an indispensable element for developing future fission and fusion systems: screening, design, optimisation, processing, licensing, and lifetime assessment of a new generation of structure materials and fuels, which will withstand high fast neutron flux at high in-service temperatures with the production of elements like helium and hydrogen.JANNUS and other analytical experimental tools are developed for this objective. However, a purely analytical approach is not sufficient: there is a need for flexible experiments integrating higher scales and coupled phenomena and offering high quality measurements; these experiments are performed in material testing reactors (MTR). Moreover, complementary representative experiments are usually performed in prototypes or dedicated facilities such as IFMIF for fusion. Only such a consistent set of tools operating on a wide range of scales, can provide an actual prediction capability. A program such as the development of silicon carbide composites (600–1200 °C) illustrates this multiscale strategy.Facing the long term needs of experimental irradiations and the ageing of present MTRs, it was thought necessary to implement a new generation high performance MTR in Europe for supporting existing and future nuclear reactors. The Jules Horowitz Reactor (JHR) project copes with this context. It is funded by an international consortium and will start operation in 2014. JHR will provide improved performances such as high neutron flux (10¹⁵ n/cm²/s above 0.1 MeV) in representative environments (coolant, pressure, temperature) with online monitoring of experimental parameters (including stress and strain control). Experimental devices designing, such as high dpa and small thermal gradients experiments, is now a key objective requiring a broad collaboration to put together present scientific state of art, end-users requirements and advanced instrumentation. To cite this article: D. Iracane et al., C. R. Physique 9 (2008).     

Around <Emphasis Type="Italic">q</Emphasis>-Appell polynomial sequences

First we show that the quadratic decomposition of the Appell polynomials with respect to the q-divided difference operator is supplied by two other Appell sequences with respect to a new operator \(\mathcal{M}_{q;q^{-\varepsilon}}\), where ε represents a complex parameter different from any negative even integer number. While seeking all the orthogonal polynomial sequences invariant under the action of \(\mathcal{M}_{\sqrt{q};q^{-\varepsilon/2}}\) (the \(\mathcal{M}_{\sqrt{q};q^{-\varepsilon/2}}\)-Appell), only the Wall q-polynomials with parameter q ^ε/2+1 are achieved, up to a linear transformation. This brings a new characterization of these polynomial sequences.     

Relationship between the ligand structure and the luminescent properties of water-soluble lanthanide complexes containing bis(bipyridine) anionic arms

A series of six new ligands (L(1)-L(6)) suitable for the formation of luminescent lanthanide complexes in water is described. Ligands L(1)-L(4) are constructed from two 6'-carboxy-6-methylene-2,2'-bipyridine chromophoric arms bonded to the amino function of a 2-aminomethylene-6-carboxy-pyridine (L(1)), an N,N-diacetate-ethylene diamine (L(2)), a serine (L(3)), or an aminomalonic acid (L(4)). For ligands L(5) and L(6), the linking amino function is provided by a glutamic acid, and the anionic functions at the 6'-position of the bipyridyl arms are made of the sodium salts of monoethylphosphonic ester (L(5)) and phosphonic acid (L(6)). The synthesis and characterisation of the ligands are described, together with the study of the formation of lanthanide complexes with europium and terbium. In the case of L(3), the europium complex obtained in acidic conditions was crystallised and the X-ray crystal structure is depicted. Photophysical properties of the complexes were studied by means of UV-visible absorption, and steady-state and time-resolved luminescence spectroscopy. Excited-state luminescence lifetimes of the complexes were determined in water and deuterated water to gain insight into the number of water molecules directly coordinated in the first coordination sphere of the complexes. The coordination behaviour of the series of ligands is questioned in the light of the spectroscopic data and discussed in terms of protection of the cation towards water molecules and their impact on the luminescence efficiency.