1D to 3D NMR study of microporous alumino‐phosphate AlPO4‐40

From one‐ to two‐ and three‐dimensional MAS NMR solid‐state experiments involving ³¹P and ²⁷Al, we show that the structure of microporous alumino‐phosphate AlPO₄‐40 contains at least four times more sites than expected, and we attribute two types of Al_IV sites. The newly described ²⁷Al‐³¹P MQ‐HMQC opens new possibilities of describing details of three‐dimensional bounded networks. Copyright © 2009 John Wiley & Sons, Ltd.     

Dynamique multi-contact d'un système de solides tridimensionnels rigidesMulti-contact dynamics of a set of three-dimensional rigid bodies

This study is in keeping with the general pattern of dynamical simulations of a set of rigid three-dimensional bodies submitted to unilateral contact constraints with dry friction. An exact formulation (respecting the contact and friction laws) of the problem of predicting the system accelerations and the contact status, in further evolution is proposed. A numerical treatment of this kind of nonlinear problem is presented. This approach is applied to a simple multi-contact example, and yields results in agreement with those of analytical and numerical type, known for this example. To cite this article: C. Le Saux et al., C. R. Mecanique 331 (2003).     

Multicentered effective group potentials: ligand-field effects in organometallic clusters and dynamical study of chemical reactivity

A new multicentered effective group potential (EGP) is obtained for η⁶-benzene. Applications on $[\hbox{Ru}_{4}(\hbox{H})_{4}(\hbox{C}_{6}\hbox{H}_{6})_{4}]^{n+}$ clusters (n = 0 or 2) are in excellent agreement with reference DFT studies in terms of geometries, energies and electronic structures. In particular, the small singlet–triplet energy difference (3.8 kcal mol^?1) in [Ru₄(H)₄(C₆H₆)₄]²⁺ is very well reproduced. This new EGP is nevertheless not free from the limitations associated to this first generation of molecular pseudopotentials. A cautious analysis of the nature and exact role of this EGP is made, which provides new directions for the elaboration of the next generation of EGPs. In addition, the η⁵-cyclopentadienyl EGP has been used to perform a constrained dynamical simulation for the reaction of Cp₂LaH with H₂. The energy conservation during the simulation as well as the activation barrier extracted from the simulation clearly demonstrate the good behavior of this EGP in the context of molecular dynamics. Anharmonic effects on this reaction are underlined, further demonstrating the high accuracy of the potential energy surface obtained with EGPs. From a more general point of view, such EGPs are expected to provide accurate albeit low-cost ligand-field effects in organometallic clusters or nanoparticles and to allow dynamical studies at the surface of such compounds.     

Application of a multi-component Eulerian approach to capture interface evolution and vorticity generation in compressible multiphase flow

The hyperbolic Eularian model is used as a mathematical framework for compressible multiphase flows. The formulation was obtained after an averaging process of the single phase Navier-Stokes equations. The closure of multi-component system leads to the volume fraction equation containing a non-conservative term and a pressure equilibrium condition. As a result the model equations cannot be written in a conservative form. To solve the equations a finite volume Godunov type computational approach is developed which uses an approximate Riemann solver combined with a numerical scheme to tackle the non-conservative terms. The approach accounts for pressure non-equilibrium. It enables resolving interfaces separating compressible fluids and captures the baroclinic source of vorticity generation. The computations are performed for various initial conditions and compared with theoretical and experimental data for a shock-bubble interaction problem. The investigated cases include acoustic wave transmission through isolated bubbles of helium and krypton. The numerical results illustrate the characteristic features of the evolving interfaces. The impulsively generated flow perturbations are dominated by the reflection and refraction of the shock and by the vorticity generation within the media. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Ionic Liquid Crystals Formed by Self‐Assembly around an Anionic Anthracene Core

We have designed and synthesised a series of modular, mesogenic complexes based on anthracene‐2,6‐disulfonate and trialkoxybenzyl‐functionalised imidazolium cations. Each complex contains a central, rigid, dianionic anthracene core and two flexible monocations bearing paraffin chains anchored on imidazolium rings. Anthracene‐2,6‐disulfonate can be crystallised with various simple alkylammonium ions and, in the case of ⁺N(CH₃)₂(C₁₆H₃₃)₂, a crystal structure determination has shown that the long paraffinic chains are intercalated between the anthracene moieties. The dianion forms columnar mesophases with trialkoxybenzylimidazolium cations, as identified by polarising optical microscopy and X‐ray scattering measurements. Differential scanning calorimetry studies confirmed mesomorphic behaviour from room temperature to about 200 °C for alkyl chains containing 8, 12 and 16 carbon atoms. The strong luminescence of anthracene is maintained in the mesophase and fluorescence measurements confirmed the presence of J aggregates in all cases. The new functional materials described herein provide an easy access to stable and luminescent mesomorphic materials engineered by an ionic self‐assembly process.     

Two channel multilayer mirrors for astrophysics

A two-channel mirror reflecting both Fe-IX/X (λ = 17.1 nm) and He-II (30.4 nm) resonance lines at near normal incidence has been designed, fabricated and characterized. These two passbands are often chosen in space instruments designed for the observation of the solar corona. The mirror structure used for optimization is a superposition of two periodic multilayers with three components per period. It has been designed by using optimization software with an appropriate merit function. The theoretical reflectivity for both resonance lines can reach 0.25. It is shown that, by using a set of filters, one can select either the Fe-IX/X or the He-II channel. The spectral response of the two-channel mirror has been measured on synchrotron radiation source on a large wavelength range, from 12 nm to 35 nm. Experimental reflectivity reaches 0.32 for the Fe-IX/X line and 0.19 for the He-II line.     

An efficient numerical scheme for precise time integration of a diffusion-dissolution/precipitation chemical system

A numerical scheme based on an operator splitting method and a dense output event location algorithm is proposed to integrate a diffusion-dissolution/precipitation chemical initial-boundary value problem with jumping nonlinearities. The numerical analysis of the scheme is carried out and it is proved to be of order 2 in time. This global order estimate is illustrated numerically on a test case.

     

Hydroxylamine-functionalised silica surfaces for biochip applications

The syntheses of triethoxy and trimethoxy silanes possessing an unprotected hydroxylamine group are described. The grafting of these coupling agents at the surface of oxidised silicon wafers was studied. Accessibility of the hydroxylamine group at the surface was demonstrated with chemical reagents, and the surface proved efficient for covalent immobilisation of peptides possessing the COCHO function.