Bismuth (III) coordination to cyclen and cyclam bearing four appended groups

The synthesis of new cyclam and cyclen derivatives (respectively L₁ and L₂), able to efficiently coordinate to Bi(III) are presented here. The two ligands bearing two different pendant arms (two-pycolyl and two (2-(2-hydroxyethoxy)ethyl)-2-aminoacetamide in trans position) were synthesized in the aim to obtain stable and water soluble complexes. The thermodynamic and kinetic of the formation of the corresponding complexes in aqueous solution were studied by means of NMR and potentiometric investigations. The fast kinetic of complexation and the high stability of the complexes are encouraging for further application with the alpha-emitting ²¹³Bi isotope.     

Molecular hydrogen "pairing" interaction in a metal organic framework system with unsaturated metal centers (MOF-74)

Infrared (IR) absorption spectroscopy measurements of molecular hydrogen in MOF-74-M (M = metal center) are performed as a function of temperature and pressure [to 45 kTorr (60 bar) at 300 K, and at lower pressures in the 20-200 K range] to investigate the nature of H(2) interactions with the unsaturated metal centers. A small shift (～?-30 cm(-1) with respect to the unperturbed H(2) molecule) is observed for the internal stretch frequency of H(2) molecules adsorbed on the metal site at low loading. This finding is in contrast to much larger shifts (～?-70 cm(-1)) observed in previous studies of MOFs with unsaturated metal centers (including MOF-74) and the general assumption that H(2) stretch shifts depend on adsorption energies (FitzGerald et al., Phys. Rev. B 2010, 81, 104305). We show that larger shifts (～?-70 cm(-1)) do occur, but only when the next available site ("oxygen" site) is occupied. This larger shift originates from H(2)-H(2) interactions on neighboring sites of the same pore, consistent with the short distance between H(2) in these two sites ～2.6 ? derived from an analysis of neutron diffraction experiments of D(2)-D(2) at 4 K (Liu et al., Langmuir 2008, 24, 4772-4777). Our results at 77 K and low loading can be explained by a diffusion barrier against pair disruption, which should be enhanced by this interaction. Calculations indicate that the vibrational shifts do not correlate with binding energies and are instead very sensitive to the environment (interaction potential and H(2)-H(2) interactions), which complicates the use of variable temperature IR methods to calculate adsorption energies of specific adsorption sites.     

Gold-catalyzed oxidative coupling reactions with aryltrimethylsilanes

During continuing studies with a novel oxidative gold oxyarylation reaction, arylsilanes were found to be competent coupling partners, providing further evidence for an intramolecular electrophilic aromatic substitution mechanism. While providing yields complementary to those of the previously described boronic acid methods, the use of trimethylsilanes reduces the observation of homocoupling byproducts and allows for facile intramolecular coupling reactions.     

Problème de Cauchy non autonome pour des équations d'évolution

Nous étudions dans un espace de Banach le problème de Cauchy pour des équations d'évolution gouvernées par des opérateurs dépendant du temps dans un cadre plus général que les hypothèses d'accrétivité. D'une part, ce cadre s'adapte bien à des perturbations continues vérifiant des conditions de type Osgood, d'autre part, l'essentiel des résultats de la théorie moderne des équations d'évolution abstraites se trouve prolongé à ce nouveau contexte.     

Conception and Evaluation of a Library of Cleavable Mass Tags for Digital Polymers Sequencing

A library of phosphoramidite monomers containing a main-chain cleavable alkoxyamine and a side-chain substituent of variable molar mass (i.e. mass tag) was prepared in this work. These monomers can be used in automated solid-phase phosphoramidite chemistry and therefore incorporated periodically as spacers inside digitally-encoded poly(phosphodiester) chains. Consequently, the formed polymers contain tagged cleavable sites that guide their fragmentation in mass spectrometry sequencing and enhance their digital readability. The spacers were all prepared via a seven steps synthetic procedure. They were afterwards tested for the synthesis and sequencing of model digital polymers. Uniform digitally-encoded polymers were obtained as major species in all cases, even though some minor defects were sometimes detected. Furthermore, the polymers were decoded in pseudo-MS³ conditions, thus confirming the reliability and versatility of the spacers library.     

Direct numerical simulation of the interaction of isotropic turbulence with a shock wave using shock-fitting

The interaction of three-dimensional isotropic turbulence with a plane shock at Mach numbers of $M=2.0$ and $M=3.0$ is investigated via direct numerical simulation. The numerical scheme is based on a characteristic-type formulation of the Navier–Stokes equations and uses fifth-order upwind schemes in space, a fourth order Runge Kutta scheme in time and a shock-fitting as inlet condition. The isotropic turbulence was generated in a separate computation based on a prescribed energy spectrum. This turbulent flow is considered as frozen, and is convected through the shock with a prescribed average shock speed. An FFT interpolation is used to obtain the upstream values at the instantaneous shock location. Turbulence enhancement is observed, and the evolution of velocity fluctuations as well as turbulence microscales are in good agreement with the behaviour observed using shock-capturing. To cite this article: J. Sesterhenn et al., C. R. Mecanique 333 (2005).     

Compliance and Hill polarization tensor of a crack in an anisotropic matrix

This work aims at developing an efficient method to compute the compliance due to a crack modeled as a flat ellipsoid of any shape in an infinite elastic matrix of arbitrary anisotropy (Eshelby problem) when no closed-form solution seems currently available. Whereas the solution of this problem usually requires the calculation of the so-called fourth-order Hill polarization tensor if the ellipsoid is not singular, it is shown that the crack compliance can be derived from the first-order term in the Taylor expansion of the Hill tensor with respect to the smallest aspect ratio of the ellipsoidal inclusion. For a 3D ellipsoidal crack model, this first-order term is expressed as a simple integral thanks to the Cauchy residue theorem. A similar method allows to express the same term in the case of a cylindrical crack model without any integral. A numerical example is finally treated.     

Designing liquid-crystalline dendronised hexa-adducts of [60]fullerene via click chemistry

ABSTRACT

Liquid-crystalline [60]fullerodendrimers were constructed via click chemistry based on the reaction between hexa-adducts of [60]fullerene (C₆₀) bearing 12 azide groups and alkyne-terminated cyanobiphenyl dendrons of first- and second-generation. The structure of all the new compounds was confirmed by IR, UV, ¹H and ¹³C NMR spectroscopies and mass spectrometry. The mesomorphic properties were studied by polarised optical microscopy, differential scanning calorimetry and small-angle X-ray scattering. The hexa-adduct of C₆₀ functionalised with the first-generation dendrons gave rise to the formation of a smectic A phase and a rectangular columnar phase (c2mm symmetry) while the hexa-adduct of C₆₀ decorated with the second-generation dendrons displayed only a rectangular columnar phase (c2mm symmetry). Our results show that the hexa-adduct of C₆₀ is a unique synthetic platform for the design of fullerodendrimers and dendronised materials.