Atomic scale insights on chlorinated gamma-alumina surfaces

The thermochemistry of chlorinated gamma-alumina surfaces is explored by means of density functional calculations as a function of relevant reaction conditions used in experiments and in high-octane fuel production in the refining industry such as hydrocarbon isomerization and reforming. The role of chlorine as a dope of the Br?nsted acidity of gamma-alumina surfaces is investigated at an atomic scale. Combining infrared spectroscopy and density functional theory calculations, the most favorable location of chlorine atoms on the (110), (100) and (111) surfaces of gamma-alumina is found to result either from direct adsorption or from the exchange of basic hydroxyl groups. Moreover, the modification of the hydrogen bond network upon chlorine adsorption is put forward as a key parameter for changing the Br?nsted acidity. In a second step, we use a thermodynamic approach based on DFT total energy calculations corrected by the chemical potentials of HCl and H2O to determine the adsorption isotherms of chlorine and the relative surface concentration of hydroxyl groups and chlorine species on the gamma-alumina surfaces. The determination of chlorine content as a function of temperature and partial pressures of H2O and HCl offers new quantitative data required for optimizing the state of the support surface in industrial conditions. The mechanisms of chlorination are also discussed as a function of reaction conditions.     

Sustainable concepts in olefin metathesis

Ruthenium-catalyzed olefin metathesis reactions represent an attractive and powerful transformation for the formation of new carbon-carbon double bonds. This area is now quite familiar to most chemists as numerous catalysts are available that enable a plethora of olefin metathesis reactions. Nevertheless, with the exception of uses in polymerization reactions, only a limited number of industrial processes use olefin metathesis. This is mainly due to difficulties associated with removing ruthenium from the final products. In this context, a number of studies have been carried out to develop procedures for the removal of the catalyst or the products of catalyst decomposition, however, none are universally attractive so far. This situation has resulted in tremendous activity in the area dealing with supported or tagged versions of homogeneous catalysts. This Review summarizes the numerous studies focused on developing cleaner ruthenium-catalyzed metathesis processes.     

Biphasic aqueous organometallic catalysis promoted by cyclodextrins: can surface tension measurements explain the efficiency of chemically modified cyclodextrins?

Methylated and hydroxypropylated cyclodextrins (CDs) are highly efficient mass transfer promoters in biphasic aqueous organometallic processes. The surface tension measurements demonstrated that these CDs adsorb at air-water interface and allowed to determine surface excess of CD by using Gibbs adsorption equation. Interestingly, a good correlation between surface excess and catalytic activity was obtained in the case of hydroformylation and Tsuji-Trost reactions. These results point out the importance of CD adsorption at the interface in biphasic aqueous organometallic processes.     

Smart Poly(styrene)/Carbon Black Conductive Polymer Composites Films for Styrene Vapour Sensing

Conductive Polymer Composites (CPC) can be used to elaborate sensing elements able to detect solvent vapours at very low concentrations (some ppm). Our experiments have shown that combining atactic PS or syndiotactic PS to five carbon black of different specific surfaces, allows obtaining a wide range of electrical resistances and surface morphologies. The CPC films have been elaborated from solutions by spraying and spin coating, the former being more adequate to design sensitive films with tuneable electrical properties. The larger electrical responses were obtained with an initial resistance close to 10⁴ Ω. Our sensors gave a response for very low styrene concentration (some ppm) increasing as a function of vapour concentration.     

Copper-catalyzed asymmetric conjugate addition of Grignard reagents to trisubstituted enones. Construction of all-carbon quaternary chiral centers

The copper-catalyzed asymmetric conjugate addition of Grignard reagents to trisubstituted cyclic enones affords enantioenriched all-carbon quaternary centers with up to 96% ee. The chiral ligand is a diaminocarbene, directly generated in situ. The combination of Grignard reagent and diaminocarbene is unprecedented in conjugate addition, and the additon of the phenyl group, on such enones, cannot be done by other conjugate addition methods.     

Refractive-index saturation-mediated multiple line emission in polymer thin-film distributed-feedback lasers

We report experimental and theoretical investigations of multiple laser-line emission in a distributed-feedback dye laser pumped by two coherent optical beams. We have used a Lloyd interferometer configuration with second- and third-order Bragg reflections to study the interaction between the two incident pumps in an organic thin film. We demonstrated theoretically that the number of laser emission lines can be interpreted with reference to the saturation effect in the refractive index.     

Terahertz,X-ray and neutron computed tomography of an Eighteenth Dynasty Egyptian sealed pottery

An Eighteenth Dynasty Egyptian sealed pottery stored at the Museum of Aquitaine (Bordeaux, France) has been investigated using terahertz radiation, X-rays and neutrons. THz computed tomography revealed nondestructively the presence of content, whereas X-rays and neutrons analyzed more precisely the fabrication process and conservation of the pottery together with the nature of this content owing to higher spatial resolution and contrast. With neutron tomography, we determined the method used to seal the jar as well as the finer structure of the inner content. Neutron-induced prompt gamma spectroscopy was finally applied to measure the elemental composition of the content, which is supposed to consist of dried germinated seeds.     

Engineering protein therapeutics: predictive performances of a structure-based virtual affinity maturation protocol

The implementation of a structure based virtual affinity maturation protocol and evaluation of its predictivity are presented. The in silico protocol is based on conformational sampling of the interface residues (using the Dead End Elimination/A* algorithm), followed by the estimation of the change of free energy of binding due to a point mutation, applying MM/PBSA calculations. Several implementations of the protocol have been evaluated for 173 mutations in 7 different protein complexes for which experimental data were available: the use of the Boltzamnn averaged predictor based on the free energy of binding (ΔΔG(*)) combined with the one based on its polar component only (ΔΔE(pol*)) led to the proposal of a subset of mutations out of which 45% would have successfully enhanced the binding. When focusing on those mutations that are less likely to be introduced by natural in vivo maturation methods (99 mutations with at least two base changes in the codon), the success rate is increased to 63%. In another evaluation, focusing on 56 alanine scanning mutations, the in silico protocol was able to detect 89% of the hot-spots.