Characterization of Linear Structures

We study the notionof linear structure of a function defined from F^mto Fⁿ, and in particular of a Boolean function.We characterize the existence of linear structures by means ofthe Fourier transform of the function. For Boolean functions,this characterization can be stated in a simpler way. Finally,we give some constructions of resilient Boolean functions whichhave no linear structure.     

Structure, microstructure, and size dependent catalytic properties of nanostructured ruthenium dioxide

Nanostructured powders of ruthenium dioxide RuO₂ were synthesized via a sol gel route involving acidic solutions with pH varying between 0.4 and 4.5. The RuO₂ nanopowders were characterized by X-ray diffraction, scanning and transmission electron microscopy (SEM and TEM). Rietveld refinement of mean crystal structure was performed on RuO₂ nanopowders and crystallized standard RuO₂ sample. Crystallite sizes measured from X-ray diffraction profiles and TEM analysis varied in the range of 4-10 nm, with a minimum of crystallite dimension for pH=1.5. A good agreement between crystallite sizes calculated from Williamson Hall approach of X-ray data and from direct TEM observations was obtained. The tetragonal crystal cell parameter (a) and cell volumes of nanostructured samples were characterized by values greater than the values of standard RuO₂ sample. In addition, the [Ru-O₆] oxygen octahedrons of rutile structure also depended on crystal size. Catalytic conversion of methane by these RuO₂ nanostructured catalysts was studied as a function of pH, catalytic interaction time, air methane composition, and catalysis temperature, by the way of Fourier transform infrared (FTIR) spectroscopy coupled to homemade catalytic cell. The catalytic efficiency defined as FTIR absorption band intensities I(CO₂) was maximum for sample prepared at pH=1.5, and mainly correlated to crystallite dimensions. No significant catalytic effect was observed from sintered RuO₂ samples.     

Characterizing the ZrC(111)/c-ZrO2(111) Hetero-Ceramic Interface: First Principles DFT and Atomistic Thermodynamic Modeling

The mechanical and physical properties of zirconium carbide (ZrC) are limited to its ability to deteriorate in oxidizing environments. Low refractory oxides are typically formed as layers on ZrC surfaces when exposed to the slightest concentrations of oxygen. However, this carbide has a wide range of applications in nuclear reactor lines and nozzle flaps in the aerospace industry, just to name a few. To develop mechanically strong and oxygen-resistant ZrC materials, the need for studying and characterizing the oxidized layers, with emphasis on the interfacial structure between ZrC and the oxidized phases, cannot be understated. In this paper, the ZrC(111)//c-ZrO₂ (111) interface was studied by both finite temperature molecular dynamic simulation and DFT. The interfacial mechanical properties were characterized by the work of adhesion which revealed a Zr|OO|Zr|OO//ZrC(111) interface model as the most stable with an oxygen layer from ZrO₂ being deposited on the ZrC(111) surface. Further structural analysis at the interface showed a crack in the first ZrO₂ layer at the interfacial region. Investigations of the electronic structure using the density of state calculations and Bader charge analysis revealed the interfacial properties as local effects with no significant impacts in the bulk regions of the interface slab.     

High-efficiency single-mode Raman generation in a liquid-filled photonic bandgap fiber

Single-spatial-mode Raman generation in an ethanol-filled photonic bandgap fiber is demonstrated. Due to the limited bandwidth of the fiber, the generation is limited to the first Stokes order only, allowing high generated power without any visible decrease of the conversion efficiency. The realization of these two key properties opens the way to the realization of optimized compact nonlinear wavelength converters that will accommodate a large variety of usable liquids.     

Solvent/base effects in the selective domino synthesis of phenanthridinones that involves high-valent palladium species: experimental and theoretical studies

The domino reaction of o-bromobenzamides 1a-m in the presence of K(2)CO(3) and the [PdCl(2)(PPh(3))(2)] catalyst granted a selective access to phenanthridinones 2 or to the new 1-carboxamide phenanthridinones 3 depending on the solvent, DMF or 1,4-dioxane, respectively. Investigations of the reaction parameters provided the first example of a direct correlation between the base dissociation and the solvent polarity on the selectivity observed. Moreover, mechanistic studies (NMR spectroscopy and ESI-MS monitoring) allowed us to characterize Pd(II) palladacycle 4 and biaryl species as common intermediates for these two domino processes. On that basis, C(sp(2))-C(sp(2)) bond formation is envisaged by generation of a Pd(IV) complex after oxidative addition of 1 into Pd(II) palladacycle 4, a rationale that is supported by DFT calculations. A general catalytic cycle is proposed to account for these observations.     

Physical-chemistry of silica/alkaline silicate interactions during consolidation. Part 1: Effect of cation size

The purpose of this work is to identify the effect of the cation nature on mechanisms of the sand consolidation with alkaline silicate solution at low temperature (70 °C). Three diluted lithium, sodium and potassium silicate solutions with [Si] = 2.8 mol/l were used to agglomerate sand composed of grains which mean diameter is 340 μm. According to the cation, different behaviors were observed in terms of the drying time and the material cohesion. Essentially, the drying time increases with decreasing cation size. In contrast, the compressive strength raises when the cation size increases inducing intra-granular rupture highlighted by SEM observations. This could find an explanation in the cation hydration sphere of cations. The strength of the cation–water electrostatic interaction becomes less important as the size of the cations increase leading to more ionic bonds. Despite their strong consolidation, potassium-based materials have a high solubility in water. This result is consistent with the ionic nature of bonds.     

Bio-dissolution of colloidal-size clay minerals entrapped in microporous silica gels

Four colloidal-size fractions of strongly anisotropic particles of nontronite (NAu-2) having different ratios of basal to edge surfaces were incubated in the presence of heterotrophic soil bacteria to evaluate how changes in mineral surface reactivity influence microbial dissolution rate of minerals. To avoid any particle aggregation, which could change the reactive surface area available for dissolution, NAu-2 particles were immobilized in a biocompatible TEOS-derived silica matrix. The resulting hybrid silica gels support bacterial growth with NAu-2 as the sole source of Fe and Mg. Upon incubation of the hybrid material with bacteria, between 0.3% and 7.5% of the total Fe included in the mineral lattice was released with a concomitant pH decrease. For a given pH value, the amount of released Fe varied between strains and was two to twelve-fold higher than under abiotic conditions. This indicates that complexing agents produced by bacteria play an important role in the dissolution process. However, in contrast with proton-promoted NAu-2 dissolution (abiotic incubations) that was negatively correlated with particle size, bacterial-enhanced dissolution was constant for all size fractions used. We conclude that bio-dissolution of nontronite particles under acidic conditions seems to be controlled by bacterial metabolism rather than by the surface reactivity of mineral.     

Copolyimides containing alicyclic and fluorinated groups: Characterization of the film microstructure

The microstructures of a series of copolyimide films were characterized with different experimental methods such as density measurements, X‐ray diffraction, ultraviolet‐visible spectrophotometry, positron annihilation spectroscopy, and dynamic mechanical analysis. The experimental data were linked to the chemical structures of the polymers and especially the alicyclic and fluorinated monomers. Some analysis responses were directly dependent on the fluorine atoms and, therefore, did not provide clear information about the microstructures. The chain organization in the amorphous films appeared to be significantly dependent on the effect of the casting solvent. The influence of the alicyclic group content was quite significant for a nonsubstituted diamine but was strongly attenuated with a fluorinated diamine. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2998–3010, 2003     

Action de l'acide fluorhydrique sur les azirines : synthèse d'α-fluorocétones et de difluoroamines - étude de l'orientation de la réaction

Addition of Olah's reagent in benzene or methylene chloride to azirines leads to the formation of difluoroamines or α-fluoroketones. This reaction has been applied to the synthesis of 17 α-fluoropregnenolone. The formation of fluoroketone proceeds via a cationic intermediate. Yield is improved when using a more nucleophilic fluorinating reagent obtained by addition of triethylamine to Olah's reagent.     

Theoretical description of the electronic structure of the alkali hydride cation NaH+

A theoretical determination of the electronic structure of NaH+ is presented. Potential energy curves and dipole moments have been computed for 48(2)Lambda(+) electronic states (i.e., correlated adiabatically up to Na(6s) + H+) through a model-potential-type method over a wide range of R. Equilibrium distances, transition energies, depths of wells, and/or heights of humps predicted at short and large interatomic separations are reported and compared with available experimental and theoretical values. Variations of the static dipole polarizabilities versus internuclear distance have been determined for the two lowest states.