Nano Design of Alumina Supported Monometallic Catalysts: A Promising Way to Improve the Selective Hydrogenation of Poly-Unsaturated Hydrocarbons

In the field of catalysis by metals, a new insight for the nanodesign of supported heterogeneous catalysts is the tailoring of metallic nanoparticles. In this work, well-faceted monometallic nanoparticles (Pd, Pt, Ni) exposing mostly the {111} crystallographic facet are obtained in aqueous solution and are deposited on an alumina support. The involved mechanisms of nanoparticles formation are determined and are evidenced to be different as a function of the nature of the metal. In the case of palladium the mechanism consists in an oriented attachment of palladium nanoparticles leading to the energetically most favourable stacking of nanoparticles, at the origin of the early differentiation of the nanoparticles shapes and of the formation of the well-faceted palladium nanoparticles. In the case of platinum, the mechanism seems to be a combination of aggregation of already reduced nuclei and direct reduction depending on the experimental conditions. In the case of the less reductible metal, nickel, well-faceted nanoparticles are not obtained during the synthesis and only a thermal activation under hydrogen can engender their formation. The impact of the {111} crystallographic facet for platinum and nickel is very important and induces a drastic increase of selectivity towards olefins formation with a selectivity close to the one of a palladium catalyst which is the most selective metal for the selective hydrogenation of poly-unsaturated hydrocarbons.     

Compression dewatering of municipal activated sludge: effects of salt and pH

Even after mechanical dewatering, activated sludge contains a large amount of water. Due to its composition and biological nature this material is usually highly compressible and known to be difficult to dewater. In the present work, two treatments (salt addition and pH modification) are proposed to highlight some aspects which could explain the poor dewaterability of activated sludge. Dewatering tests are carried out in a pressure-driven device in order to well examine both, filtration and compression stages. Physico-chemical parameters, such as surface charge, hydrophobicity, extracellular polymeric substances (EPS) content and filtrate turbidity are measured on the tested sludge, for a better analysis of dewatering results.The dewatering ability of the sludge is widely linked to the cohesion of the flocculated matrix and the presence of fine particles. Both treatments alter the flocculated matrix and release fine particles. The release of fine particles tends to clog both, the filter cake and the filter medium. Consequently, the filtration rate decreases due to higher resistances to the flow. On another hand, the polymeric matrix breakdown enables to release some water trapped within the floc to the bulk liquid phase and thus facilitates its removal, which tends to decrease the moisture content of the filter-cake. It also impacts the compression dewatering step. The more destroyed structures lead to less elastic cakes and thus a slower primary consolidation stage. At the opposite, the mobility of the broken aggregates within the filter-cake does not seem to be improved by size reduction (the kinetics of the secondary consolidation stage are not significantly modified).     

Grape berry bacterial microbiota: Impact of the ripening process and the farming system

Wine grapes are a primary source of microbial communities that play a prominent role in the quality of grapes prior to harvesting, as well as in the winemaking process. This study investigated the dynamics and diversity of the epiphytic bacteria on the grape berry surface during maturation. The quantitative and qualitative effects of conventional and organic farming systems on this microbial community were investigated, using both cultivation-dependent and independent approaches. Analyses of grape berry bacterial microbiota revealed changes in the size and structure of the population during the berry ripening process, with levels rising gradually and reaching their highest value when the berries were over ripe. As the season progressed to maturity, Gram-negative bacterial communities (mostly Pseudomonas spp.) declined whereas Gram-positive communities (mostly Micrococcus spp.) increased. The 16S rRNA gene sequences of cultured isolates were analysed and over 44 species were identified from 21 genera in the Proteobacteria, Actinobacteria, and Firmicutes phyla. Copper concentrations originating from phytosanitary treatments varied according to the vineyard and farming system. A negative correlation between copper concentrations and cell densities provided clear evidence that copper inhibited bacterial communities. The bacterial community structure was analysed by targeting the 16S rRNA genes, using PCR-DGGE on cultivable populations and T-RFLP on whole communities in cell suspension. The results suggest that the farming system has a clear impact on the bacterial community structure.     

Mechanical and Thermodynamic Properties of Non-Muscle Contractile Tissues: The Myofibroblast and the Molecular Motor Non-Muscle Myosin Type IIA

Myofibroblasts are contractile cells found in multiple tissues. They are physiological cells as in the human placenta and can be obtained from bone marrow mesenchymal stem cells after differentiation by transforming growth factor-β (TGF-β). They are also found in the stroma of cancerous tissues and can be located in non-muscle contractile tissues. When stimulated by an electric current or after exposure to KCl, these tissues contract. They relax either by lowering the intracellular Ca²⁺ concentration (by means of isosorbide dinitrate or sildenafil) or by inhibiting actin-myosin interactions (by means of 2,3-butanedione monoxime or blebbistatin). Their shortening velocity and their developed tension are dramatically low compared to those of muscles. Like sarcomeric and smooth muscles, they obey Frank-Starling’s law and exhibit the Hill hyperbolic tension-velocity relationship. The molecular motor of the myofibroblast is the non-muscle myosin type IIA (NMIIA). Its essential characteristic is the extreme slowness of its molecular kinetics. In contrast, NMIIA develops a unitary force similar to that of muscle myosins. From a thermodynamic point of view, non-muscle contractile tissues containing NMIIA operate extremely close to equilibrium in a linear stationary mode.     

Phase formation and crystal structure determination in the Y2O3–TeO2 system prepared in an oxygen atmosphere

The solid state synthesis of phases in the Y₂O₃–TeO₂ system under oxygen atmosphere is presented here as a method of obtaining pure material starting from simple oxides such as Y₂O₃ and α-TeO₂. In the composition range of 0–100% of TeO₂, the compounds Y₆TeO₁₂, Y₂TeO₆, Y₂Te₄O₁₁, Y₂Te₅O₁₃ and Y₂Te₆O₁₅ were synthesized after annealing at 770–1100 °C. The reactions of decomposition of the phases at higher temperatures are also reported.The crystal structure of Y₆TeO₁₂ has been refined by the Rietveld method from X-ray powder diffraction data. It crystallizes with the rhombohedral space group R-3 (S.G. no. 148) as the homologous compound In₆TeO₁₂. It is based on a three dimensional arrangement of isolated TeO₆ octahedra (TeO = 1.94 Å) and edge-shared YO₇ polyhedra (YO bond lengths ranging from 2.18 to 2.65 Å).     

Effects of H2S addition on hydrogen ignition behind reflected shock waves: Experiments and modeling

Hydrogen sulfide is a common impurity that can greatly change the combustion properties of fuels, even when present in small concentrations. However, the combustion chemistry of H₂S is still poorly understood, and this lack of understanding subsequently leads to difficulties in the design of emission-control and energy-production processes. During this study, ignition delay times were measured behind reflected shock waves for mixtures of 1% H₂/1% O₂ diluted in Ar and doped with various concentration of H₂S (100, 400, and 1600 ppm) over large pressure (around 1.6, 13, and 33 atm) and temperature (1045–1860 K) ranges. Results typically showed a significant increase in the ignition delay time due to the addition of H₂S, in some cases by a factor of 4 or more over the baseline mixtures with no H₂S. The magnitude of the increase is highly dependent on the temperature and pressure. A detailed chemical kinetics model was developed using recent, up-to-date detailed-kinetics mechanisms from the literature and by changing a few reaction rates within their reported error factor. This updated model predicts well the experimental data obtained during this study and from the shock-tube literature. However, flow reactor data from the literature were poorly predicted when H₂S was a reactant. This study highlights the need for a better estimation of several reaction rates to better predict H₂S oxidation chemistry and its effect on fuel combustion. Using the kinetics model for sensitivity analyses, it was determined that the decrease in reactivity in the presence of H₂S is because H₂S initially reacts before the H₂ fuel does, mainly through the reaction H₂S + H ? SH + H₂, thus taking H atoms away from the main branching reaction H + O₂ ? OH + O and inhibiting the ignition process.     

Nanocrystalline/Nanosized Ni1−γFe2+γO4 Ferrite Obtained by Contamination with Fe During Milling of NiO–Fe2O3 Mixture. Structural and Magnetic Characterization

The nanocrystalline nickel ferrite (NiFe₂O₄) was synthesized by reactive milling starting from equimolar mixture of oxides. The iron contamination during milling leads to a solid state reaction between Fe and NiFe₂O₄ spinel. This reaction starts for a milling time longer than 30 h. A mixed nickel–iron ferrite (Ni_1?γFe_2+γO₄) and elemental Ni are obtained. The evolution of the nickel–iron mixed ferrite during milling and its properties were investigated using X‐ray diffraction, Fourier Transform Infrared Spectroscopy (FTIR), Laser Particles Size Analyzer and magnetic measurements. Annealing treatment (350°C/4 h in vacuum) is favorable to the reaction between phases. Replacement of Ni²⁺ cations by iron cations provided by contamination leads to the increase of lattice parameter value of the spinel structure. The magnetization of the nickel–iron mixed ferrite newly formed is larger than the nickel ferrite magnetization (13.6 μ_B/f.u. and 6.22 μ_B/f.u., respectively), due to the magnetic moment of Fe²⁺ cation which is double as compared to the Ni²⁺ cation. Magnetization of the milled samples decreases during milling due to the structural changes induced by milling in the nickel–iron mixed ferrite. The annealing induces a reordering of the cations which leads to a larger magnetization.     

AC Impedance Behaviour of Black Diamond Films

The first measurement of impedance on free-standing diamond films from 0.1 Hz to 10 MHz up to 300℃ were reported. A wide range of chemical vapour deposition (CVD) materials were investigated, but here we concentrate are well fitted to a RC parallel circuit model and the equivalent resistance and capacitance for the diamond films have been estimated using the Zview curve fitting. The results show only one single semicircle response at each temperature measured. It was found that the resistance decreases from 62 MΩ at room temperature to 4 kΩ at300℃, with an activation energy around 0.51 eV. The equivalent capacitance is maintained at the level of 100 pF up to 300℃ suggesting that the diamond grain boundaries are dominating the conduction. At 400℃, the impedance at low frequencies shows a linear tail, which can be explained that the AC polarization of diamond/Au interface occurs.     

Mixed‐mode analysis of the sensitivity of a radiofrequency oscillator disturbed by parasitic signals

The first step of this work is to study the susceptibility of a radiofrequency oscillator to deterministic disturbance sources. A Colpitts oscillator, working around a 4 GHz frequency, contains a heterojunction bipolar transistor with a silicon–germanium base as an active device. A mixed‐mode analysis is involved, applying a microscopic drift diffusion model to the device, whereas the rest of the circuit used is governed by Kirchhoff's laws. We assume that this tool is very relevant to grasp the influence of intrinsic or extrinsic noisy sources of the oscillator. Our first simulation raw results motivate us to discuss, and perhaps extend, via some analytical models, the so‐called impulse sensitivity function model. In this paper, we try to develop quantitative predictions about the phase noise of such oscillators, and to give some new tracks on this field. Copyright © 2008 John Wiley & Sons, Ltd.     

Platelet Innate Immune Receptors and TLRs: A Double-Edged Sword

Platelets are hematopoietic cells whose main function has for a long time been considered to be the maintenance of vascular integrity. They have an essential role in the hemostatic response, but they also have functional capabilities that go far beyond it. This review will provide an overview of platelet functions. Indeed, stress signals may induce platelet apoptosis through proapoptotis or hemostasis receptors, necrosis, and even autophagy. Platelets also interact with immune cells and modulate immune responses in terms of activation, maturation, recruitment and cytokine secretion. This review will also show that platelets, thanks to their wide range of innate immune receptors, and in particular toll-like receptors, and can be considered sentinels actively participating in the immuno-surveillance of the body. We will discuss the diversity of platelet responses following the engagement of these receptors as well as the signaling pathways involved. Finally, we will show that while platelets contribute significantly, via their TLRs, to immune response and inflammation, these receptors also participate in the pathophysiological processes associated with various pathogens and diseases, including cancer and atherosclerosis.