Nanocrystal Shape Control: Synthesis and Structure–Property Correlation in Shape‐Controlled ZnO Nanoparticles Prepared by Chemical Vapor Synthesis and their Application in Dye‐Sensitized Solar Cells (Adv. Funct. Mater. 6/2009)

Here, the large scale synthesis of nanocrystalline ZnO spheres and tetrapods in the size range of 8–40 nm by chemical vapor synthesis using zinc metal as precursor is described. A detailed study of the effect of experimental parameters on the morphology and yield is presented. High‐resolution transmission electron microscopy images of the tetrapods show that they are formed by the self assembly of four nanorods in the vapor phase. The tetrapods have optical absorption coefficients that are one order of magnitude greater than the spheres and show intense UV luminescence whereas the spheres show only the green emission. The observed differences in the optical properties are related to the presence of surface defects present in the nanospheres. The tetrapods have increased efficiencies for application in dye sensitized solar cells when compared to spheres.     

Experimental study and detailed kinetic modeling of the effect of exhaust gas on fuel combustion: mutual sensitization of the oxidation of nitric oxide and methane over extended temperature and pressure ranges

New experimental results were obtained for the mutual sensitization of the oxidation of NO and methane in a fused silica jet-stirred reactor operating at 1-10 atm, over the temperature range 800-1150 K. Probe sampling followed by on-line FTIR analyses and off-line GC-TCD/FID analyses allowed the measurement of concentration profiles for the reactants, stable intermediates, and final products. Detailed chemical kinetic modeling of the experiments was performed. An overall reasonable agreement between the present data and modeling was obtained, whereas previously published models failed to properly represent these new data. According to the proposed model, the mutual sensitization of the oxidation of methane and NO proceeds through the NO to NO₂ conversion by HO₂ and CH₃O₂. The modeling showed that at 1-10 atm, the conversion of NO to NO₂ by CH₃O₂, is more important at low temperatures (800 K) than at higher temperatures (850-900 K), where the reaction of NO with HO₂ dominates the production of NO₂. The NO to NO₂ conversion is enhanced by the production of HO₂ and CH₃O₂ radicals from the oxidation of the fuel. The production of OH resulting from the oxidation of NO promotes the oxidation of the fuel: NO + HO₂ ? OH + NO₂ is followed by OH + CH₄ ? CH₃. At low temperature, the reaction further proceeds via CH₃ + O₂ ? CH₃O₂, CH₃O₂ + NO ? CH₃O + NO₂. At higher temperatures, the production of CH₃O involves NO₂: CH₃ + NO₂ ? CH₃O. The sequence is followed by CH₃O ? CH₂O + H, CH₂O + OH ? HCO, HCO + O₂ ? HO₂, and H + O₂ ? HO₂. ? CH₂O + H, CH₂O + OH ? HCO, HCO + O₂ ? HO₂, and H + O₂ ? HO₂.     

Data confidentiality: to which extent cryptography and secured hardware can help

Data confidentiality has become a major concern for individuals as well as for companies and administrations. In a classical client-server setting, the access control management is performed on the server, relying on the assumption that the server is a trusted party. However, this assumption no longer holds given the increasing vulnerability of database servers facing a growing number of external and even internal attacks. This paper studies different alternatives exploiting cryptographic techniques and/or tamper-resistant hardware to fight against these attacks. The pros and cons of each alternative are analyzed in terms of security, access control granularity and preserved database features (performance, query processing, volume of data). Finally, this paper sketches a hybrid approach mixing data encryption, integrity control and secured hardware that could pave the way for future highly securedDbmsS.     

Chemical oxidation decreases proteolytic susceptibility of skeletal muscle myofibrillar proteins

The objective of this study was to investigate the effect of chemical oxidation on proteolysis susceptibility of myofibrillar proteins. Myofibrils were prepared from pig M. longissimus dorsi and oxidised by a hydroxyl radical generating system. Protein oxidation level was measured by the carbonyl content, free thiol group content and bityrosine formation. Oxidised or non-oxidised myofibrillar proteins were exposed to papain and proteolysis was estimated by fluorescence using fluorescamine. Oxidation of myofibrillar proteins was dependent upon the oxidising agent concentration. Disulfide bridge and bityrosine formation indicated that oxidation by OH° can induce protein polymerization. Electrophoretic study showed that myosin was the protein most sensitive to oxidation. Results showed a direct and quantitative relationship between protein damages by hydroxyl radical and decreased proteolytic susceptibility. Electrophoretic observations suggest that polymerization and aggregation may explain in part decreased susceptibility of myofibrillar proteins to proteolysis.     

Numerical Simulations of Intra-voxel Dephasing Effects and Signal Voids in Gradient Echo MR Imaging using different Sub-grid Sizes

Signal void artifacts in gradient echo imaging are caused by the intra-voxel dephasing of the spins. Intra-voxel dephasing can be estimated by computing the field distribution on a sub-grid inside each picture element, followed by integration of all magnetization components. The strategy of computing the artifacts based on the integration of the sub-voxel signal components is presented here for different sub-grids. The coarseness of the sub-grid is directly related to computational effort. The possibility to save memory space and computing time for the dipole model by computing the field only on a sub-grid is addressed in the presented article. It is investigated as to how far computational time and memory space can be reduced by using an appropriate sub-grid. Numerical results for a model of a partially diamagnetically coated needle shaft are compared to experimental findings. In the case of a pure titanium needle, it is shown as being sufficient to compute the field distribution on a sub-grid that is at least four times coarser in each direction than the grid used to discretize the object in the related MR image. Due to three nested loops over the 3D grid, the need for memory space and time is saved by a factor 64. Deviations between measurements and simulations for the broad side of the artifact (uncompensated) and for the small side of the artifact (compensated) were 15.5%, respectively, 19.1% for orientation parallel to the exterior field, and 22.7%, respectively, 23.1% for orientation perpendicular to the exterior field.     

Impact of 20∶4n−6 supplementation on the fatty acid composition and hemocyte parameters of the pacific oyster crassostrea gigas

Arachidonic acid (20∶4n−6, ArA) and its eicosanoid metabolites have been demonstrated to be implicated in immune functions of vertebrates, fish, and insects. Thus, the aim of this study was to assess the impact of ArA supplementation on the FA composition and hemocyte parameters of oysters Crassostrea gigas. Oyster dietary conditioning consisted of direct addition of ArA solutions at a dose of 0, 0.25, or 0.41 μg ArA per mL of seawater into tanks in the presence or absence of T-Iso algae. Results showed significant incorporation of ArA into gill polar lipids when administered with algae (up to 19.7%) or without algae (up to 12.1%). ArA supplementation led to an increase in hemocyte numbers, phagocytosis, and production of reactive oxygen species by hemocytes from ArA-supplemented oysters. Moreover, the inhibitory effect of Vibrio aestuarianus extracellular products on the adhesive proprieties of hemocytes was lessened in oysters fed ArA-supplemented T-Iso. All changes in oyster hemocyte parameters reported in the present study suggest that ArA and/or eicosanoid metabolites affect oyster hemocyte functions.     

Effect of Purity of Raw Materials and Processing on the Microstructure and Properties of High-Tc Ba2YCu3O7-x

Microstructure and properties of high- T _c Ba₂YCu₃O_{7- x} ceramics were studied as a function of purity of raw materials and processing conditions. Technical-grade (TG) and reagent-grade (RG) raw materials were used to prepare the precursor superconducting powders, the characteristics of which were monitored by XRD, chemical analysis, and SEM. Bulk specimens were then prepared with the two master batches. XRD microphase analysis and SEM-EDS investigation did not show phase differences. J _c and normal-state resistivity measurements indicated that the TG specimens had more resistive grain boundaries than did RG specimens.     

Photocatalytic degradation of phenol on MWNT and titania composite catalysts prepared by a modified sol–gel method

Multi-walled carbon nanotubes (MWNT) and nanocrystalline titania composite catalysts were prepared by a modified sol–gel method. Thermogravimetric analysis, N₂ adsorption–desorption isotherm measurements, powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray analysis, transmission electron microscopy and UV–vis spectra were carried out to characterize the composite catalysts with different MWNT contents. The results suggest that the presence of MWNT embedding in the composite catalysts matrix prevents TiO₂ particle agglomeration. Additionally, a correlation exists between the MWNT content and the changes in the UV–vis absorption properties. The photocatalytic degradation of phenol was chosen as a model reaction to evaluate the photocatalytic activities of the composite catalysts. An optimum of the synergetic effect was found for a weight ratio MWNT/TiO₂ equal to 20%. The effects induced by MWNT on the composite catalysts may be explained in terms of a strong interphase interaction between MWNT and TiO₂ in the composite catalysts.     

Scanning and transmission electron microscopy for evaluation of order/disorder in bone structure

A comparative characterization of the structure of normal and abnormal (osteoporotic) human lumbar and thoracic vertebrae samples was carried out to reveal the type of possible disorder. Samples from the bone fragments extracted during the surgery due to vertebra fractures were examined by scanning electron microscopy (SEM), conventional and high resolution transmission electron microscopy (TEM and HRTEM), and X-ray energy dispersive spectroscopy (EDS). Contrary to what might be expected in accordance with possible processes of dissolution, formation and remineralization of hard tissues, no changes in phase composition of mineral part, crystal sizes (length, width, and thickness), and arrangement of crystals on collagen fibers were detected in abnormal bones compared to the normal ones. The following sizes were determined by HRTEM for all bone samples: 相似文献   

Green emitting β$ubeta$-SiAlON:Eu2+ phosphors derived from chemically modified perhydropolysilazanes

We report the first synthesis of β-SiAlON:Eu²⁺ phosphors from single-source precursors, perhydropolysilazane (PHPS), chemically modified with Al(OCH(CH₃)₂)₃, and EuCl₂. The reactions occurring during the precursor synthesis and the subsequent thermal conversion of polymeric precursors into β-SiAlON:Eu²⁺ phosphors have been studied by a complementary set of analytical techniques, including infrared spectroscopy, gas chromatography–mass spectrometry, thermogravimetry–mass spectrometry, X-ray diffraction (XRD), photoluminescence spectroscopy, and scanning electron microscopy. It has been clearly established that Al(OCH(CH₃)₂)₃ immediately reacted with PHPS to afford N–Al bonds at room temperature, whereas N–Eu bond formation was suggested to proceed above 600°C accompanied by the elimination of HCl up to 1000°C in flowing N₂. The subsequent 1800°C-heat treatment for 1 h under an N₂ gas pressure at 980 kPa allowed converting the single-source precursors into fine-grained β-SiAlON:Eu²⁺ phosphors. XRD analysis revealed that the Al/Si of .09 was the critical atomic ratio in the precursor synthesis to afford single-phase β-SiAlON (z = .55). Moreover, Eu²⁺-doping was found to efficiently reduce the carbon impurity in the host β-SiAlON. The polymer-derived β-SiAlON:Eu²⁺ phosphors exhibited green emission under excitation at 460 nm and achieved the highest green emission intensity at the critical dopant Eu²⁺ concentration at 1.48 at%.