The grain-boundary resistance of CeO2 ceramics: A combined microscopy-spectroscopy-simulation study of a dilute solution

Weakly acceptor-doped ceria ceramics were characterized structurally and compositionally with advanced transmission electron microscopy (TEM) techniques and electrically with electrochemical impedance spectroscopy (EIS). The grain boundaries studied with TEM were found to be free of second phases. The impedance spectra, acquired in the range 703 ≤ T/K ≤ 893 in air, showed several arcs that were analyzed in terms of bulk, grain-boundary, and electrode responses. We ascribed the grain-boundary resistance to the presence of space-charge layers. Continuum-level simulations were used to calculate charge-carrier distributions (of acceptor cations, oxygen vacancies, and electrons) in these space-charge layers. The acceptor cations were assumed to be mobile at high (sintering) temperatures but immobile at the temperatures of the EIS measurements. Space-charge formation was assumed to be driven by the segregation of oxygen vacancies to the grain-boundary core. Comparisons of data from the simulations and from the EIS measurements yielded space-charge potentials and the segregation energy of vacancies to the grain-boundary core. The space-charge potentials from the simulations are compared with values obtained by applying the standard, analytical (Mott–Schottky and Gouy–Chapman) expressions. The importance of modelling space-charge layers from the thermodynamic level is demonstrated.     

Structural and Functional Characterization of 4-Hydroxyphenylacetate 3-Hydroxylase from Escherichia coli

The hydroxylation of phenols into polyphenols, which are valuable chemicals and pharmaceutical products, is a challenging reaction. The search for green synthetic processes has led to considering microorganisms and pure hydroxylases as catalysts for phenol hydroxylation. Herein, we report the structural and functional characterization of the flavin adenine dinucleotide (FAD)-dependent 4-hydroxyphenylacetate 3-monooxygenase from Escherichia coli, named HpaB. It is shown that this enzyme enjoys a relatively broad substrate specificity, which allows the conversion of a number of non-natural phenolic compounds, such as tyrosol, hydroxymandelic acid, coumaric acid, hydroxybenzoic acid and its methyl ester, and phenol, into the corresponding catechols. The reaction can be performed by using a simple chemical assay based on formate as the electron donor and the organometallic complex [Rh(bpy)Cp*(H₂O)]²⁺ (Cp*: 1,2,3,4,5-pentamethylcyclopentadiene, bpy: 2,2′-bipyridyl) as the catalyst for FAD reduction. The availability of a crystal structure of HpaB in complex with FAD at 1.8 Å resolution opens up the possibility of the rational tuning of the substrate specificity and activity of this interesting class of phenol hydroxylases.     

Identification of ritual blood in African artifacts using TOF-SIMS and synchrotron radiation microspectroscopies

A new protocol is implemented to demonstrate the presence of blood in the patina of African art objects from Mali. Divided into three steps, the protocol first consists in demonstrating the presence of proteins and localizing them in the sample's cross sections using time-of-flight secondary ion mass spectrometry (TOF-SIMS) and synchrotron-based infrared microspectrometry (microFT-IR). In a second time, TOF-SIMS is used to investigate heme, which is a blood marker. If heme is missing, which could mean that it is too degraded to be detected, X-ray microfluorescence (microXRF) and X-ray absorption near-edge microspectroscopy (microXANES) are used to prove the presence of iron in the protein area and to get a fingerprint of its chemical environment. This permits us thus to demonstrate that iron is indeed linked with proteins and not with mineral phases of the sample. Coupled with the ritual context of the objects, this constitutes a proof of the use of blood. Thanks to this protocol, which has the major advantage of avoiding false positive results, the presence of blood has been demonstrated in seven out of the eight studied samples.     

Synthesis of AlN nanopowder coated with a thin layer of C,using a thermal plasma reactor

High-purity nanocrystalline aluminum nitride powders were synthesized by using a 12?kW non-transferred arc plasma. The synthesis was conducted in a versatile, new designed, one-chamber thermal plasma reactor (TPR). The novel experimental assembly incorporated better working conditions like: high temperature gradient between the crucible and reactor's wall, and high super-saturation of the system by nitrogen and carbon. Thermodynamic modelling of the synthesis was conducted in order to achieve the best conditions for AlN formation. In this study, aluminum discs of Al 1100 were used as precursor material and pure nitrogen was the only gas used as reagent and plasmogenic gas.Nanopowders collected from reactor's wall were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-Ray diffraction (XRD). Synthesized h-AlN nano-powders were found to be free of oxides and aluminum metal. A thin carbon-layer around the particles was detected. TEM results indicated that the carbon-layer was around 5 and 10?nm. This outcome could make a significant difference with other synthesis reported in the literature since the occurrence of the carbon-layer, could delay AlN oxidation, prevent hydration, and could avoid the agglomeration of the particles.     

Electromagnetic modeling of waveguide amplifier based on Nd<Superscript>3+</Superscript> Si-rich SiO<Subscript>2</Subscript> layers by means of the ADE-FDTD method

By means of ADE-FDTD method, this paper investigates the electromagnetic modelling of a rib-loaded waveguide composed of a Nd³⁺ doped Silicon Rich Silicon Oxide active layer sandwiched between a SiO₂ bottom cladding and a SiO₂ rib. The Auxilliary Differential Equations are the rate equations which govern the levels populations. The Finite Difference Time Domain (FDTD) scheme is used to solve the space and time dependent Maxwell equations which describe the electromagnetic field in a copropagating scheme of both pumping (λ _pump = 488 nm) and signal (λ _signal = 1064 nm) waves. Such systems are characterized by extremely different specific times such as the period of electromagnetic field ~ 10^-15 s and the lifetimes of the electronic levels between ~ 10^-10s and ~ 10^-4 s. The time scaling method is used in addition to specific initial conditions in order to decrease the computational time. We show maps of the Poynting vector along the propagation direction as a function of the silicon nanograin (Si-ng) concentrations. A threshold value of 10²⁴ Si-ng m^-3 is extracted below which the pump wave can propagate so that a signal amplication is possible.     

Experimental and modelling of supercritical oil extraction from rapeseeds and sunflower seeds

The supercritical oil extraction from oleaginous seeds (sunflower and rapeseeds) is presented here through experimental and modelling results. The experimental setup allows an accurate following of the mass of the oil extracted and to derive the experimental influences of pressure, temperature and supercritical CO₂ flowrate on the extraction curves. These parameters are very sensitive and highlight the necessity of precise optimisation of experimental conditions. In order to complete the behaviour of supercritical fluids extraction, an improved modelling is proposed. The modelling basic equations are based on others modelling published previously. In this work, the determination of several parameters comes from correlations and the other constants are fitted with all the experimental results. Thus the modelling is more representative and predictive as other ones. The modelling results present a good agreement with the experimental results, and hence it can be used for the dimensioning of some extraction autoclaves.     

Measurement of enzymatic activity and specificity of human and avian influenza neuraminidases from whole virus by glycoarray and MALDI-TOF mass spectrometry

Influenza neuraminidases hydrolyze the ketosidic linkage between N-acetylneuraminic acid and its adjacent galactose residue in sialosides. This enzyme is a tetrameric protein that plays a critical role in the release of progeny virions. Several methods have been described for the determination of neuraminidase activity, usually based on colorimetric, fluorescent, or chemiluminescent detection. However, only a few of these tests allow discrimination of the sialyl-linkage specificity (i.e., α2-3- versus α2-6-linked sialyllactosides) of the neuraminidase. Herein we report a glycoarray-based assay and a MALDI-TOF study for assessing the activity and specificity of two influenza neuraminidases on whole viruses. The human A(H3N2) and avian A(H5N2) neuraminidase activities were investigated. The results from both approaches demonstrated that α2-3 sialyllactoside was a better substrate than α2-6 sialyllactoside for both viruses and that H5N2 virus had a lower hydrolytic activity than H3N2.     

Correlation between mechanical properties and orientation of the crystalline and mesomorphic phases in isotactic polypropylene fibers

The microstructure and mechanical properties of melt-spun isotactic polypropylene (iPP) fibers were studied for different take-up velocities and throughputs with a combination of small- and wide-angle X-ray scattering, calorimetry and tensile tests. With the increase of take-up velocity the mesomorphic fraction of the fibers steadily decreases while the crystalline fraction increases. The addition of an alpha-nucleating agent led to an increase of crystallinity and a slight decrease of the orientation factor. By contrast, a beta-nucleator resulted in a complete suppression of the fiber crystallinity. The orientation factor of the mesophase and/or crystalline phase is found to have a one-to-one correlation with the fiber tenacity and deformation at break. At the same time, the absolute values of crystallinity and/or mesomorphicity are fully uncorrelated with these mechanical characteristics. The observed correlations can be used for example to design and control the fiber mechanical properties by tuning the processing conditions such as take-up velocity, throughput and addition of nucleating agents.     

Simulation of pH-controlled dissolution of aluminium based on a modified Scanning Electrochemical Microscope experiment to mimic localized trenching on aluminium alloys

Some constituent intermetallic (IMPs) particles at the surface of aluminium alloys are considered as preferential sites for the initiation of structural corrosion resulting in localized trenching around the particles and the surrounding Al matrix. In this work, a modified scanning electrochemical microscope (SECM) experiment was used to induce such phenomena via a local alcalinisation on 200 nm thick aluminium coatings promoting their local dissolution in an aerated 0.1 M NaCl electrolyte. The local alcalinisation was induced by the oxygen reduction reaction on the tip of a SECM which mimics the surface of an isolated IMP. From a phenomenological point of view, reproducible cylindrical damage develops in front of the platinum ultramicroelectrode (UME). Using a 2D finite element modelling to simulate the SECM experiments, the role of the local alcalinisation was validated and the calculated Al dissolution rate was found in agreement with the experimental evaluation.