Characterization of Cu/CeO2/γ-Al2O3 Thin Film Catalysts by Thermal Desorption Spectroscopy

Thermal desorption spectroscopy (TDS) under ultra high vacuum (UHV) condition has been used to investigate the desorption characteristics of Cu/CeO₂/γ-Al₂O₃ thin film catalysts coated onto the microchannel of a microreactor. TDS results demonstrate that surface desorption profiles and chemical properties (acid–base and redox properties) are remarkably influenced by the catalyst composition, i.e. the loading of copper and ceria. The enhanced basicity with the increase of ceria loading and the decrease of copper loading is evident from the shifted desorption maximum of CO₂ in TDS spectra. Three oxygen species, ranging from weakly bound oxygen desorbed at low temperature to the strongly held lattice oxygen desorbed at high temperature, are easily discernible and clearly identified by O₂ TDS spectra, depending on the catalyst compositions. The concomitant thermal desorption of O₂, CO₂, and H₂O at low temperature indicates the unique chemical properties of copper/ceria catalyst with appropriate copper and ceria contents. The observed low-temperature feature is ascribed to the role of porthole of copper/ceria interfacial area for several desorbed species. The weakly bound oxygen species is attributed to the enhanced abundance of copper/ceria interfacial anionic vacancies created by the intimate contact between copper and ceria entities and its impact on steam reforming of methanol (SRM) reaction is tentatively discussed in terms of reverse oxygen spillover.     

A systematic comparison of PCA‐based Statistical Process Monitoring methods for high‐dimensional,time‐dependent Processes

High‐dimensional and time‐dependent data pose significant challenges to Statistical Process Monitoring. Most of the high‐dimensional methodologies to cope with these challenges rely on some form of Principal Component Analysis (PCA) model, usually classified as nonadaptive and adaptive. Nonadaptive methods include the static PCA approach and Dynamic Principal Component Analysis (DPCA) for data with autocorrelation. Methods, such as DPCA with Decorrelated Residuals, extend DPCA to further reduce the effects of autocorrelation and cross‐correlation on the monitoring statistics. Recursive Principal Component Analysis and Moving Window Principal Component Analysis, developed for nonstationary data, are adaptive. These fundamental methods will be systematically compared on high‐dimensional, time‐dependent processes (including the Tennessee Eastman benchmark process) to provide practitioners with guidelines for appropriate monitoring strategies and a sense of how they can be expected to perform. The selection of parameter values for the different methods is also discussed. Finally, the relevant challenges of modeling time‐dependent data are discussed, and areas of possible further research are highlighted. © 2016 American Institute of Chemical Engineers AIChE J, 62: 1478–1493, 2016     

miR-16-5p Is a Stably-Expressed Housekeeping MicroRNA in Breast Cancer Tissues from Primary Tumors and from Metastatic Sites

For quantitative microRNA analyses in formalin-fixed paraffin-embedded (FFPE) tissue, expression levels have to be normalized to endogenous controls. To investigate the most stably-expressed microRNAs in breast cancer and its surrounding tissue, we used tumor samples from primary tumors and from metastatic sites. MiRNA profiling using TaqMan^® Array Human MicroRNA Cards, enabling quantification of 754 unique human miRNAs, was performed in FFPE specimens from 58 patients with metastatic breast cancer. Forty-two (72%) samples were collected from primary tumors and 16 (28%) from metastases. In a cross-platform analysis of a validation cohort of 32 FFPE samples from patients with early breast cancer genome-wide microRNA expression analysis using SurePrintG3 miRNA (8 × 60 K)^® microarrays from Agilent^® was performed. Eleven microRNAs could be detected in all samples analyzed. Based on NormFinder and geNorm stability values and the high correlation (rho ≥ 0.8) with the median of all measured microRNAs, miR-16-5p, miR-29a-3p, miR-126-3p, and miR-222-3p are suitable single gene housekeeper candidates. In the cross-platform validation, 29 human microRNAs were strongly expressed (mean log2-intensity > 10) and 21 of these microRNAs including miR-16-5p and miR-29a-3p were also stably expressed (CV < 5%). Thus, miR-16-5p and miR-29a-3p are both strong housekeeper candidates. Their Normfinder stability values calculated across the primary tumor and metastases subgroup indicate that miR-29a-3p can be considered as the strongest housekeeper in a cohort with mainly samples from primary tumors, whereas miR-16-5p might perform better in a metastatic sample enriched cohort.     

Preparation of morphology controlled Th1 − xUxO2 sintered pellets from low-temperature precursors

Dense sintered samples of Th_1 − xU_xO₂ solid solutions were prepared from the initial precipitation of oxalate precursors through two different wet chemical routes, based either on the direct precipitation of the cations or on the use of hydrothermal method. For both low-temperature precursors, the specific surface area was followed versus the heating temperature and the influence of the conversion step on the oxide powder reactivity was evidenced since it allowed to obtain reactive surfaces in the range of 15-45 m² g⁻¹ without any additional grinding step. From dilatometric studies, the operating conditions required for the complete densification of the Th_1 − xU_xO₂ pellets were set to a heat treatment of 3 h at 1500 °C. In these conditions, the density of the samples lies between 94% and 99% of the calculated value whatever the preparation method chosen which appeared very promising compared to the results already reported under inert atmosphere. The initial precipitation of low-temperature precursors thus allowed to lower the sintering temperature by about 100 °C while the use of hydrothermal conditions significantly improved the cationic distribution in the sintered samples, as shown from EPMA statistical experiments.     

Oxidative catabolism of α-tocopherol in rat liver microsomes

The goal of this study was to clarify the mechanism responsible for the catabolism of α-tocopherol. The vitamin, bound to albumin, was incubated with rat liver microsomes and appeared to be broken down. Optimal production of the metabolite was obtained when 1 mg of microsomal protein was incubated with 36 μM of α-tocopherol in the presence of 1.5 mM of NADPH. Chromatographic and mass spectrometric analyses of the metabolite led to the conclusion that it consists of an ω-acid with an opened chroman ring, although we could not perform nuclear magnetic resonance analysis to confirm this. Our data show that α-tocopherol is ω-oxidized to a carboxylic acid and that this process can occur in rat liver microsomes in the presence of NADPH and O₂. The oxidation to the quinone structure appears to be a subsequent event that may be artifactual and/or catalyzed by a microsomal enzyme(s).     

The synthesis of tetrahedral bipyridyl metallo-octupoles with large second- and third-order nonlinear optical properties

Two new 4,4′-bis(donor)-6,6′-diphenyl- 2,2′-bipyridine ligands and their corresponding D_2d (Cu^I, Ag^I, Zn^II) octupolar metal complexes were synthesized, and their linear and nonlinear optical properties were investigated. A single crystal X-ray structure was also determined for the bis[4,4′-bis(diethylaminostyryl)-6,6′-diphenyl-bipyridine]copper(I) complex, which revealed a distorded pseudo-tetrahedral geometry. Molecular second-order nonlinear optical properties were determined for the complexes using the Harmonic Light Scatterring technique at 1.91 μm. These metallo-chromophores display large first hyperpolarizabilities β_1.91 in the range of 211-340 × 10⁻³⁰ esu, which increase with the Lewis acidity of the metal ion. The two-photon absorption properties of the bipyridyl ligands and related complexes were determined using either the two-photon emission method for fluorescent compounds or the open aperture Z-scan technique for non emissive ones. The complexes display red-shifted two-photon absorption bands compared to their metal-ion free chromophores, as well as a large increase of the maximum two-photon absorption cross-sections.     

The effect of microstructure on hydrogen permeability of high strength steels

Hydrogen diffusivity and trapping have been studied in two advanced high strength steel grades and model samples using electrochemical permeation test. Microstructures of CP1000 and DP1000 steels consist of ferrite, martensite and a small fraction of retained austenite. In addition, bainite is present in CP1000. Model phases with predominance of a particular phase have been prepared by specific heat treatment. DP1000 has shown the lowest diffusivity among all materials, while ferritic model sample has shown the highest. Differences in hydrogen diffusion coefficient values are linked to trapping microstructural characteristics and grain size.     

The Electrodeposition of Chromium from Tervalent Chromium Salt Solutions. Part I. Chromium Chloride and Chromium Sulphate Baths

The “imponderables” which affect the framework within which the Plating Shop must be planned are listed. The grouping of vats, cleaners and rinses are discussed and alternative methods of hand operation of plating vats described. The importance of depth of plating vats is stressed and various methods of constructing floors, drainage and vat supports are briefly indicated. Layouts for barrel plating shops both with inclined and horizontal barrels are suggested, and the importance of correct housing for electrical and other ancillary plant is emphasised.     

Evidence by EIS of the interaction between proteins and tin oxide electrode surface

Macromolecules like proteins are able to adhere to tin oxide electrodes at open circuit potential as proved by electrogravimetry experiments. In this work, electrochemical impedance studies were performed at aqueous electrolyte/F- or Sb-doped semiconducting tin oxide interfaces, including natural seawater. By this way, it was possible to characterize the potential dependence of the interfacial capacitance in various physicochemical conditions, without or in the presence of bovine serum albumin (BSA). In the potential range where tin oxide is in the depletion regime (blocking interface), a capacitance excess is evidenced which can be attributed to the formation of surface states which are the signature of chemical bonding. By simulating the so-called surface state capacitance, three states have been pointed out. They are centred at 0.7, 0.9 and 1.1 eV in the tin oxide bandgap. On the basis of experimental arguments, the state at 1.1 eV was ascribed to the OH-terminated tin oxide surface, the two other states were found to be specific of the interaction of organic matter with the oxide surface. In the presence of BSA, the density of surface atoms (about 10¹³ cm⁻²) involved in bonding is of the order of magnitude of the surface concentration of one BSA monolayer. The lasting character of these bonds was also shown. This finding shows the definitive protein immobilisation at the SnO₂ surface.