Atomic vapor deposition approach to In2O3 thin films

In2O3 thin films were grown by atomic vapor deposition (AVD) on Si(100) and glass substrates from a tris-guanidinate complex of indium [In(N(i)Pr2guanid)3] under an oxygen atmosphere. The effects of the growth temperature on the structure, morphology and composition of In2O3 films were investigated. X-ray diffraction (XRD) measurements revealed that In2O3 films deposited in the temperature range 450-700 degreesC crystallised in the cubic phase. The film morphology, studied by scanning electron microscopy (SEM) and atomic force microscopy (AFM), was strongly dependent on the substrate temperature. Stoichiometric In2O3 films were formed under optimised processing conditions as was confirmed by X-ray photoelectron and X-ray excited Auger electron spectroscopies (XPS, XE-AES), as well as by Rutherford backscattering spectrometry (RBS). Finally, optical properties were investigated by photoluminescence (PL) measurements, spectroscopic ellipsometry (SE) and optical absorption. In2O3 films grown on glass exhibited excellent transparency (approximately 90%) in the Visible (Vis) spectral region.     

Heterogeneous reactive extraction for secondary butyl alcohol liquid phase synthesis: Microkinetics and equilibria

The reaction kinetics for the liquid phase synthesis of a racemic mixture of the secondary butyl alcohols (SBA) from linear butene isomers (1-butene (1B); cis-2-butene (c2B); trans-2-butene (t2B)) and water (W) using a macroporous sulfonic acid ion exchange resin as catalyst were determined experimentally in a multiphase CSTR in the temperature range 39–433 K at 6–8 MPa. This range of pressures is necessary to dissolve butenes in the aqueous phase and to ensure a liquid state of all components. For temperatures higher than 423 K the reaction kinetics for the used catalyst size are influenced by mass transfer resistances within the catalyst matrix. The reaction takes place in the water swollen gel phase of the catalysts microspheres. Due to the large excess of water in the gel phase the compositions in the gel phase, in the macropore fluid, and in the catalyst surrounding aqueous phase are assumed to be identical. According to the literature the reaction is rather catalyzed by hydrated acid protons (specific catalysis) than by polymer-bonded-SO₃H groups (general catalysis). The experimental results can therefore be described sufficiently by a pseudo-homogeneous 3-parameter rate expression in aqueous phase activities. The forward reaction is first-order in butene. The reverse reaction is first-order in secondary butyl alcohol. The activation energy was determined to be 108 kJ/mol. Practically no pressure dependence could be observed for pressures exceeding 6 MPa. The ever-present isomerization of the linear butenes on acid catalysts was found to be remarkably faster than the hydration of butenes to SBA. Therefore, the isomerization is considered to be always in equilibrium during the olefin hydration. The formation of the possible by-product di-sec-butyl ether (DSBE) was never observed to a measurable extent. Simultaneous chemical and phase equilibria were investigated theoretically using the volume translated Peng–Robinson equation of state (VTPR-EoS) in combination with a g^E-mixing rule. Parameters of the used g^E-model were adjusted to experimental ternary liquid–liquid equilibrium (LLE) data.     

Semiconductor-mediated Photocatalyzed degradation of a herbicide derivative, chlorotoluron, in aqueous suspensions

The photocatalytic degradation of a herbicide derivative, chlorotoluron [3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 1], has been investigated in aqueous suspensions of titanium dioxide (TiO2) under a variety of conditions. The degradation was studied by monitoring the change in substrate concentration employing UV spectroscopic analysis technique and depletion in total organic carbon (TOC) content as a function of irradiation time. The degradation kinetics of the model compound was investigated under different conditions such as type of TiO2, pH, catalyst concentration, substrate concentration, temperature, and in the presence of different electron acceptors such as hydrogen peroxide (H2O2), potassium persulfate (K2S2O8), and potassium bromate (KBrO3) besides molecular oxygen. TiO2 Degussa P25 was found to be a more efficient photocatalyst for the degradation of the model compound as compared with other photocatalysts. The degradation products were analyzed using GC/MS analysis technique and probable pathways for the formation of different products have been proposed.     

Comparison of single-cell testing,short-stack testing and mathematical modeling methods for a direct methanol fuel cell

In this paper, a comparison between direct methanol fuel cell (DMFC) measurements performed on a single cell and a short-stack, and the results of a mathematical model for a DMFC, is presented. The testing of a short-stack, which consists of 5 cells with an active area of 315 cm², was performed at various current densities, permeation current densities, and cathode flow rates (CFR) in order to determine the voltage outputs of each cell. Methanol concentration and stack temperature results obtained from short-stack testing were then integrated into the single cell test and single cell mathematical model as the input parameters. For the mathematical modelling, transport equations originating from methanol, water, and oxygen were coupled with the electrochemical relations. Therefore, a comparison between these three methods is made in order to gain a deeper understanding of the effects of the operating parameters on DMFC performance. This study showed that the model could describe experimental results well when lower methanol concentrations (under 1.2 M) and temperature (under 60 °C) values are used as input parameters. The results also show very good agreement at lower methanol permeation rates and therefore lower temperatures. It is found that the voltage output for a given current density is higher for the theoretical model than that of the experimental studies; and the differences in the results can be up to 0.04 V for a cell.     

New 3-Aryl-2-(2-thienyl)acrylonitriles with High Activity Against Hepatoma Cells

New 2-(thien-2-yl)-acrylonitriles with putative kinase inhibitory activity were prepared and tested for their antineoplastic efficacy in hepatoma models. Four out of the 14 derivatives were shown to inhibit hepatoma cell proliferation at (sub-)micromolar concentrations with IC₅₀ values below that of the clinically relevant multikinase inhibitor sorafenib, which served as a reference. Colony formation assays as well as primary in vivo examinations of hepatoma tumors grown on the chorioallantoic membrane of fertilized chicken eggs (CAM assay) confirmed the excellent antineoplastic efficacy of the new derivatives. Their mode of action included an induction of apoptotic capsase-3 activity, while no contribution of unspecific cytotoxic effects was observed in LDH-release measurements. Kinase profiling of cancer relevant protein kinases identified the two 3-aryl-2-(thien-2-yl)acrylonitrile derivatives 1b and 1c as (multi-)kinase inhibitors with a preferential activity against the VEGFR-2 tyrosine kinase. Additional bioinformatic analysis of the VEGFR-2 binding modes by docking and molecular dynamics calculations supported the experimental findings and indicated that the hydroxy group of 1c might be crucial for its distinct inhibitory potency against VEGFR-2. Forthcoming studies will further unveil the underlying mode of action of the promising new derivatives as well as their suitability as an urgently needed novel approach in HCC treatment.     

Photokatalytische Systeme. XXI. Zum Mechanismus der Photoreduktion von Kaliumchromat in Alkoholen

Photocatalytic Systems. XXI. On the Mechanism of the Photoreduction of Potassium Chromate in Alcohols The photolysis of crown ether complexes of potassium chromate in several alcohols has been investigated by e.s.r.-spectroscopy. Two different relatively long-lived Cr(V) intermediates formed by different reaction pathways have been observed. Radicalic oxidation products of the alcohols (alkoxy and hydroxyalkyl radicals as well as fragmentation products) and of the crown ether have been detected by spin trapping.