Structure sensitivity of the catalytic oxidative coupling of methane on lanthanum oxide

The oxidative coupling of methane (OCM) has been found to be structure sensitive on La₂O₃ catalysts exhibiting different crystallite morphologies. Thin plates obtained by thermal decomposition of lanthanum nitrate at 650 °C are more selective on OCM reaction performed at 750 °C than the particles obtained by decomposition of the nitrate at 800 °C. It is assumed that the oxycarbonate observed is formed from the methane deep oxidation on the catalyst surface. This compound appears to act as an intermediate in the production of CO₂ and is thus important hi the resulting selectivity.     

A compact photomicroreactor design for kinetic studies of gas‐liquid photocatalytic transformations

A compact photomicroreactor assembly consisting of a capillary microreactor and small‐scale light emitting diodes was developed for the study of reaction kinetics in the gas‐liquid photocatalytic oxidation of thiophenol to phenyl disulfide within Taylor flow. The importance of photons was convincingly shown by a suction phenomenon due to the fast consumption of oxygen. Mass transfer limitations were evaluated and an operational zone without mass transfer effects was chosen to study reaction kinetics. Effects of photocatalyst loading and light sources on the reaction performance were investigated. Reaction kinetic analysis was performed to obtain reaction orders with respect to both thiophenol and oxygen based on heterogeneous and homogeneous experimental results, respectively. The Hatta number further indicated elimination of mass transfer limitations. Reaction rate constants at different photocatalyst loadings and different photon flux were calculated. Furthermore, the advantages of this photomicroreactor assembly for studying gas‐liquid photocatalytic reaction kinetics were demonstrated as compared with batch reactors. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2215–2227, 2015     

Synthesis and characterization of the polyols by air oxidation of soybean oil and its effect on the morphology and dynamic mechanical properties of poly(vinyl chloride) blends

The use of natural additives, with low toxicity and good compatibility, for PVC is becoming increasingly attractive. In this study, soybean oil additives were prepared by air oxidation reactions and blending with PVC. The oxidation reaction produced a significant increase in the number of hydroxyl groups in soybean oil; however, this kind of reaction results in the formation of a heterogeneous structure due to free radical reactions in the medium. The oxidized soybean oil improved the compatibility with PVC due to an increase in the number of polar groups, such as hydroxyls, and thus a reduction in the amount of atactic polymer was observed. Furthermore, an increase in the molecular weight of the oxidized oil, as well as large amounts of polar groups contributes to reducing the migration of oil in the PVC. Regarding the crystallinity of PVC, the use of pure and oxidized soybean oil causes small changes in the crystalline phase of the polymer. Oxidized soybean oil has great potential for usage as a secondary plasticizer for PVC. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42102.     

A 2D finite element analysis of the effect of numerical parameters on the reliability of Ti6Al4V machining modeling

Abstract

The numerical analysis, based on the finite element modeling (FEM), presents nowadays an efficient computational tool. It allows a better understanding of several thermo-mechanical phenomena involved during the machining process. However, its reliability heavily depends on the accurate definition of the numerical model. In this regard, a FE analysis focused on the 2D modeling of the Ti6Al4V dry orthogonal machining was carried out in this study. The relevance of different numerical meshing approaches and finite elements topologies was studied. The effect of the friction coefficient on the numerical chip morphology, its geometry, the cutting and the feed forces was investigated. The adequacy of several compared adaptive meshing approaches, in terms of the modeling of severe contact conditions taking place around the cutting-edge radius, was underlined in the current study. However, numerical serrated chips, closer to the experimental ones, were only predicted when the pure Lagrangian formulation was adopted and a proper determination of the failure energy was carried out. The definition of different mesh topologies highlighted the efficiency of the 4-node quadrangular mesh, with a suitable edge length, in increasing the agreement with the experimental data, while reducing the computing times.     

A two-step cloning-free PCR-based method for the deletion of genes in the opportunistic pathogenic yeast Candida lusitaniae

We describe a new cloning-free strategy to delete genes in the opportunistic pathogenic yeast Candida lusitaniae. We first constructed two ura3 Δ strains in C. lusitaniae for their use in transformation experiments. One was deleted for the entire URA3 coding sequence; the other possessed a partial deletion within the coding region, which was used to determine the minimum amount of homology required for efficient homologous recombination by double crossing-over of a linear DNA fragment restoring URA3 expression. This amount was estimated to 200 bp on each side of the DNA fragment. These data constituted the basis of the development of a strategy to construct DNA cassettes for gene deletion by a cloning-free overlapping PCR method. Two cassettes were necessary in two successive transformation steps for the complete removal of a gene of interest. As an example, we report here the deletion of the LEU2 gene. The first cassette was constituted by the URA3 gene flanked by two large fragments (500 bp) homologous to the 5' and 3' non-coding regions of LEU2. After transformation of an ura3 Δ recipient strain and integration of the cassette at the LEU2 locus, the URA3 gene was removed by a second transformation round with a DNA cassette made by the fusion between the 5' and 3' non-coding regions of the LEU2 gene. The overall procedure takes less than 2 weeks and allows the creation of a clean null mutant that retains no foreign DNA sequence integrated in its genome.     

The catalysis of the Ruff oxidative degradation of aldonic acids by titanium‐containing zeolites

Ti‐BEA and Ti‐FAU, obtained by post‐synthesis treatment, and TS‐1, obtained by direct hydrothermal synthesis, have been tested as catalysts for the Ruff oxidative degradation of calcium d‐gluconate to d‐arabinose using diluted hydrogen peroxide as oxidant. Only large‐pore zeolites Ti‐BEA and Ti‐FAU were found to be active. It was shown, in particular, that a very rapid leaching of titanium occurred and that the titanium species present in the solution were responsible for the catalytic activity observed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Urban identity policies in Berlin: From critical reconstruction to reconstructing the Wall

After the fall of the Iron Curtain, the East-Central European cities had to re-invent themselves to quickly adapt to a globalising world. Urban identity production policies were usually geared to connect to a chosen pre-socialist “Golden Age”, ignoring the socialist past as a simple disturbance of a “normal” development path. This story the cities were to tell, however, frequently conflicted with the socio-economic realities of a rather unsmooth transformation process, making the socialist past part of the urban identity. In the case of Berlin, a post-socialist and at the same time a post-western-stronghold city, urban identity production is bound to be more complicated than anywhere else. After the failure of the policy to “critically reconstruct” the cosmopolitan metropolis of the 1920s and thus erasing the past of the divided city, policies developed in the run-up to the 20th anniversary of the fall of the Wall aim at turning the Cold War past into a central element of the story that is to support its urban identity, notably leading to the comprehensive re-emergence of the Berlin Wall in the cityscape. This policy – unmatched in other East-Central European cities – has its origins in a historic struggle for identity, leading to the questionable attempt to make “change” the main story Berlin is to tell. This theme however – in conjunction with the reconstructed Wall as image brand – may fall short of creating an urban identity accepted by large population parts.