Acetaldehyde as an Intermediate in the Electroreduction of Carbon Monoxide to Ethanol on Oxide‐Derived Copper

Oxide‐derived copper (OD‐Cu) electrodes exhibit unprecedented CO reduction performance towards liquid fuels, producing ethanol and acetate with >50 % Faradaic efficiency at ?0.3 V (vs. RHE). By using static headspace‐gas chromatography for liquid phase analysis, we identify acetaldehyde as a minor product and key intermediate in the electroreduction of CO to ethanol on OD‐Cu electrodes. Acetaldehyde is produced with a Faradaic efficiency of ≈5 % at ?0.33 V (vs. RHE). We show that acetaldehyde forms at low steady‐state concentrations, and that free acetaldehyde is difficult to detect in alkaline solutions using NMR spectroscopy, requiring alternative methods for detection and quantification. Our results represent an important step towards understanding the CO reduction mechanism on OD‐Cu electrodes.     

Effect of Synthesis Parameters on Sol–Gel Silica Modified by Zirconia

An experimental strategy was developed to obtain mesoporous SiO₂-ZrO₂ mixed oxides via a sol–gel process, which involved the use of tetraethylorthosilicate (TEOS) and an inorganic Zr-containing salt. The effects of key process parameters on the properties of the materials were investigated, including the choice of Zr(IV) source (zirconium oxychloride or nitrate), the ZrO₂ content and the synthesis pressure (i.e. ambient pressure or hydrothermal conditions). The resulting solids were dried, calcined at 500 °C, and characterized by nitrogen physisorption, pyridine chemisorption, ²⁹Si Nuclear Magnetic Resonance and X-ray diffraction. The data revealed that mesoporous materials with very narrow pore diameter distribution were obtained when using the autoclave procedure from both zirconium nitrate and oxychloride salts. The surface areas and pore size distributions were a function of ZrO₂ content. Differences in acidity, as determined by pyridine adsorption, were observed depending on the synthesis parameters.     

Parallel and automated library synthesis of 2-long alkyl chain benzoazoles and azole[4,5-<Emphasis Type="BoldItalic">b</Emphasis>]pyridines under microwave irradiation

Summary A versatile route to 40-membered library of 2-long alkyl chain substituted benzoazoles (1 and 2) and azole[4,5-b]pyridines (3 and 4) via microwave-assisted combinatorial synthesis was developed. The reactions were carried out in both monomode and multimode microwave oven. With the latter, all reactions were performed in high-throughput experimental settings consisting of an 8×5 combinatorial library designed to synthesize 40 compounds. Each step, from the addition of reagents to the recovery of final products, was automated. The microwave-assisted N-long chain alkylation reactions of 2-alkyl-1H-benzimidazole (1) and 2-alkyl-1H-benzimidazole[4,5-b] pyridines (3) were also studied.     

Determination of carbaryl, carbofuran and methiocarb in cucumbers and strawberries by monoclonal enzyme immunoassays and high-performance liquid chromatography with fluorescence detection. An analytical comparison

Carbaryl, carbofuran and methiocarb are three of the most important N-methylcarbamate pesticides. In the present work, the application of laboratory-developed monoclonal antibody-based enzyme-linked immunosorbent assays (ELISAs) to the determination of these compounds in fruits and vegetables is described. Cucumbers and strawberries were spiked with the three carbamates at 10, 50 and 200 ppb. After extraction and clean-up, samples were analyzed by immunoassay and by HPLC with post-column derivatization and fluorescence detection (US Environmental Protection Agency Method 531.1). Results obtained by ELISA correlated well with those obtained by HPLC, both in terms of accuracy and precision. Recoveries were in the 60-90% range by ELISA and in the 50-90% range by HPLC, depending on the particular combination of commodity, pesticide, and fortification level under consideration. ELISAs were also applied to the analysis of non-purified sample extracts with excellent results: recoveries close to 100% were obtained, while maintaining similar precision values. This approach avoids the use of solid-phase extraction columns, saves time, and considerably increases the sample throughput. Results clearly indicate that the developed immunoassays may be suitable for the quantitative and reliable determination of carbaryl, carbofuran and methiocarb in fruits and vegetables even without including clean-up steps. These considerations make these ELISAs very useful analytical tools for monitoring and regulatory programs, without the need of complex and expensive instrumentation.     

Pentacyclic Triterpene Profile and Its Biosynthetic Pathway in Cecropia telenitida as a Prospective Dietary Supplement

Promising research over the past decades has shown that some types of pentacyclic triterpenes (PTs) are associated with the prevention of type 2 diabetes (T2D), especially those found in foods. The most abundant edible sources of PTs are those belonging to the ursane and oleanane scaffold. The principal finding is that Cecropia telenitida contains abundant oleanane and ursane PT types with similar oxygenation patterns to those found in food matrices. We studied the compositional profile of a rich PT fraction (DE16-R) and carried out a viability test over different cell lines. The biosynthetic pathway connected to the isolated PTs in C. telenitida offers a specific medicinal benefit related to the modulation of T2D. This current study suggests that this plant can assemble isobaric, positional isomers or epimeric PT. Ursane or oleanane scaffolds with the same oxygenation pattern are always shared by the PTs in C. telenitida, as demonstrated by its biosynthetic pathway. Local communities have long used this plant in traditional medicine, and humans have consumed ursane and oleanane PTs in fruits since ancient times, two key points we believe useful in considering the medicinal benefits of C. telenitida and explaining how a group of molecules sharing a closely related scaffold can express effectiveness.     

A general view of pseudoharmonics and pseudoantiharmonics to calculate external arguments of Douady and Hubbard

Harmonics give us a compact formula and a powerful tool in order to calculate the external arguments of the last appearance hyperbolic components and Misiurewicz points of the Mandelbrot set in some particular cases. Antiharmonics seem however to have no application. In this paper, we give a general view of pseudoharmonics and pseudoantiharmonics, as a generalization of harmonics and antiharmonics. Pseudoharmonics turn out to be a more powerful tool than harmonics since they allow the calculation of external arguments of the Mandelbrot set in many more cases. Likewise, unlike antiharmonics, pseudoantiharmonics turn out to be a powerful tool to calculate external arguments of the Mandelbrot set in some cases.     

Interlayer Exchange Coupling,Spin Pumping and Spin Transport in Metallic Magnetic Single and Bilayer Structures

Journal of Experimental and Theoretical Physics - Interlayer exchange coupling in thin films is one of the cornerstones of modern spintronics-based technology. This phenomena has been an active...     

Correction to “On the linear combination of normal and Laplace random variables”, by Nadarajah,S., <Emphasis Type="Italic">Computational Statistics</Emphasis>, 2006, <Emphasis Type="Bold">21</Emphasis>, 63–71

In the above mentioned paper, some errors were found in the expressions given for the distribution of a linear combination of Normal and Laplace random variables, Z, given in formulae (3, Theorem 1), (6), and (7) that can lead to obtaining negative values for the mentioned distribution. The corrected versions for these expressions are presented here. In addition, the density function of Z is also provided.     

Modeling of three-phase heavy oil–water–gas bubbly flow in upward vertical pipes

A bubbly gas–bubbly oil flow pattern may occur when water, heavy oil and gas flow simultaneously in vertical pipes in such a way that water is the continuous phase. In this work, a one-dimensional, thermal, transient two-fluid mathematical model, for such flow, is presented. The model consists of mass, momentum and energy conservation equations for every phase whose numerical solution is based on the finite difference technique in the implicit scheme. The model is able to predict pressure, temperature, volumetric fraction and velocity profiles. For accurate modeling of multiphase flows, the key issue is to specify the adequate closure relationships, thus drag and virtual mass forces for the gas and oil phases were taken into account and special attention was paid on the gas–oil drag force. When this force was included into the model it was found that: (1) such force had the same order of magnitude than the oil drag force and both forces were smaller than the gas drag force, (2) the pressure, gas and oil velocities and gas and oil volume fraction profiles were affected, (3) the numerical stability was increased. The model predictions are in agreement with experimental data reported in literature.