The Chemical Evolution of the La<Subscript>0.6</Subscript>Sr<Subscript>0.4</Subscript>CoO<Subscript>3−δ</Subscript> Surface Under SOFC Operating Conditions and Its Implications for Electrochemical Oxygen Exchange Activity

Owing to its extraordinary high activity for catalysing the oxygen exchange reaction, strontium doped LaCoO₃ (LSC) is one of the most promising materials for solid oxide fuel cell (SOFC) cathodes. However, under SOFC operating conditions this material suffers from performance degradation. This loss of electrochemical activity has been extensively studied in the past and an accumulation of strontium at the LSC surface has been shown to be responsible for most of the degradation effects. The present study sheds further light onto LSC surface changes also occurring under SOFC operating conditions. In-situ near ambient pressure X-ray photoelectron spectroscopy measurements were conducted at temperatures between 400 and 790 °C. Simultaneously, electrochemical impedance measurements were performed to characterise the catalytic activity of the LSC electrode surface for O₂ reduction. This combination allowed a correlation of the loss in electro-catalytic activity with the appearance of an additional La-containing Sr-oxide species at the LSC surface. This additional Sr-oxide species preferentially covers electrochemically active Co sites at the surface, and thus very effectively decreases the oxygen exchange performance of LSC. Formation of precipitates, in contrast, was found to play a less important role for the electrochemical degradation of LSC.     

Tetraacylgermanes as highly efficient photoinitiators for visible light cured dimethacrylate resins and dental composites

Tetrabenzoylgermane 1 and various substituted tetrabenzoylgermanes 2 – 7 were investigated as visible light (VL) photoinitiators (PIs) for dental dimethacrylate resins and dimethacrylate‐based composites. The tetrabenzoylgermanes 1 – 7 show a very strong VL absorption between 400 and 450 nm. Substituents on the benzoyl chromophore strongly influence their properties such as melting point, solubility, absorption behavior, or PI reactivity. A good photobleaching behavior and a very high reactivity as VL PI was found in photo‐differential scanning calorimeter experiments for selected tetrabenzoylgermanes. Composite pastes containing only ～0.1 wt % of Ge‐PI exhibited a sufficient photocuring due to the high PI‐reactivity of the tetraacylgermanes. Among the investigated germane PIs, tetrakis(2‐methylbenzoyl)germane 2 shows the best performance as VL PI for restorative composites and enables the composites to be photocured using an LED with an emission maximum of 500 nm. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46115.     

Measurement of fat content of food with single-sided NMR

Fat content is one of the important parameters of quality control in many food products. Several techniques are used to determine the amount of fat in a given product. In this work, the applicability of a portable dedicated nuclear magnetic resonance (NMR) analyzer to measure the fat content in a packaged product without destruction of the material was examined. Two different low-field NMR methods, namely, a ratio method and a relaxation time method, were applied and discussed. The processed NMR signal was linearly correlated with the fat content obtained by reference methods. The linear correlation allowed the application of single-sided NMR for fat measurements. In memoriam     

Biocatalytic Synthesis of Nitriles through Dehydration of Aldoximes: The Substrate Scope of Aldoxime Dehydratases

Nitriles, which are mostly needed and produced by the chemical industry, play a major role in various industry segments, ranging from high‐volume, low‐price sectors, such as polymers, to low‐volume, high‐price sectors, such as chiral pharma drugs. A common industrial technology for nitrile production is ammoxidation as a gas‐phase reaction at high temperature. Further popular approaches are substitution or addition reactions with hydrogen cyanide or derivatives thereof. A major drawback, however, is the very high toxicity of cyanide. Recently, as a synthetic alternative, a novel enzymatic approach towards nitriles has been developed with aldoxime dehydratases, which are capable of converting an aldoxime in one step through dehydration into nitriles. Because the aldoxime substrates are easily accessible, this route is of high interest for synthetic purposes. However, whenever a novel method is developed for organic synthesis, it raises the question of substrate scope as one of the key criteria for application as a “synthetic platform technology”. Thus, the scope of this review is to give an overview of the current state of the substrate scope of this enzymatic method for synthesizing nitriles with aldoxime dehydratases. As a recently emerging enzyme class, a range of substrates has already been studied so far, comprising nonchiral and chiral aldoximes. This enzyme class of aldoxime dehydratases shows a broad substrate tolerance and accepts aliphatic and aromatic aldoximes, as well as arylaliphatic aldoximes. Furthermore, aldoximes with a stereogenic center are also recognized and high enantioselectivities are found for 2‐arylpropylaldoximes, in particular. It is further noteworthy that the enantiopreference depends on the E and Z isomers. Thus, opposite enantiomers are accessible from the same racemic aldehyde and the same enzyme.     

Interaction of 1-allyl-3-methyl-imidazolium chloride and carbon black and its influence on carbon black filled rubbers

The interactions of the ionic liquid 1-allyl-3-methyl-imidazolium chloride (AMIMCl) with different grades of carbon black have been investigated using rheological measurements, differential scanning calorimetry and Raman spectroscopy. We could prove strong attractive interactions of AMIMCl with the carbon black surface, which result, for example, in the formation of an AMIMCl–carbon black–bucky gel and in an increased glass transition temperature of the ionic liquid in the presence of carbon black. Raman spectroscopy revealed that the AMIMCl is preferably attached to the edges of graphitic crystals at the carbon black surface, which have the highest adsorption energies. A surface treatment of different grades of carbon black with AMIMCl led to significant changes of the mechanical and electrical properties of different rubber compounds filled with carbon black, which can be attributed to a decreased filler–polymer interaction and a local plasticising effect of the AMIMCl at the carbon black surface.     

A Peroxygenase from Chaetomium globosum Catalyzes the Selective Oxygenation of Testosterone

Unspecific peroxygenases (UPO, EC 1.11.2.1) secreted by fungi open an efficient way to selectively oxyfunctionalize diverse organic substrates, including less‐activated hydrocarbons, by transferring peroxide‐borne oxygen. We investigated a cell‐free approach to incorporate epoxy and hydroxyl functionalities directly into the bulky molecule testosterone by a novel unspecific peroxygenase (UPO) that is produced by the ascomycetous fungus Chaetomium globosum in a complex medium rich in carbon and nitrogen. Purification by fast protein liquid chromatography revealed two enzyme fractions with the same molecular mass (36 kDa) and with specific activity of 4.4 to 12 U mg^?1. Although the well‐known UPOs of Agrocybe aegerita (AaeUPO) and Marasmius rotula (MroUPO) failed to convert testosterone in a comparative study, the UPO of C. globosum (CglUPO) accepted testosterone as substrate and converted it with total turnover number (TTN) of up to 7000 into two oxygenated products: the 4,5‐epoxide of testosterone in β‐configuration and 16α‐hydroxytestosterone. The reaction performed on a 100 mg scale resulted in the formation of about 90 % of the epoxide and 10 % of the hydroxylation product, both of which could be isolated with purities above 96 %. Thus, CglUPO is a promising biocatalyst for the oxyfunctionalization of bulky steroids and it will be a useful tool for the synthesis of pharmaceutically relevant steroidal molecules.     

Method for Characterization of Solvents for Physical Absorption Processes

A method for solvent screening and searching for additives in the field of physical absorption processes is presented. A model based on the concept of virtual components and on the concept of a simplified abstract flow sheet is created. An estimation procedure for thermodynamically consistent property sets for the virtual component is developed. The model is implemented into MATLAB®. Its application is demonstrated in two studies including a study for a solvent additive. Potential candidates can be characterized and ranges for properties of the solvent or additive are found by means of the model. Conclusions obtained from the model support the screening process by a reduction of the number of further investigated components.     

Field intercomparison of the gas/particle partitioning of oxygenated organics during the Southern Oxidant and Aerosol Study (SOAS) in 2013

We present results of the first intercomparison of real-time instruments for gas/particle partitioning of organic species. Four recently-developed instruments that directly measure gas/particle partitioning in near-real time were deployed in Centreville, Alabama during the Southern Oxidant Aerosol Study (SOAS) in 2013. Two instruments were filter inlet for gases and aerosols high-resolution chemical ionization mass spectrometers (FIGAERO-HRToF-CIMS) with acetate (A-CIMS) and iodide (I-CIMS) ionization sources, respectively; the third was a semi-volatile thermal desorption aerosol GC-MS (SV-TAG); and the fourth was a high-resolution thermal desorption proton-transfer reaction mass spectrometer (HR-TD-PTRMS). Signals from these instruments corresponding to several organic acids were chosen for comparison. The campaign average partitioning fractions show good correlation. A similar level of agreement with partitioning theory is observed. Thus the intercomparison exercise shows promise for these new measurements, as well as some confidence on the measurement of low versus high particle-phase fractions. However, detailed comparison show several systematic differences that lie beyond estimated measurement errors. These differences may be due to at least eight different effects: (1) underestimation of uncertainties under low signal-to-noise; (2) inlet and/or instrument adsorption/desorption of gases; (3) differences in particle size ranges sampled; (4) differences in the methods used to quantify instrument backgrounds; (5) errors in high-resolution fitting of overlapping ion groups; (6) differences in the species included in each measurement due to different instrument sensitivities; and differences in (7) negative or (8) positive thermal decomposition (or ion fragmentation) artifacts. The available data are insufficient to conclusively identify the reasons, but evidence from these instruments and available data from an ion mobility spectrometer shows the particular importance of effects 6–8 in several cases. This comparison highlights the difficulty of this measurement and its interpretation in a complex ambient environment, and the need for further improvements in measurement methodologies, including isomer separation, and detailed study of the possible factors leading to the observed differences. Further intercomparisons under controlled laboratory and field conditions are strongly recommended.

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