Photooxidation von Leukofarbstoffen. X. Untersuchungen zur Photooxidation von Di-kalium-anthracen-9,10-ylen-bis-sulfat

Photooxidation of Leuco Dyes. X. Investigation of the Photooxidation of Di-potassiumanthracene 9,10-ylene-di-sulfate Photolysis of the title compound (DHAE) in water or ethanol produces anthraquinone and anthrone. In deoxygenated solutions 9,10-dihydroxyanthracene is detected as a long lived intermediate. Laser and conventional flash photolysis reveals three short-lived transients with lifetimes of 200 ns, 2 and 410 ms. Different temperature dependencies are observed for the fluorescence and the photolysis quantum yields. This is interpreted by two successive thermally activated processes: photohomolysis of O S bond and escape of the radical pair from the solvent cage. The results are discussed with the help of a reaction scheme proposed for the photolysis of DHAE.     

Photooxidation von Leukofarbstoffen. XII. Kurzzeitspektroskopische Untersuchungen zur Photooxidation von Bis-schwefelsäuremonoestern der Leukoformen von Thioindigoverbindungen

Photooxidation of Leuco Dyes. XII. Time Resolved Investigations on the Photooxidation of Bis-sulfuric Acid Monoesters of Leucothioindigoid Compounds The photooxidation of 4, 4′-dimethyl-6, 6′-dichlorothioindigosol ( 1 ) was studied by means of laser and conventional flash photolysis. Three transients were detected and assigned to a radical R generated by homolytic splitting of one O S-bond of the parent compound and to two further radicals which are formed from R by hydrolytic cleavage of the second ester group. The latter two radicals are in a protolytic equilibrium with each other and react, depending on the nature of the solvent by H-atom abstraction, or by disproportionation forming the leuco-thioindigoid dye or both dye and leuco dye. A mechanistic scheme is proposed.     

Photochemische Primärprozesse von Xanthenfarbstoffen. I. Blitzlichtspektroskopische Untersuchung der Primärprozesse von Selenopyronin

Photochemical Primary Processes of Xanthene Dyes. I. Investigations of the Primary Processes of Selenopyronine by Flash Excitation The triplet-state of selenopyronine absorbs light in the whole investigated spectral range (λ_max = 400 nm, 480 nm, 690 nm). As results of the bimolecular triplet decay a half-reduced (λ_max = 430 nm) and a half-oxidized (λ_max = 475 nm) form of the dye are observed. p-Benzoquinone quenches the triplet-state (k₇ = 1,5 · 10⁹ l/mol s) and the results are the half-oxidized form and the p-benzosemiquinone ion. For these two products different decay processes exist. The reducing agents DABCO, EDTA and Hydroquinone also quench the triplet state (k₁₀ = 1,2 · 10⁶ l/mol s, k₁₁ = 1,0 · 10⁶ l/mol s, k₁₂ = 1,0 · 10⁹ l/mol s) and as result the half-reduced form is observed. Measurements with thiopyronine give analogous results, which are in good agreement with investigations published in the literature.     

Spurenstoffabtrennung mit keramischen Nanofiltrationsmembranen als Rotationsscheibenfilter

Reducing micropollutant pollution of water bodies is an important objective of water management and an integral part of environmental policy. Ceramic nanofiltration membranes were developed as multichannel membranes of increased membrane area and rotating disk filters. The membranes developed show retention of over 80 % for PEG 400. The membranes are currently being tested for the separation of micropollutants from wastewater contaminated with pharmaceuticals. With the help of a downstream oxidative process, the trace substances remaining in the permeate are degraded.     

Robotic technologies for solar‐powered UAVs: Fully autonomous updraft‐aware aerial sensing for multiday search‐and‐rescue missions

Large‐scale aerial sensing missions can greatly benefit from the perpetual endurance capability provided by high‐performance low‐altitude solar‐powered unmanned aerial vehicles (UAVs). However, today these UAVs suffer from small payload capacity, low energetic margins, and high operational complexity. To tackle these problems, this paper presents four individual technical contributions and integrates them into an existing solar‐powered UAV system: First, a lightweight and power‐efficient day/night‐capable sensing system is discussed. Second, means to optimize the UAV platform to the specific payload and to thereby achieve sufficient energetic margins for day/night flight with payload are presented. Third, existing autonomous launch and landing functionality is extended for solar‐powered UAVs. Fourth, as a main contribution an extended Kalman filter (EKF)‐based autonomous thermal updraft tracking framework is developed. Its novelty is that it allows the end‐to‐end integration of the thermal‐induced roll moment into the estimation process. It is assessed against unscented Kalman filter and particle filter methods in simulation and implemented on the aircraft's low‐power autopilot. The complete system is verified during a 26 h search‐and‐rescue aerial sensing mock‐up mission that represents the first‐ever fully autonomous perpetual endurance flight of a small solar‐powered UAV with a day/night‐capable sensing payload. It also represents the first time that solar‐electric propulsion and autonomous thermal updraft tracking are combined in flight. In contrast to previous work that has focused on the energetic feasibility of perpetual flight, the individual technical contributions of this paper are considered core functionality to guarantee ease‐of‐use, effectivity, and reliability in future multiday aerial sensing operations with small solar‐powered UAVs.     

Short communication: Evaluation of 5 different ELISA for the detection of bovine leukemia virus antibodies

Although Canadian dairy herds have been infected with bovine leukemia virus (BLV) for years, recent research has put new emphasis on the potential negative effects of this infection. Consequently, BLV control is becoming more favorable; however, BLV control cannot be successful without identifying infected animals. Bovicheck BLV (Biovet, Saint-Hyacinthe, QC, Canada) is currently the only assay licensed by the Canadian Centre for Veterinary Biologics. The first goal of this study was, therefore, to determine the reproducibility of the Bovicheck BLV assay for serum samples derived from Canadian cattle. The second goal was to evaluate and compare 5 different ELISA and determine their test characteristics using serum samples from Canadian herds. The considered ELISA were Bovicheck BLV, ID Screen BLV Competition (IDvet, Grabels, France), Idexx Leukosis Serum X2 Ab Test (Idexx Europe B.V., Hoofddorp, the Netherlands), Svanovir BLV gp51-Ab (Svanova, Uppsala, Sweden), and the Serelisa BLV Ab Mono Indirect (Synbiotics, Lyon, France). Eighty serum samples from Canadian cattle provided by Prairie Diagnostic Services (PDS; Saskatoon, SK, Canada) and an additional 80 serum samples from Canadian dairy and beef herds were used for the study. The Bovicheck BLV assay yielded the same results for all PDS-derived samples, implying a high level of reproducibility and robustness of this assay. Additionally, the comparison of the assays' results showed high agreement between assays, with Cohen's kappa values between κ = 0.91 and κ = 1. Furthermore, using original test results of the field samples as true status, relative diagnostic sensitivity and specificity were calculated. Relative diagnostic sensitivity of all tests was 100%. False-positive results were probable; therefore, the following relative diagnostic specificities were determined: 100% for Bovicheck BLV, Idexx Leukosis Serum X2, and Svanovir BLV; 95% for ID Screen BLV; and 97% for Serelisa BLV. When considering other test characteristics, ID Screen BLV is exceptional due to considerable practical advantages.     

Selective Hydrogenation of Fatty Nitriles to Primary Fatty Amines: Catalyst Evaluation and Optimization Starting from Octanenitrile

In this contribution, an evaluation of the potential of various homogeneous and heterogeneous catalysts for a selective hydrogenation of fatty nitriles toward primary amines is reported exemplified for the conversion of octanenitrile into octane‐1‐amine as a model reaction. When using heterogeneous catalysts such as the ruthenium catalyst Ru/C, the palladium catalyst Pd/C, and the platinum catalyst Pt/Al₂O₃, low selectivities in the hydrogenation are observed, thus leading to a large portion of secondary and tertiary amine side‐products. For example, when using Ru/C as a heterogeneous catalyst, high conversions of up to 99% are obtained but the selectivity remains low with a percentage of the primary amine being at 60% at the highest. The study further reveals a high potential of homogeneous ruthenium and manganese catalysts. When also taking into account economical considerations with respect to the metal price, in particular, manganese catalysts turn out to be attractive for the desired transformation and their application in the model reaction leads to the desired primary amine product with excellent conversion, selectivity, and high yield. Practical Applications: This work describes an optimized hydrogenation process for transforming fatty nitriles to their corresponding primary amines. In general, fatty amines belong to the most applied fatty acid‐derived compounds in the chemical industry with an annual product volume exceeding 800 000 tons per year in 2011 and are widely required in the chemical industry since such compounds are either directly used in home products such as fabric softeners, dishwashing liquids, car wash detergents, or carpet cleaners or in a broad range of industrial products, for example, lubricating additives, flotation agents, dispersants, emulsifiers, corrosion inhibitors, fungicides, and bactericides, showing additional major applications, e.g., in the detergents industry. Among them primary amines play an important industrial role. However, a major concern of current processes is the lack of selectivity and the formation of secondary and tertiary amines as side‐products. By modifying a recently developed catalytic system based on manganese as economically attractive and environmentally benign metal component an efficient and selective access to fatty amines when starting from the corresponding nitriles is achieved. For example, hydrogenation of octanenitrile leads to a synthesis of octane‐1‐amine with >99% conversion and excellent selectivity with formation of secondary and tertiary amine side‐products being suppressed to an amount of <1%.     

Lipid interference in the determination of the concentration of haemoglobin in plasma using the ACA SX analyzer

In comparison to a triple wavelength procedure, the dual wavelength method for the determination of plasma haemoglobin concentration using the ACA analyzer showed considerable interference with hypertriglyceridaemic (triacylglycerols > 2.3 mmol/l) plasma. By addition of isolated human lipoprotein fractions to normotriglyceridaemic plasma, chylomicrons were identified as a major source of interference with the ACA plasma haemoglobin method, whereas VLDL was without effect up to a triacylglycerol concentration of 5.7 mmol/l. Airfuge ultracentrifugation proved to be a reliable means for removal of interfering lipid. We conclude that the extent of lipid interference with the ACA plasma haemoglobin method is highly dependent on the type of lipoprotein present. An accurate measurement of plasma haemoglobin concentrations in non-fasting plasma can only be ensured after lipid removal through airfuge ultracentrifugation.     

The persistent pay gap between Easterners and Westerners in Germany: A quarter-century after reunification

A quarter of a century after Germany's reunification, Eastern Germans still earn substantially less than Western Germans. This paper revisits the German wage differential and isolates the effect of differing returns to human capital endowments, the possibility of a location effect, and human capital depreciation on the regional wage gap. While the endowment effect, location effect, and human capital depreciation jointly account for the wage differential between Easterners and Westerners living in the West, the same does not hold true for individuals settled in the East, where part of the wage gap remains unexplained.