Photokatalytische Bildung von Wasserstoff aus Thiolen in Gegenwart von Vitamin B12-Modellverbindungen mit Azid als photochemischem Opferliganden

Photocatalytic Hydrogen Formation from Thioles in the Presence of Vitamin-B₁₂ Model Complexes with Azide as Photochemical Sacrificial Ligand The photolysis of [N₃Co(chelat)B] complexes ( 1–3 ) (chelat = dimethylglyoxime, dmg; N,N′-o-phynylenebis(salicylidenimine), salphen; N,N′-ethylene-bis(salicylidenimine), salen; B = pyridine) leads by homolytic cleavage of the Co–N₃ bond to both coordinatively unsaturated cobalt(II) chelates [Co(chelat)B] and N₃ ligand radicals that undergo fast decay to dinitrogen. The photolysis of the cobalt (III) complexes 1–3 in the presence of thiophenole and other thioles proceeds catalytically and yields the corresponding disulphides and dihydrogen. The mechanism of this photocatalytic generation of dihydrogen is due to the catalytic activity of the coordinatively unsaturated cobalt(II) species formed photochemically. A photocatalytic cycle is proposed describing the generation of hydrogen. Possible photochemical and thermal steps of that cycle are discussed.     

The Deubiquitinase OTUB1 Is a Key Regulator of Energy Metabolism

Dysregulated energy metabolism is a major contributor to a multitude of pathologies, including obesity and diabetes. Understanding the regulation of metabolic homeostasis is of utmost importance for the identification of therapeutic targets for the treatment of metabolically driven diseases. We previously identified the deubiquitinase OTUB1 as substrate for the cellular oxygen sensor factor-inhibiting HIF (FIH) with regulatory effects on cellular energy metabolism, but the physiological relevance of OTUB1 is unclear. Here, we report that the induced global deletion of OTUB1 in adult mice (Otub1 iKO) elevated energy expenditure, reduced age-dependent body weight gain, facilitated blood glucose clearance and lowered basal plasma insulin levels. The respiratory exchange ratio was maintained, indicating an unaltered nutrient oxidation. In addition, Otub1 deletion in cells enhanced AKT activity, leading to a larger cell size, higher ATP levels and reduced AMPK phosphorylation. AKT is an integral part of insulin-mediated signaling and Otub1 iKO mice presented with increased AKT phosphorylation following acute insulin administration combined with insulin hypersensitivity. We conclude that OTUB1 is an important regulator of metabolic homeostasis.     

Bioraffinerien auf Basis schwach verholzter Biomasse

Weakly lignified biomass, like brewers' spent grain and grass silage, is good feedstock for biorefineries. The biomass can be separated and converted into valuable products in different ways. In this study, brewers' spent grain is used to investigate solid state fermentations with Cellulomonas uda. Additionally, hydrothermal pretreatment and subsequent enzymatic saccharification, as well as formation of inhibitory compounds, is demonstrated. Hydrothermal pretreatment combined with simultaneous saccharification and fermentation is shown as an example for the utilization of grass silage.     

Dissolution,Transport and Reaction at a DICY/DGEBA Interface

The curing of an epoxy consisting of the solid hardener dicyandiamide (DICY) and the resin diglycidyl ether of bisphenol A (DGEBA) is studied in a system consisting of a tablet of DICY embedded in liquid DGEBA. Dissolution of DICY within the liquid DGEBA in combination with the transport of dissolved DICY from the tablet border into DGEBA and the chemical reaction of both reactants is studied by scanning Brillouin microscopy and infrared spectroscopy. Scanning Brillouin microscopy demonstrates the spatial and temporal evolution of the static and dynamic hypersonic properties in the course of curing in the vicinity of the DICY tablet. Infrared spectroscopy performed on epoxy pieces extracted from the final sample at different distances from the tablet surface give information about the spatial evolution of the curing process. The results achieved by both techniques are finally combined to yield a better understanding of the curing of DICY-based epoxies, which transform upon curing from strongly heterogeneous systems towards increasingly homogeneous systems.     

Dual,Site‐Specific Modification of Antibodies by Using Solid‐Phase Immobilized Microbial Transglutaminase

Microbial transglutaminase (MTG) was stably solid‐phase immobilized on glass microbeads by using a second‐generation dendronized polymer. Immobilized MTG enabled the efficient generation of site‐specifically conjugated proteins, including antibody fragments, as well as whole antibodies through distinct glutamines and, unprecedentedly, also through lysines with various bifunctional substrates with defined stoichiometries. With this method, we generated dual, site‐specifically modified antibodies comprising a fluorescent probe and a metal chelator for radiolabeling—a strategy anticipated to design antibodies for imaging and simultaneous therapy. Furthermore, we provide evidence that immobilized MTG features higher siteselectivity than soluble MTG.     

Extraction of heavy metals from soils using biodegradable chelating agents

Metal pollution of soils is widespread across the globe, and the clean up of these soils is a difficulttask. One possible remediation technique is ex-situ soil washing using chelating agents. Ethylenediaminetetraacetic acid (EDTA) is a very effective chelating agent for this purpose but has the disadvantage that it is quite persistent in the environment due to its low biodegradability. The aim of our work was to investigate the biodegradable chelating agents [S,S]-ethylenediaminedisuccinic acid (EDDS), iminodisuccinic acid (IDSA), methylglycine diacetic acid (MGDA), and nitrilotriacetic acid (NTA) as potential alternatives and compare them with EDTA for effectiveness. Kinetic experiments showed for all metals and soils that 24 h was the optimum extraction time. Longer times only gave minor additional benefits for heavy metal extraction but an unwanted increase in iron mobilization. For Cu at pH 7, the order of the extraction efficiency for equimolar ratios of chelating agent to metal was EDDS > NTA> IDSA > MGDA > EDTA and for Zn it was NTA > EDDS > EDTA >MGDA > IDSA. The comparatively low efficiency of EDTA resulted from competition between the heavy metals and co-extracted Ca. For Pb the order of extraction was EDTA > NTA >EDDS due to the much stronger complexation of Pb by EDTA compared to EDDS. At higher concentration of complexing agent, less difference between the agents was found and less pH dependence. There was an increase in heavy metal extraction with decreasing pH, but this was offset by an increase in Ca and Fe extraction. In sequential extractions EDDS extracted metals almost exclusively from the exchangeable, mobile, and Mn-oxide fractions. We conclude that the extraction with EDDS at pH 7 showed the best compromise between extraction efficiency for Cu, Zn, and Pb and loss of Ca and Fe from the soil.     

Short communication: Evaluation of an automated in-house hematology analyzer for bovine blood

The objective of this study was to evaluate the suitability of the V-Sight hematology analyzer (A. Menarini Pharma GmbH, Vienna, Austria) for bovine blood by a comparison with a reference device (Advia 2120i, Siemens AG, Erlangen, Germany). In total, 97 blood samples were obtained from 75 dairy cows. Analyzed parameters included counts of white blood cells (WBC), lymphocytes, monocytes, granulocytes, red blood cells (RBC), and platelets (PLT), as well as hemoglobin concentration (HGB), hematocrit (HCT), mean corpuscular volume, mean corpuscular hemoglobin (MCH), MCH concentration (MCHC), mean platelet volume (MPV), and plateletcrit (PCT). Based on Passing-Bablok regression, the V-Sight provided accurate and precise results for MCH and MCHC only. The PCT results were comparable to the reference method, but precision was inconclusive. Significant proportional differences were detected for monocytes, granulocytes, HCT, and PLT. For all other analytes, significant proportional and systemic differences were observed. The WBC and lymphocyte results from the V-Sight were characterized by poor accuracy, poor precision, and a high number of false positive outliers. Bland-Altman analysis indicated negative biases for all WBC parameters, the erythrocyte indices, and PLT. Positive biases were observed for RBC, HGB, HCT, MPV, and PCT. Correlation coefficients of >0.9 between the V-Sight and the reference method were found only for RBC, HGB, HCT, and MPV. Intraassay precision of the V-Sight analyzer was acceptable (coefficient of variation <5%) for granulocytes, the erythrocyte indices, and MPV. It was unacceptable (coefficient of variation ≥5%) for WBC, lymphocytes, monocytes, as well as RBC, and inconclusive for HGB, HCT, PLT, and PCT. Sensitivity was high for all RBC counts and indices as well as PLT, but low for monocytes, granulocytes, and MPV. Specificity was high for monocytes and granulocytes, but low for RBC, HCT, MCH, and MCHC. With accurate and precise results for only 2 out of 13 parameters, the V-Sight cannot be recommended for analysis of bovine blood.     

Zur Kenntnis des thermoplastischen Verhaltens von Holz

Ohne Zusammenfassung Mitteilung aus der Bundesanstalt für Forst- und Holzwirtschaft, Reinbek bei Hamburg.     

Model forecasts of atrazine in Lake Michigan in response to various sensitivity and potential management scenarios

For more than forty years, the herbicide atrazine has been used on corn crops in the Lake Michigan basin to control weeds. It is usually applied to farm fields in the spring before or after the corn crop emerges. A version of the WASP4 mass balance model, LM2-Atrazine, was used to assess the impact of the historical and future usage of this chemical on lake water concentrations. Long-term model forecasts were performed under various sensitivity and potential management scenarios. The model was calibrated to available lake data and results indicate that atrazine, under average conditions, is decaying very slowly in the lake (0.009/year). This kinetic decay translates into a half-life estimate of 77 years. If the average condition scenario were assumed to remain constant into the future and reflective of conditions in January 1, 2005, it is expected that the lake (excluding Green Bay) would eventually reach a volume-weighted average atrazine concentration of approximately 67 ng/L in the year 2157 (current model prediction is 48 ng/L for year 2011). These forecasted lake-wide concentrations are below known water quality criteria for the protection of aquatic ecosystems.