Low temperature fabrication of magnesium phosphate cement scaffolds by 3D powder printing

Synthetic bone replacement materials are of great interest because they offer certain advantages compared with organic bone grafts. Biodegradability and preoperative manufacturing of patient specific implants are further desirable features in various clinical situations. Both can be realised by 3D powder printing. In this study, we introduce powder-printed magnesium ammonium phosphate (struvite) structures, accompanied by a neutral setting reaction by printing farringtonite (Mg₃(PO₄)₂) powder with ammonium phosphate solution as binder. Suitable powders were obtained after sintering at 1100°C for 5 h following 20–40 min dry grinding in a ball mill. Depending on the post-treatment of the samples, compressive strengths were found to be in the range 2–7 MPa. Cytocompatibility was demonstrated in vitro using the human osteoblastic cell line MG63.     

No security: A meta-analysis and review of job insecurity and its consequences.

Meta-analytic techniques were used to estimate how job insecurity relates to its postulated outcomes. Consistent with the conceptual framework, the results indicate that job insecurity has detrimental consequences for employees' job attitudes, organizational attitudes, health, and, to some extent, their behavioral relationship with the organization. Moderator analyses suggest that these relationships may be underestimated in studies relying on single-item measures of job insecurity and that the behavioral consequences of insecurity are more detrimental among manual, as compared with nonmanual, workers. Recommendations made for future research include utilization of multidimensional measures, consideration of a broader spectrum of outcomes and moderators, and use of longitudinal designs. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Aryl Bis‐Sulfonamide Inhibitors of IspF from Arabidopsis thaliana and Plasmodium falciparum

2‐Methylerythritol 2,4‐cyclodiphosphate synthase (IspF) is an essential enzyme for the biosynthesis of isoprenoid precursors in plants and many human pathogens. The protein is an attractive target for the development of anti‐infectives and herbicides. Using a photometric assay, a screen of 40 000 compounds on IspF from Arabidopsis thaliana afforded symmetrical aryl bis‐sulfonamides that inhibit IspF from A. thaliana (AtIspF) and Plasmodium falciparum (PfIspF) with IC₅₀ values in the micromolar range. The ortho‐bis‐sulfonamide structural motif is essential for inhibitory activity. The best derivatives obtained by parallel synthesis showed IC₅₀ values of 1.4 μm against PfIspF and 240 nm against AtIspF. Substantial herbicidal activity was observed at a dose of 2 kg ha^?1. Molecular modeling studies served as the basis for an in silico search targeted at the discovery of novel, non‐symmetrical sulfonamide IspF inhibitors. The designed compounds were found to exhibit inhibitory activities in the double‐digit micromolar IC₅₀ range.     

STD‐NMR‐Based Protein Engineering of the Unique Arylpropionate‐Racemase AMDase G74C

Structure‐guided protein engineering achieved a variant of the unique racemase AMDase G74C, with 40‐fold increased activity in the racemisation of several arylaliphatic carboxylic acids. Substrate binding during catalysis was investigated by saturation‐transfer‐difference NMR (STD‐NMR) spectroscopy. All atoms of the substrate showed interactions with the enzyme. STD‐NMR measurements revealed distinct nuclear Overhauser effects in experiments with and without molecular conversion. The spectroscopic analysis led to the identification of several amino acid residues whose substitutions increased the activity of G74C. Single amino acid exchanges increased the activity moderately; structure‐guided saturation mutagenesis yielded a quadruple mutant with a 40 times higher reaction rate. This study presents STD‐NMR as versatile tool for the analysis of enzyme–substrate interactions in catalytically competent systems and for the guidance of protein engineering.     

Tagging Glycoproteins with Fluorescently Labeled GDP‐Fucoses by Using α1,3‐Fucosyltransferases

Fucose‐containing glycans mediate a variety of biological processes, but there is little information on reaction processes and mechanisms mediated by fucosyltransferases. We recently reported on fluorescently labeled GDP‐β‐L ‐fucose‐ATTO 550, which enabled monitoring of α1,3‐fucosyltransferase activity. Here we present an extension to the previously described results, based on the synthesis of a fluorescein‐isothiocyanate (FITC)‐labeled and two carboxyfluorescein‐labeled (FAM‐labeled) NDP‐β‐L ‐fucose derivatives, and applied all four compounds in labeling of different glycoproteins with the aid of four different fucosyltransferases. The labeling processes were analyzed by in‐gel fluorescence and fluorescence polarization measurements. Comparison with the ATTO‐labeled sugar revealed that the FITC‐labeled fucose was the best of these substrates, and that the bacterial enzyme HP‐FucT tolerated the fluorescent substrates better than human fucosyltransferases.     

P450 BM3 Monooxygenase as an Efficient NAD(P)H‐Oxidase for Regeneration of Nicotinamide Cofactors in ADH‐Catalysed Preparative Scale Biotransformations

Enzymatic oxidations of primary and secondary alcohols catalysed by nicotinamide dependent alcohol dehydrogenases on the preparative scale require cofactor regeneration systems. Of critical value from an economic and ecological perspective is the application of NAD(P)H‐oxidases, which utilise molecular oxygen as a cost‐effective, atom‐efficient and environmentally benign oxidant to regenerate the cofactor NAD(P)⁺. Herein, the P450 BM3 monooxygenase from Bacillus megaterium is presented as an NAD(P)H‐oxidase for the successful regeneration of both NADP⁺ and NAD⁺ on the preparative scale. This enzyme was exemplarily applied for ADH‐catalysed oxidative kinetic resolutions of racemic secondary alcohols and the desymmetrisation of a meso‐diol leading to enantiomerically enriched secondary alcohols in both cases. Furthermore, the ADH‐catalysed oxidation of a primary alcohol targeting the corresponding aldehyde was performed. The obtained results significantly broaden the scope of feasible oxidative biotransformations, thereby increasing the number of synthetic reactions complying with key challenges of a modern and sustainable chemistry such as mild reaction conditions, environmentally benign solvents, and biodegradable non‐toxic catalysts.

     

Systematische Untersuchung der Azikularferritbildung in Stählen

The formation of acicular ferrite is mainly influenced by the steel composition, cooling rate, austenite grain size, and inclusion landscape. However, their precise effects have not been clarified in literature yet. Within the FWF project TRP 266-N19, a systematic methodology to study the influencing factors of the acicular ferrite formation as well as their interactions on laboratory scale was developed. The present work exemplarily demonstrates the application of this methodology for studying the effect of cooling rate and boron on the formation of acicular ferrite in a low-carbon HSLA steel.     

Trans octadecenoic fatty acid (TFA) isomers in German foods and bakery goods

In the present study, 122 food samples from the German food market were analysed for their C18:1 trans fatty acid (TFA) content and profile. A particular focus of the survey were baked and fried foods. TFA analysis was performed by means of silver ion SPE (Ag⁺‐SPE) in combination with high‐resolution GC (HRGC‐FID). Overall, 51 bakery product samples were analysed of which 25 samples were prepacked bakery products purchased from local retail stores and 26 samples of unpacked bakery products purchased from local bakery shops. In addition, 14 French fries samples obtained from small local fast food restaurants as well as from internationally operating fast food chains, 27 potato and tortillas chips, 15 instant soups as well as 15 dry culinary sauces were analysed. The highest amounts of C18:1 TFA isomers were found in deep‐fried bakery products. Prepacked branded cookies and biscuits on the other hand contained only negligible C18:1 TFA amounts. Regarding their C18:1 trans isomer profile most deep‐fried bakery products exhibited a Gaussian‐distributed isomer profile. The analysed prepacked croissants, cookies and biscuits contained predominantly ruminant TFA (TFA) as suggested by the presence of vaccenic acid (C18:1 trans 11), which was the major C18:1 TFA isomer in these products. All non‐bakery samples (n = 71) contained less than 3 g C18:1 TFA per 100 g fat. In conclusion, TFA still occur in considerable amounts in a few German food products, especially in some deep‐fried bakery products (‘Berliner’ type of doughnuts). Practical applications: Trans fatty acids, in particular the trans octadecenoic fatty acid isomers (C18:1), are generally considered from the nutritional point of view as undesirable food components due to their negative health effects. Tremendous efforts have been made by major food processors in order to decrease or even eliminate the presence of TFA in some foodstuffs (e.g. in margarines in European countries). However, some food processors of other food sectors are still applying oils and fats containing partially hydrogenated vegetable oils, whereas others within the same food category have already switched their processing conditions and/or raw materials towards TFA alternatives. Therefore, actual TFA data of foodstuffs determined by means of state‐of‐the‐art analytical procedures (Ag⁺‐SPE in combination with GC‐FID) is necessary to detect areas of further improvement in the food supply chain and to provide data for an update of dietary TFA intake.