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- Wirtschaftsingenieurwesen (33) (entfernen)
The diffusion of hydrogen adsorbed inside layered MoS2 crystals has been studied by means of quasi- elastic neutron scattering, neutron spin-echo spectroscopy, nuclear reaction analysis, and X-ray photoelectron spectroscopy. The neutron time-of-flight and neutron spin-echo measurements demonstrate fast diffusion of hydrogen molecules parallel to the basal planes of the two dimensional crystal planes. At room temperature and above, this intra-layer diffusion is of a similar speed to the surface diffusion that has been observed in earlier studies for hydrogen atoms on Pt surfaces. A significantly slower hydrogen diffusion was observed perpendicular to the basal planes using nuclear reaction analysis.
Bone morphogenetic protein 2 (BMP21) is a highly interesting therapeutic growth factor due to its strong osteogenic/osteoinductive potential. However, its pronounced aggregation tendency renders recombinant and soluble production troublesome and complex. While prokaryotic expression systems can provide BMP2 in large amounts, the typically insoluble protein requires complex denaturation-renaturation procedures with medically hazardous reagents to obtain natively folded homodimeric BMP2. Based on a detailed aggregation analysis of wildtype BMP2, we designed a hydrophilic variant of BMP2 additionally containing an improved heparin binding site (BMP2-2Hep-7M). Consecutive optimization of BMP2-2Hep-7M expression and purification enabled production of soluble dimeric BMP2-2Hep-7M in high yield in E. coli. This was achieved by a) increasing protein hydrophilicity via introducing seven point mutations within aggregation hot spots of wildtype BMP2 and a longer N-terminus resulting in higher affinity for heparin, b) by employing E. coli strain SHuffle® T7, which enables the structurally essential disulfide-bond formation in BMP2 in the cytoplasm, c) by using BMP2 variant characteristic soluble expression conditions and application of L-arginine as solubility enhancer. The BMP2 variant BMP2-2Hep-7M shows strongly attenuated although not completely eliminated aggregation tendency.
The activated sludge respiration inhibition test and the luminescent bacteria test with Vibrio fischeri are important bacterial test systems for evaluation of the toxicity of chemical compounds. These test systems were further optimized to result in better handling, reliability and sensitivity. Concerning the Vibrio fischeri test, media components such as yeast extract and bivalent cation concentrations like Ca2+ and Mg2+ were optimized. The cultivation, storage conditions and reactivation process of the stored bacteria were also improved, which enabled simpler handling and led to good reproducibility. Additionally, the respiration inhibition test with a prolonged incubation time was further analyzed using different chlorinated phenols as reference compounds. It could be stated that a longer incubation period significantly improved the sensitivity of the test system.
Digitalisierung im Verkehr
(2019)
Preparation, catalytical activity and crystal structure of a heptanuclear zinc acetate cluster
(2017)
Under ambient conditions, almost all metals are coated by an oxide. These coatings, the result of a chemical reaction, are not passive. Many of them bind, activate and modify adsorbed molecules, processes that are exploited, for example, in heterogeneous catalysis and photochemistry. Here we report an effect of general importance that governs the bonding, structure formation and dissociation of molecules on oxidic substrates. For a specific example, methanol adsorbed on the rutile TiO2(110) single crystal surface, we demonstrate by using a combination of experimental and theoretical techniques that strongly bonding adsorbates can lift surface relaxations beyond their adsorption site, which leads to a sig- nificant substrate-mediated interaction between adsorbates. The result is a complex super- structure consisting of pairs of methanol molecules and unoccupied adsorption sites. Infrared spectroscopy reveals that the paired methanol molecules remain intact and do not depro- tonate on the defect-free terraces of the rutile TiO2(110) surface.
Three dinuclear zinc carboxylate complexes [L1−3Zn(μ,η2-O2CPh)]2 (1, 2, 4) containing either the bidentate N,N′-chelating β-diketiminate ligand RNC(Me)C(H)C(Me)NR (R = 2,6-iPr2-C6H3, L1, complex 1), the tridentate O,N,N-chelating ligand OC(Me)C(H)C(Me)NCH2CH2NMe2 (L2, complex 2) or the bis-N,N′-chelating bis-β-diketiminate ligand RNC(Me)C(H)C(Me)NNC(Me)C(H)C(Me)NR (R = 2,6-iPr2-C6H3, L3, complex 4) were synthesized and characterized including single-crystal X-ray diffraction. Reaction of the neutral bis-β-diketimine (L3(H)2) with two equivalents of ZnMe2 leads to the expected heteroleptic dinuclear zinc complex L3(ZnMe)2 3 in 93 % yield. Further reaction with benzoic acid PhCO2H leads to complex 4. Complex 2 forms a rather strong carboxylate-bridged dimer, whereas the carboxylate groups in complexes 1 and 4 act as asymmetrical bridges between both Zn atoms, pointing to the formation of a weakly bonded dimer. The zinc atoms in 1 and 4 are tetrahedrally coordinated, whereas in 2 the coordination number is increased to five due to the coordination of the pendant donor arm. The ring opening polymerization (ROP) of rac-lactide was investigated with the zinc complexes 1–4 and diazabicycloundec-7-ene (DBU) as a co-catalyst. Complexes 2 and 3 are active polymerization catalysts, which in the presence of DBU converted 200 equiv. of rac-lactide into polylactide within 10 min at ambient temperature. The analysis of the crude polymer showed that the lactide polymerization with catalyst 2 occurs via a slightly modified activated-monomer mechanism.