Einfluß der polymerisationsbedingungen auf die morphologie von schwefel-styrol-polymerisaten

For a polymer system sulfur-styrene containing 10 wt.-% styrene the morphologie depending on the polymerization temperature and time is described. Besides the characteristical orthorhombic phase a monoclinic and a pseudoorthorhombic phase were detected. Moreover amorphous material exists, depending on the polymerisation parameters.     

A balanced accumulation scheme for parallel PDE solvers

We present a tailored load balancing technique that addresses specific performance issues in the boundary data accumulation algorithm for non-overlapping domain decompositions. The technique is used to speed up a parallel conjugate gradient algorithm with an algebraic multigrid preconditioner to solve a potential problem on an unstructured tetrahedral finite element mesh. The optimized accumulation algorithm significantly improves the performance of the parallel solver and we show up to 50 % runtime improvements over the standard approach in benchmark runs with up to 48 MPI processes. The load balancing problem itself is a global optimization problem that is solved approximately by local optimization algorithms in parallel that require no communication during the optimization process.     

Divergence-based vector quantization

Supervised and unsupervised vector quantization methods for classification and clustering traditionally use dissimilarities, frequently taken as Euclidean distances. In this article, we investigate the applicability of divergences instead, focusing on online learning. We deduce the mathematical fundamentals for its utilization in gradient-based online vector quantization algorithms. It bears on the generalized derivatives of the divergences known as Fréchet derivatives in functional analysis, which reduces in finite-dimensional problems to partial derivatives in a natural way. We demonstrate the application of this methodology for widely applied supervised and unsupervised online vector quantization schemes, including self-organizing maps, neural gas, and learning vector quantization. Additionally, principles for hyperparameter optimization and relevance learning for parameterized divergences in the case of supervised vector quantization are given to achieve improved classification accuracy.     

Optochemical Control of Bacterial Gene Expression: Novel Photocaged Compounds for Different Promoter Systems

Photocaged compounds are applied for implementing precise, optochemical control of gene expression in bacteria. To broaden the scope of UV-light-responsive inducer molecules, six photocaged carbohydrates were synthesized and photochemically characterized, with the absorption exhibiting a red-shift. Their differing linkage through ether, carbonate, and carbamate bonds revealed that carbonate and carbamate bonds are convenient. Subsequently, those compounds were successfully applied in vivo for controlling gene expression in E. coli via blue light illumination. Furthermore, benzoate-based expression systems were subjected to light control by establishing a novel photocaged salicylic acid derivative. Besides its synthesis and in vitro characterization, we demonstrate the challenging choice of a suitable promoter system for light-controlled gene expression in E. coli. We illustrate various bottlenecks during both photocaged inducer synthesis and in vivo application and possibilities to overcome them. These findings pave the way towards novel caged inducer-dependent systems for wavelength-selective gene expression.     

Development and Characterization of New Peptidomimetic Inhibitors of the West Nile Virus NS2B–NS3 Protease

A series of new substrate analogue inhibitors of the WNV NS2B–NS3 protease containing decarboxylated arginine mimetics at the P1 position was developed. Among the various analogues, trans‐(4‐guanidino)cyclohexylmethylamide (GCMA) was identified as the most suitable P1 residue. In combination with dichloro‐substituted phenylacetyl groups at the P4 position, three inhibitors with inhibition constants of <0.2 μM were obtained. These GCMA inhibitors have a better selectivity profile than the previously described agmatine analogues, and possess negligible affinity for the trypsin‐like serine proteases thrombin, factor Xa, and matriptase. A crystal structure in complex with the WNV protease was determined for one of the most potent inhibitors, 3,4‐dichlorophenylacetyl‐Lys‐Lys‐GCMA (K_i=0.13 μM ). The inhibitor adopts a horseshoe‐like conformation, most likely due to a hydrophobic contact between the P4 phenyl ring and the P1 cyclohexyl group, which is further stabilized by an intramolecular hydrogen bond between the P1 guanidino group and the P4 carbonyl oxygen atom. These inhibitors are stable, readily accessible, and have a noncovalent binding mode. Therefore, they may serve as suitable lead structures for further development.     

Fabrication of Zein-Based Fibrous Scaffolds for Biomedical Applications—A Review

Zein, which accounts for around 80% of the total protein composition in corn, is a biocompatible and biodegradable substance derived from renewable sources. Although insoluble in water, its amphiphilic characteristics are utilized to generate nanoparticles, nanofibers, microparticles, and even films. Numerous recent studies have demonstrated the potential of zein as a prospective biomaterial to develop fibrous scaffolds for biomedical functions owing to its biocompatibility, fibrous formation, and encapsulating qualities. Fabrication of zein-based fibrous scaffolds for biomedical applications is achieved by a wide variety of techniques, including electrospinning, wet spinning, freeze drying, and additive manufacturing. This article overviews current advancements in manufacturing techniques for zein-based fibrous scaffolds. In addition, it summarizes the most recent biomedical applications and research activities utilizing zein-based fibrous scaffolds. Overall, zein is proposed as a potential biomaterial for the production of fibrous scaffolds that stimulate cell adhesion and proliferation in a number of exciting biomedical applications due to its biodegradability, biocompatibility, and other unique features related to its structure.     

Catalytic Flue Gas Treatment from Nitriding Processes

Efficient control and minimization of emissions from technical processes is of major concern in industrial development and process operation. The technical process in the focus of the present contribution is the nitriding process of metallic specimen. The ammonia content in nitriding process flue gases reaches up to 618 g·m^–3 (80 vol.‐%) and needs to be reduced to less than 30 mg·m^–3 (40 ppm) to fulfill present regulations. Exhaust gases from nitriding processes today are burnt in flares without emission control where fuels need to be added that produce additional exhaust gas components. The objective of this investigation is to develop an alternative gas cleaning route for nitriding processes based on catalytic dissociation of ammonia. The decomposition was studied for different catalysts at varying process conditions. With these results a dissociation pilot plant was successfully tested in a technical‐scale nitriding process.     

<Superscript>29</Superscript>Si NMR Chemical Shift Tensor and Electronic Structure of 7-Silanorbornadienes

The structure and bonding of 7-silanorbornadienes was investigated using X-ray Diffraction (XRD), solid-state NMR spectroscopy and density functional calculations. The solid state structures of four benzo-7-silanorbornadienes (4a, c, d, e) and of one dibenzo-7-silabenzonorbornadiene (5a) are reported and compared with the results of previous structural investigations. The most prominent features of the molecular structures of all 7-silanorbornadienes are very long Si-C(bridgehead) bonds (d(SiC) = 190.6–196.8 pm) and very acute CSiC bond angles α (α(CSiC) = 78.7–83.9°). All newly investigated 7-silanorborndienes show for tetracoordinated silicon nuclei extremely deshielded ²⁹Si NMR resonances (δ²⁹Si = 65.6–31.6). Solid State NMR investigations for 7-silanorbornadienes anti-4a, b reveal highly anisotropic chemical shift tensors of axial or nearly axial symmetry (4a: δ₁₁ = 161, δ₂₂ = δ₃₃ = −11; 4b: δ₁₁ = 113, δ₂₂ = 14, δ₃₃ = −15). The dominating, strongly deshielding δ₁₁ component is oriented almost perpendicular to the plane spanned by the two bridgehead carbon atoms and the bridging silicon atom. The DFT calculations suggest that the origin of the strong deshielding is a small energy difference between the frontier orbitals, which are strongly localized at the silicon atom. In addition the computations reveal that both the long SiC bonds and the strongly deshielded ²⁹Si NMR chemical shift are direct consequences of the bonding situation in 7-silanorbornadienes which are characterized by through space interaction of the C=C double bonds and by hyperconjugation between the SiC σ-bonds and the unoccupied orbitals of the C=C double bonds.     

Surface Cleaning or Activation？Control of Surface Condition Prior to Thermo-Chemical Heat Treatment

Actual heat treatment processes must face increasing specifications with reference to process quality, safety and results in terms of reproducibility and repeatability. They can be met only if the parts‘ surface condition is controlled during manufacturing and, especially, prior to the treatment. An electrochemical method for the detection of a steel part‘s surface condition is presented, together with results, consequences, and mechanisms concerning surface pre-treatment before the thermochemical process. A steel surface‘s activity or passivity can be detected electrochemically, independently from the chemical background. The selected method was the recording of potential vs. time curves at small constant currents, using a miniaturized electrochemical cell, a (nearly) non-destructive electrolyte and a potentio-galvanostatic setup. The method enables to distinguish types of surface contamination which do not interfere with the thermochemical process, from passive layers which do and must be removed. Whereas some types of passive layers can be removed using conventional cleaning processes and agents, others are so stable that their effects can only be overcome by applying an additional activation pre-treatment, e.g. oxynitriding.