Aktivierung von CO2 an Übergangsmetallzentren: Zum Ablauf der CO2-Reduktion an Nickel(0)-Fragmenten

Activation of CO₂ at Transition Metal Centres: The Route of the CO₂ Reduction at Nikel(0) Moieties A competing reaction in the catalytic cyclooligomerization of hex-3-yne and CO₂ at the (TMED)Ni(0)-fragment (TMED = N,N,N′,N′-tetramethylethylendiamine) is the formation of carbon monoxide and (TMED)Ni(CO₃). So it is possible to explain the generation of II (TMED)Ni(diethylmalicacidanhydride) and III (a nickel trimer with two (TMED)Ni(CO₃) units). Both complexes are characterized by X-ray analysis. The reduction of CO₂ to CO most likely proceeds via an intermediate in which two molecules of carbon dioxide are coupled head-to-tail to form a metallacycle. An ab initio scf geometry optimization supports the existence of such an intermediate.     

Reaction of Ni2+ and SnS as a Way to Form Ni@SnS and Sn2Ni3S2 Nanocrystals: Control of Product Formation and Shape

Reductive diffusion of Ni²⁺ into SnS particles was shown to selectively form Sn₂Ni₃S₂, hybrid, or even core‐shell Ni@SnS, Ni_1.523Sn, and Ni₃S₂, by tuning the reaction conditions at low temperatures. The mechanism of Ni²⁺ reduction and diffusion into SnS was observed in ethylene glycol, which served both as solvent and reducing agent. Tuning of reaction temperature and duration, morphology of the template SnS, and the application of ethylenediamine as supporting chelating agent, influence the formation of the final products. Their formation was controlled by carefully adjusting redox and equilibrium reactions. The products were characterized by X‐ray diffraction (XRD), scanning electron microscopy (SEM), and energy dispersive X‐ray spectroscopy analysis (EDX).     

A Rechargeable Hydrogen Battery Based on Ru Catalysis

Apart from energy generation, the storage and liberation of energy are among the major problems in establishing a sustainable energy supply chain. Herein we report the development of a rechargeable H₂ battery which is based on the principle of the Ru‐catalyzed hydrogenation of CO₂ to formic acid (charging process) and the Ru‐catalyzed decomposition of formic acid to CO₂ and H₂ (discharging process). Both processes are driven by the same catalyst at elevated temperature either under pressure (charging process) or pressure‐free conditions (discharging process). Up to five charging–discharging cycles were performed without decrease of storage capacity. The resulting CO₂/H₂ mixture is free of CO and can be employed directly in fuel‐cell technology.     

Parallel radial basis function methods for the global optimization of expensive functions

We introduce a master–worker framework for parallel global optimization of computationally expensive functions using response surface models. In particular, we parallelize two radial basis function (RBF) methods for global optimization, namely, the RBF method by Gutmann [Gutmann, H.M., 2001a. A radial basis function method for global optimization. Journal of Global Optimization 19(3), 201–227] (Gutmann-RBF) and the RBF method by Regis and Shoemaker [Regis, R.G., Shoemaker, C.A., 2005. Constrained global optimization of expensive black box functions using radial basis functions, Journal of Global Optimization 31, 153–171] (CORS-RBF). We modify these algorithms so that they can generate multiple points for simultaneous evaluation in parallel. We compare the performance of the two parallel RBF methods with a parallel multistart derivative-based algorithm, a parallel multistart derivative-free trust-region algorithm, and a parallel evolutionary algorithm on eleven test problems and on a 6-dimensional groundwater bioremediation application. The results indicate that the two parallel RBF algorithms are generally better than the other three alternatives on most of the test problems. Moreover, the two parallel RBF algorithms have comparable performances on the test problems considered. Finally, we report good speedups for both parallel RBF algorithms when using a small number of processors.     

Untersuchungen von Sorptions- und Transportvorgängen bei Erhöhten Temperaturen und Drücken ALS Beitrag zur Aufklärung des Mechanismus der Bildung Radioaktiver Ablagerungen im Primärkreislauf von Druckwasser-Reaktoren

Radioactivity build-up in primary circuits of nuclear power reactors is a serious problem in reactor operation and maintenance. The mechanism and the possibilities for decreasing this build-up are briefly discussed. Experimental results on cobalt ion sorption at corrosion product surfaces as a function of pH are dealed with and interpreted as a hydrolysis phenomenon. Experiments on mass transport of corrosion product oxides into and through solution are also described.      

Zerstörungsfreie risstiefenbestimmung in Betonbauwerken mittels Radiotracerverfahren

At the Leipzig Technical University a method was developed, which allows to determine nondestructive the crack depth in concrete up to 15 cm. Based on a radiotracer technique the access to only one side of the object is required. The labelling of artificial-made cracks was carried out by use of a transport medium (not miscible with water) on the base of methyl isobutyl ketone (MIBK) and In- 113m as radionuclide. For the calculation of crack depth, measure-geometrical parameters were used. The improvement of the reliability of building-diagnostical interpretation using radio-physical parameters is described. A first application is provided for concrete structures below chemical equipments built as a barrier against ecologically harmful substances (petrol tanks). The intersectional aspect of further qualifications of the technique is emphasized.     

K-Carrageenan Stimulates Pre-Osteoblast Proliferation and Osteogenic Differentiation: A Potential Factor for the Promotion of Bone Regeneration?

Current cell-based bone tissue regeneration strategies cannot cover large bone defects. K-carrageenan is a highly hydrophilic and biocompatible seaweed-derived sulfated polysaccharide, that has been proposed as a promising candidate for tissue engineering applications. Whether κ-carrageenan can be used to enhance bone regeneration is still unclear. In this study, we aimed to investigate whether κ-carrageenan has osteogenic potential by testing its effect on pre-osteoblast proliferation and osteogenic differentiation in vitro. Treatment with κ-carrageenan (0.5 and 2 mg/mL) increased both MC3T3-E1 pre-osteoblast adhesion and spreading at 1 h. K-carrageenan (0.125–2 mg/mL) dose-dependently increased pre-osteoblast proliferation and metabolic activity, with a maximum effect at 2 mg/mL at day three. K-carrageenan (0.5 and 2 mg/mL) increased osteogenic differentiation, as shown by enhanced alkaline phosphatase activity (1.8-fold increase at 2 mg/mL) at day four, and matrix mineralization (6.2-fold increase at 2 mg/mL) at day 21. K-carrageenan enhanced osteogenic gene expression (Opn, Dmp1, and Mepe) at day 14 and 21. In conclusion, κ-carrageenan promoted MC3T3-E1 pre-osteoblast adhesion and spreading, metabolic activity, proliferation, and osteogenic differentiation, suggesting that κ-carrageenan is a potential osteogenic inductive factor for clinical application to enhance bone regeneration.     

A stabilized mixed method applied to Stokes system with nonhomogeneous source terms: The stationary case Dedicated to Prof. R. Rodríguez,on the occasion of his 65th birthday

This article is concerned with the Stokes system with nonhomogeneous source terms and nonhomogeneous Dirichlet boundary condition. First, we reformulate the problem in its dual mixed form, and then, we study its corresponding well-posedness. Next, in order to circumvent the well-known Babuška-Brezzi condition, we analyze a stabilized formulation of the resulting approach. Additionally, we endow the scheme with an a posteriori error estimator that is reliable and efficient. Finally, we provide numerical experiments that illustrate the performance of the corresponding adaptive algorithm and support its use in practice.