Novel building blocks for oligonuclear copper complexes derived from β‐ketoenamines of histidine

Condensation products of L‐histidine with the 3‐oxoenolethers diethyl‐ethoxymethylene‐malonate ( 1 ) and ethyl‐ethoxymethylene‐cyanoacetate ( 2 ) react with copper(II) as di‐anionic ligands to give neutral 1:1 complexes Cu‐ His1 and Cu‐ His2 . Both complexes crystallize as oligonuclear units, even from strongly donating solvents like N‐methylimidazole (Meim) (Cu‐ His1 ) and pyridine (Cu‐ His2 ). X‐ray structure analyses show supramolecular structures, formed of two (Cu‐ His1 ) or four (Cu‐ His2 ) formula units of the complex, which arrange to macrocycles by means of intermolecular coordination of the imidazole‐N. Strong H‐bridges result in a face‐to‐face orientation of the hydrophilic sites of two great rings. ESI‐MS investigations in pyridine solution give evidence for the existence of dimeric, tetrameric and – in case of Cu‐ His2 – trimeric units, besides the monomeric adducts with one pyridine. In contrast to the dimeric or tetrameric (“cubane‐like”) copper(II) complexes of amino alcohols and their β‐ketoenamines, the complexes Cu‐ His1 and Cu‐ His2 show no significant spin coupling from room temperature down to 4 K. The complexes Cu‐ His1 and Cu‐ His2 give no electrochemically reversible Cu^II/I reduction in pyridine. However, the isolation of a stable diamagnetic copper(I) complex of the methylester derivative, Cu^I‐ HisMe1 , supports the assumption, that similar histidine‐derived copper complexes should display reversible redox behaviour and catalytic activity in reactions with O₂.     

A First‐Principles Investigation of the Compositional Dependent Properties of Magnetic Shape Memory Heusler Alloys

The interplay of structural and magnetic properties of magnetic shape memory alloys is closely related to their composition. In this study the influence of the valence electron concentration on the tetragonal transformation in Ni₂Mn_{1 + x}Z_{1 ? x} (Z = Ga, In, Sn, Sb) and Co₂Ni_{1 + x}Ga_{1 ? x} is investigated by means of ab initio calculations. While the type of magnetic interaction is different for the two series, the trends of the total energy changes under a tetragonal transformation are very similar. We find that tetragonal structures become energetically preferred with respect to the cubic one as the valence electron concentration e/a is increased regardless of the system under consideration. In particular, the energy difference between the austenite and martensite structures increases linearly with e/a, which is in part responsible for the linear increase of the matensite transformation temperature. The substitution of nickel by platinum increases even further the transformation temperature.     

Linking Grain Boundaries and Grain Growth in Ceramics

The macroscopic properties of most materials are strongly influenced by grain size. In ceramic materials the microstructure usually results from the sintering process. Understanding the basic mechanisms of grain growth on an atomic length scale in ceramics would be beneficial to tailor the microstructure for improved macroscopic performance of devices. A method is presented using grain growth experiments to select samples for closer examination of grain boundaries with transmission electron microscopy. The growth experiments are used to identify temperatures were changes at grain boundaries occur at high temperature. Subsequently samples of interest are investigated using transmission electron microscopy (TEM) methods. The correlation between TEM results and changes in grain growth behavior can be used to gain closer insight into the processes occurring during grain growth at an atomic length scale. Strontium titanate is used as model system to demonstrate the combination of growth experiments with TEM results. Normal grain growth shows two distinct drops in growth rate in the temperature range between 1 300 and 1 425 °C, independent of the A‐site to B‐site stoichiometry of the perovskite. In previous studies a high preference for grain boundary planes oriented parallel to the 100 direction of one of the adjacent grains was found in the high temperature regime. This study shows that the preference does not exist in the low temperature regime possibly explaining the change in grain growth rate.     

Risk and protection factors in fatal accidents

This paper aims at addressing the interest and appropriateness of performing accident severity analyses that are limited to fatal accident data. Two methodological issues are specifically discussed, namely the accident-size factors (the number of vehicles in the accident and their level of occupancy) and the comparability of the baseline risk. It is argued that - although these two issues are generally at play in accident severity analyses - their effects on, e.g., the estimation of survival probability, are exacerbated if the analysis is limited to fatal accident data. As a solution, it is recommended to control for these effects by (1) including accident-size indicators in the model, (2) focusing on different sub-groups of road-users while specifying the type of opponent in the model, so as to ensure that comparable baseline risks are worked with. These recommendations are applied in order to investigate risk and protection factors of car occupants involved in fatal accidents using data from a recently set up European Fatal Accident Investigation database (Reed and Morris, 2009). The results confirm that the estimated survival probability is affected by accident-size factors and by type of opponent. The car occupants’ survival chances are negatively associated with their own age and that of their vehicle. The survival chances are also lower when seatbelt is not used. Front damage, as compared to other damaged car areas, appears to be associated with increased survival probability, but mostly in the case in which the accident opponent was another car. The interest of further investigating accident-size factors and opponent effects in fatal accidents is discussed.     

A W7-X experiment program editor––A usage driven development

The set-up of experiment programs for the complex fusion device Wendelstein 7-X has to define a multitude of parameters which have to obey large number of rules arising from physics and technical constraints. Since this is hard to automate as long as the dependencies are not known sufficiently, the W7-X CoDaC team decided to implement an editor following a constructive approach: starting from an established experiment program the user is able to modify parts of it – thus complying the usual workflow of experimenters.Already the very first implementation has been deployed at the W7-X CoDaC prototype, the WEGA stellarator. Driven by agile programming principles the weighting of the requirements has been influenced by the editor usage in the daily experiment routine, thus ensuring client-oriented development steps and short release cycles. At present, a stable program editor implementation with graphical preview, immediate feedback on user actions and instantaneous warnings about incorrect settings is under continuous operation at the CoDaC prototype. It has potential to improve together with growing knowledge about the physical and technical constraints. The experiences gained give certainty that the editor is suitable for future use during the start-up phase and the first years of W7-X operation.     

Huge increase of therapeutic window at a bioactive silver/titania nanocomposite coating surface compared to solution

A silver containing coating used in the human body, e.g., on an implant should be both effectively antimicrobial and non-cytotoxic to human cells. It is generally believed that the biologic effect originates from silver ions released from the coating. Nanocomposites with well controlled Ag filling factor were prepared by co-sputtering, and the silver surface concentration and the silver release were determined by XPS and ICP-MS, respectively. Here we show that only a small therapeutic window exists for dissolved silver but the therapeutic window is largely increased at the surface. While the toxicity observed for mammalian cells in contact with the bioactive Ag/TiO₂ nanocomposite surface and for silver ions in solution is rather similar the antimicrobial activity is drastically enhanced at the surface. A model is proposed to explain the strong increase of the antimicrobial activity at the surface. The present results not only question well-established tests for antimicrobial activity but they are also important for the design of antimicrobial coatings, e.g., for biomedical devices.