Die Massenspektren der Pyrrolidide einiger aliphatisch-alicyclischer Carbonsäuren

The mass spectra of the pyrrolidides of some long-chain carboxylic acids with alicyclic residues attached to their ω-end are discussed and compared with the spectra of the corresponding esters. Fragmentation triggered by the pyrrolidide group generates a series of peaks, which clearly exhibits the size and the structure of the carbon chain.     

Polarographie schwefelhaltiger Proteine

Zusammenfassung An kristallisierten Enzymen des biologischen Stoffwechsel wird gezeigt, daß bei der Polarographie nur die schwefelhaltigen Proteine katalytische Wasserstoffwellen geben. Von den in der Literatur beschriebenen Doppelstufen der Proteine besitzt nur die im negativeren Potentialbereich liegende Welle die eigentliche katalytische Funktion. Die erste Vorwelle von Proteinen verschwindet, wenn die polarographische Messung bei 0° C durchgeführt wird.In Proteinen sind nur Disulfidgruppen katalytisch wirksam. Sogenannte reine Sulfhydryl-Enzyme haben keinen katalytischen Effekt. Typische SH-Enzyme können jedoch polarographisch als p-Chloromercuribenzoatkomplexe gemessen werden.Durch Harnstoffzusatz bei der polarographischen Messung von Proteinen gelingt es, zwischen maskierten und freien Sulfhydryl- oder Disulfidgruppen an Enzymen zu definieren.Auszug aus der Dissertationsschrift H. Katzlmeier, Technische Hochschule München (1959).     

31P- und 195Pt-NMR-Untersuchungen an Diplatin(I)-Komplexen des Typs [Pt2(μ-SPR2)2L2] (L = PR3, PhP(OPh)2, P(OPh)3, CNR)

³¹P and ¹⁹⁵Pt N.M.R. Investigations on Diplatinum (I) Complexes of the Type [Pt₂(μ-SPR₂)₂L₂] (L = PR₃, PhP(OPh)₂, P(OPh)₃, CNR) ³¹P-, ¹⁹⁵Pt-chemical shifts and ¹⁹⁵Pt–³¹P- resp. ³¹P–³¹P-coupling constants of a series of doubly bridged diplatinum(I) complexes are reported. ³¹P-coordination chemical shifts of the terminal ligands of complexes of type [Pt₂(μ-SPR₂)₂(P′R₃′)₂] and some of the various coupling constants are strongly influenced by the π-acceptor strength of these ligands. J(¹⁹⁵Pt–¹⁹⁵Pt) is found to change the sign among the series of complexes investigated. Thermal singlett triplet exitation giving rise to the paramagnetism of these complexes observed by preliminary EPR-measurements and confirmed by EHT-calculations is deduced from the large values of ²J(P–P′) and ³J(P′P′) as well as the unusually high temperature dependence of some coupling constants and other NMR features. The chemical stability of the doubly bridged core, the coordination shifts of the bridging phosphorus atoms and EHT-calculations suggest a view of aromaticity of the [Pt₂(μ-SPR₂)₂](M–M) unit of these complexes.     

Influence of Test Specimen Geometry and Water Soaking on the In Vitro Cytotoxicity of Orthocryl®, Orthocryl® LC,Loctite® EA 9483 and Polypropylene

Depending on their composition, plastics have a cytotoxic potential that needs to be evaluated before they are used in dentistry, e.g., as orthodontic removable appliances. Relevant guidelines set out requirements that a potential new resin in the medical field must meet, with a wide scope for experimental design. In the present study, test specimens of different geometries consisting of varying polymers (Orthocryl^®, Orthocryl^® LC, Loctite^® EA 9483, Polypropylene) were soaked for different periods of time, then transferred to cell culture medium for 24 h, which was subsequently used for 24-h cultivation of A549 cells, followed by cytotoxicity assays (WST-1, Annexin V-FITC-propidium iodide (PI) flow cytometry). In this context, a reduction in the cytotoxic effect of the eluates of test specimens prepared from Orthocryl^® LC and Loctite^® EA 9483 was particularly evident in the Annexin V-FITC-PI assay when the soaking time was extended to 48 h and 168 h, respectively. Consistent with this, a reduced release of potentially toxic monomers into the cell culture medium, as measured by gas chromatography-mass spectrometry, was observed when the prior soaking time of test specimens of all geometries was extended. Remarkably, a significant increase in cytotoxic effect was observed in the WST-1 assay, which was accompanied by a higher release of monomers when the thickness of the test sample was increased from 0.5 to 1.0 mm, although an elution volume adapted to the surface area was used. However, further increasing the thickness to 3.0 mm did not lead to an increase in the observed cytotoxicity or monomer release. Test specimens made of polypropylene showed no toxicity under all test specimen sizes and soaking time conditions. Overall, it is recommended to perform toxicity studies of test specimens using different geometries and soaking times. Thereby, the influence of the different specimen thicknesses should also be considered. Finally, an extension of the test protocols proposed in ISO 10993-5:2009 should be considered, e.g., by flow cytometry or monomer analysis as well as fixed soaking times.     

Parallel simulation of large scale multibody systems

Virtual prototyping plays an ever increasing role in the engineering disciplines. Nowadays, engineers can rely on powerful tools like object oriented modeling languages, e.g., Modelica. Models written in this language can be simulated by open source software as well as commercial tools. The advantage of this approach is that the engineers can concentrate themselves on modeling, whereas the numerical intricacies of the simulation are handled by the software. On the other hand the simulations are usually slower than implementations which are parallelized and optimized manually. This can lead to computation times which are infeasible in practice, e.g., when a real time simulation is necessary for a hardware-in-the-loop simulation. In this contribution we are concerned with speeding up such automated simulations by parallelization (on desktop hardware as well as HPC systems). We examine the parallelism across the system approaches. Additionally, the influence of the problem formulation on the simulation time is discussed. The implemented methods are demonstrated on engineering examples. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Dynamic light scattering method of polymer solutions

The main features of dynamic light scattering are briefly outlined. The capability of this method to characterizing molar mass distributions and to distinguishing different molecular architectures is demonstrated with some examples. Special attention is given to the question of internal mobility and the spectrum of relaxation times. Recent results on asymptotic behavior are presented and discussed. Scaling behavior of the first cumulant with respect of space and of the time correlation function with respect of time (shape function) is found. All examples studied so far demonstrate the dynamic scaling of Zimm-Rouse chains, but the prefactors strongly depend on branching and crosslinking.     

Texture investigations of Mn?Al magnets by neutron time-of-flight diffraction

In the present work the connection between magnetic properties and texture of two samples of the tetragonal Mn Al phase is investigated. The specimens have been prepared by different cold deformation methods to get various texture types. For texture analysis neutron time-of-flight technique has been applied. Some aspects of the mathematical treatment of experimental data has been discussed. The main texture components in the inverse pole figures are inclined with respect to the direction of easy magnetization. Therefore, improved magnetic properties of the material can be expected using more optimal preparation techniques.