Pyrolysis-field ionization mass spectrometry of polyamide copolymers and blends

Nylon foils of PA 6, PA 66, PA 69, PA 12, the copolymer PA 666, and nine blends based on these polymides have been investigated by in-source pyrolysis (Py)–field ionization mass spectrometry (FIMS). These polymers and blends can be distinguished by characteristic molecular ions of oligomers, protonated amines and nitriles, and products terminated by olefinic end groups. Series of ions are formed differing in the number of additional monomeric units. Thus, polymers containing different chemical subunits were easily distinguished from each other in the spectra of the blends. Mass signals, only expected for copolymers, were found in the integrated blend spectra, indicating that amide exchange reactions occur under the experimental conditions employed. This observation was confirmed by pyrolysis of mixtures of pure polymers in the same crucible and under the same experimental conditions. Hence, the distinction by Py–MS alone between blends and copolymers with an identical averaged number of identical chemical subunits is not possible.     

Synthesis of 9,12-Dioxo-10(Z)-dodecenoic acid, a new fatty acid metabolite derived from 9-hydroperoxy-10,12-octadecadienoic acid in lentil seed (Lens culinaris medik.)

The previously unknown linoleic acid peroxidation product 9,12-dioxo-10(Z)-decenoic acid (Z5) was detected in lentil seed fluor (Lens culinaris Medik.) by electron impact mass spectrometry (El-MS) after derivatization with pentafluorobenzyl-hydroxylamine-hydrochloride, methylation of acidic groups with diazomethane, and protection of hydroxylic groups with N-methyl-N-trimethylsilyl-trifluoroacetamide. The structure of the natural product was confirmed by synthesis of Z5, 9,12-dioxo-10(E)-decenoic acid, and derivatives. EI-MS, nuclear magnetic resonance and gas chromatographic data of these compounds and synthetic intermediates are discussed.     

Results of an inter-laboratory comparison of methods for quantitative clay analysis

In a comparison of analytical methods in clay mineralogy, two clay samples (from Hennersdorf and Freydegg) of different clay composition were analyzed by 19 laboratories mainly by XRD. Participants used different methods of pre-treatment, preparation, analysis and evaluation.In spite of the diversity of analytical methods applied, reasonable conformity in quantitative results was obtained for the associated minerals (quartz, calcite and dolomite). On the other hand, qualitative identification of the clay minerals showed considerably stronger divergencies, causing a stronger deviation of quantitative data; analysis of the Freydegg sample proved to have been particularly difficult. The evaluation methods of the different participants were examined to determine whether similar methods provided results that could be more easily compared.In addition, the authors calculated the clay mineral composition according to three different recognized methods, using the same diffractograms and same preparation and measuring conditions. In spite of this, different results were obtained.In the next phase of the programme, an inter-laboratory comparison of methods will be achieved under exactly defined conditions of preparation and analysis.     

A Highly Potent and Cellularly Active β‐Peptidic Inhibitor of the p53/hDM2 Interaction

New and improved : The incorporation of a 6‐chlorotryptophan (6‐Cl‐Trp) into a β‐peptide (M)‐3₁₄ helix leads to a high‐affinity hDM2 inhibitor, as demonstrated by fluorescence fluctuation analysis at single molecule resolution. When conjugated to penetratin, the newly derived hDM2 binder specifically inhibits tumour cell growth in vitro.

     

An efficient method for solving the Signorini problem in the simulation of free-form surfaces produced by belt grinding

Industrial robots are recently introduced to the belt grinding of free-form surfaces to obtain high productive efficiency and constant surface quality. The simulation of belt grinding process can facilitate planning grinding paths and writing robotic programs before manufacturing. In simulation, it is crucial to get the force distribution in the contact area between the workpiece and the elastic contact wheel because the uneven distributed local forces are the main reason to the unequal local removals on the grated surface. The traditional way is to simplify this contact problem as a Signorini contact problem and use the finite element method (FEM) to calculate the force distribution. However, the FEM model is too computationally expensive to meet the real-time requirement. A new model based on support vector regression (SVR) technique is developed in this paper to calculate the force distribution instead of the FEM model. The new model approximates the FEM model with an error smaller than 5%, but executes much faster (1 s vs 15 min by FEM). With this new model, the real-time simulation and even the on-line robot control of grinding processes can be further conducted.     

Mg-bearing quartz solid solutions as structural intermediates between low and high quartz

Glass powder samples of cordierite composition (doped with 8 mol% TiO₂) were heat-treated to produce a series of increasingly SiO₂-enriched Mg-bearing quartz solid solutions (Qss). The obtained materials were then analyzed by X-ray diffraction: Rietveld structural refinements revealed that Mg-bearing Qss phases possess trigonal symmetry and a compositionally dependent intermediate structural arrangement between those of low and high quartz. High-temperature diffraction measurements were performed up to 700°C to characterize the thermal expansion behavior of the crystals. At SiO₂-rich compositions, a reversible high-to-intermediate inversion of the quartz structure is observed, which shifts with increasing stuffing to lower temperatures than the conventional 573°C for pure quartz. Similarities and differences to the better-established Li-bearing Qss are discussed in the text.