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61.
Patricia Dähmlow Torsten Trittel Kathrin May Kirsten Harth Ralf Stannarius 《Liquid crystals》2018,45(7):993-1003
Elongated freely floating smectic bubbles are observed during their relaxation to equilibrium sphere shape. Unlike soap bubbles that perform weakly damped oscillations into equilibrium, this relaxation is overdamped in smectics by internal structure reorganisation processes. The bubble area reduction of centimetre-sized freely floating bubbles with few nanometres film thickness is recorded with high-speed optical imaging in microgravity and analysed quantitatively. We find a nearly linear reduction of the film area with time, driven by capillary forces and inhibited by smectic layer reorganisations. Characteristic times are in the milliseconds range, with little correlation to the film thickness and bubble size. Instead, the homogeneity of the films and the number and sizes of islands of excess layers that spontaneously form on the films appear to have crucial influence on the dynamics. The efficiency of this process sets the time scale of the film area shrinkage. We discuss the limitations of a minimalistic model that captures smectic layer reorganisation processes. 相似文献
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We propose an approach to the data-driven newsvendor problem that incorporates a correction factor to account for rare events, when the decision-maker has few historical data points at his disposal but knows the range of the demand. This mitigates a weakness of pure data-driven methodologies, specifically, the fact that they under-protect the system against tail events, which are in general under-observed in the empirical demand distribution. We test the approach in extensive computational experiments and provide a summary table of the numerical experiments to help the decision maker gain further insights. 相似文献
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Oliver Wuerfel Markus Greule Frank Keppler Maik A. Jochmann Torsten C. Schmidt 《Analytical and bioanalytical chemistry》2013,405(9):2833-2841
In the environment, the methylation of metal(loid)s is a widespread phenomenon, which enhances both biomobility as well as mostly the toxicity of the precursory metal(loid)s. Different reaction mechanisms have been proposed for arsenic, but not really proven yet. Here, carbon isotope analysis can foster our understanding of these processes, as the extent of the isotopic fractionation allows to differentiate between different types of reaction, such as concerted (SN2) or stepwise nucleophilic substitution (SN1) as well as to determine the origin of the methyl group. However, for the determination of the kinetic isotope effect the initial isotopic value of the transferred methyl group has to be determined. To that end, we used hydroiodic acid for abstraction of the methyl group from methylcobalamin (CH3Cob) or S-adenosyl methionine (SAM) and subsequent analysis of the formed methyl iodide by gas chromatography (GC) isotope ratio mass spectrometry (IRMS). In addition, three further independent methods have been investigated to determine the position-specific δ 13C value of CH3Cob involving photolytic cleavage with different additives or thermolytic cleavage of the methyl-cobalt bonding and subsequent measurement of the formed methane by GC-IRMS. The thermolytic cleavage gave comparable results as the abstraction using HI. In contrast, photolysis led to an isotopic fractionation of about 7 to 9 ‰. Furthermore, we extended a recently developed method for the determination of carbon isotope ratios of organometal(loid)s in complex matrices using hydride generation for volatilization and matrix separation before heart-cut GC and IRMS to the analysis of the low boiling partly methylated arsenicals, which are formed in the course of arsenic methylation. Finally, we demonstrated the applicability of this methodology by investigation of carbon fractionation due to the methyl transfer from CH3Cob to arsenic induced by glutathione.
Position-specific isotope analysis of the methyl group in CH3Cob by abstraction using HI and subsequent analysis of formed CH3I by GC-IRMS 相似文献
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2D difference gel electrophoresis reference map of a Fusarium graminearum nivalenol producing strain
Matias Pasquali Tommaso Serchi Jenny Renaut Lucien Hoffmann Torsten Bohn 《Electrophoresis》2013,34(4):505-509
Fusarium graminearum is widely studied as a model for toxin production among plant pathogenic fungi. A 2D DIGE reference map for the nivalenol‐producing strain 453 was established. Based on a whole protein extract, all reproducible spots were systematically picked and analyzed by MALDI‐TOF/TOF, leading to the identification of 1102 protein species. The obtained map contributes to the annotation of the genome by identifying previously nondescribed hypothetical proteins and will serve as a reference for future studies aiming at deciphering F. graminearum biology and chemotype diversity. 相似文献
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Torsten Kerber Rachel Nathaniel Kerber Xavier Rozanska Philippe Sautet Paul Fleurat‐Lessard 《Journal of computational chemistry》2013,34(13):1155-1163
We present a new software to easily perform QM:MM and QM:QM' calculations called QMX. It follows the subtraction scheme and it is implemented in the Atomic Simulation Environment (ASE). Special attention is paid to couple molecular calculations with periodic boundaries approaches. QMX inherits the flexibility and versatility of the ASE package: any combination of methods namely force field, semiempirical, first principle, and ab initio, can be used as hybrid potential energy surface (PES). Its ease of use is demonstrated by considering the adsorption of Al2Cl3Me3 on silica surface and by combining different levels of theory (from standard DFT to MP2 calculations) for the so‐called High Level cluster with standard PW91 density functional theory calculations for the Low Level environment. It is shown that the High Level cluster must contain the silanol group close to the aluminum atoms. The bridging adsorption is favored by 58 kJ mol?1 at the MP2:PW91 level with respect to the terminal position. Using large clusters at the MP2:PW91 level, it is shown that PW91 calculations are sufficient for structure optimization but that embedded methods are required for accurate energy profiles. © 2013 Wiley Periodicals, Inc. 相似文献
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The evaluation of a fully automated quantitative proton nuclear magnetic resonance spectroscopy (qNMR) processing program, including the determination of its processing uncertainty, and the calculations of the combined uncertainty of the qNMR result, is presented with details on the use of a trimmed purity average. Quantitative NMR spectra (1359) were collected over a 4-month period on various concentrations of pseudoephedrine HCl dissolved in D2O (0.0610 to 93.60 mg/mL) containing maleic acid (the internal standard) to yield signal-to-noise ratios ranging from 3 to 72,000 for analyte integral regions. The resulting 5436 purities exhibited a normal distribution about the best estimate of the true value. The median absolute deviation (MAD) statistical method was used to obtain a model of uncertainty relative to the signal-to-noise of the analyte’s integral peaks. The model was then tested using different concentrations of known purity chloroquine diphosphate. qNMR results of numerous illicit heroin HCl samples were compared to those obtained by capillary electrophoresis. Graphical Abstract
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