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51.
Stephan Brox Axel P. Ritter Eberhard Küster Thorsten Reemtsma 《Analytical and bioanalytical chemistry》2014,406(20):4831-4840
An analytical method using high-performance liquid chromatography–tandem mass spectrometry was developed to determine internal concentrations of 34 test compounds such as pharmaceuticals and pesticides in zebrafish embryos (ZFE), among them, cimetidine, 2,4-dichlorophenoxyacetic acid, metoprolol, atropine and phenytoin. For qualification and quantification, multiple reaction monitoring mode was used. The linear range extends from 0.075 ng/mL for thiacloprid and metazachlor and 7.5 ng/mL for coniine and clofibrate to 250 ng/mL for many of the test compounds. Matrix effects were strongest for nicotine, but never exceeded ±20 % for any of the developmental stages of the ZFE. Method recoveries ranged from 90 to 110 % from an analysis of nine pooled ZFE. These findings together with the simple sample preparation mean this approach is suitable for the determination of internal concentrations from only nine individual ZFE in all life stages up to 96 h post-fertilization. Exemplarily, the time course of the internal concentrations of clofibric acid, metribuzin and benzocaine in ZFE was studied over 96 h, and three different patterns were distinguished, on the basis of the speed and extent of uptake and whether or not a steady state was reached. Decreasing internal concentrations may be due to metabolism in the ZFE. Figure
Quantification of polar pollutants in different life stages of the zebrafish embryo by LC-MS/MS 相似文献
52.
Motivated by the high potential of shape memory alloys (SMA) in several industrial applications, we investigate the material response under cyclic loading. In particular, the focus is set on the modelling of functional fatigue, which results in the deterioration of the specific features of SMA. In fact, functional fatigue restricts SMA in terms of its applicability for real structures and workpieces. This necessitates the development of material models which take this phenomenon into account. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
53.
Dennis Schnfeld Dilip Chalissery Franziska Wenz Marius Specht Chris Eberl Thorsten Pretsch 《Molecules (Basel, Switzerland)》2021,26(3)
For soft robotics and programmable metamaterials, novel approaches are required enabling the design of highly integrated thermoresponsive actuating systems. In the concept presented here, the necessary functional component was obtained by polymer syntheses. First, poly(1,10-decylene adipate) diol (PDA) with a number average molecular weight Mn of 3290 g·mol−1 was synthesized from 1,10-decanediol and adipic acid. Afterward, the PDA was brought to reaction with 4,4′-diphenylmethane diisocyanate and 1,4-butanediol. The resulting polyester urethane (PEU) was processed to the filament, and samples were additively manufactured by fused-filament fabrication. After thermomechanical treatment, the PEU reliably actuated under stress-free conditions by expanding on cooling and shrinking on heating with a maximum thermoreversible strain of 16.1%. Actuation stabilized at 12.2%, as verified in a measurement comprising 100 heating-cooling cycles. By adding an actuator element to a gripper system, a hen’s egg could be picked up, safely transported and deposited. Finally, one actuator element each was built into two types of unit cells for programmable materials, thus enabling the design of temperature-dependent behavior. The approaches are expected to open up new opportunities, e.g., in the fields of soft robotics and shape morphing. 相似文献
54.
Valerie Derpmann David Mueller Iustinian Bejan Hannah Sonderfeld Sonja Wilberscheid Ralf Koppmann Klaus J. Brockmann Thorsten Benter 《Journal of the American Society for Mass Spectrometry》2014,25(3):329-342
We report on a novel method for atmospheric pressure ionization of compounds with elevated electron affinity (e.g., nitroaromatic compounds) or gas phase acidity (e.g., phenols), respectively. The method is based on the generation of thermal electrons by the photo-electric effect, followed by electron capture of oxygen when air is the gas matrix yielding O2 – or of the analyte directly with nitrogen as matrix. Charge transfer or proton abstraction by O2 – leads to the ionization of the analytes. The interaction of UV-light with metals is a clean method for the generation of thermal electrons at atmospheric pressure. Furthermore, only negative ions are generated and neutral radical formation is minimized, in contrast to discharge- or dopant assisted methods. Ionization takes place inside the transfer capillary of the mass spectrometer leading to comparably short transfer times of ions to the high vacuum region of the mass spectrometer. This strongly reduces ion transformation processes, resulting in mass spectra that more closely relate to the neutral analyte distribution. cAPECI is thus a soft and selective ionization method with detection limits in the pptV range. In comparison to standard ionization methods (e.g., PTR), cAPECI is superior with respect to both selectivity and achievable detection limits. cAPECI demonstrates to be a promising ionization method for applications in relevant fields as, for example, explosives detection and atmospheric chemistry. Figure
? 相似文献
55.
The Origin of the Selectivity and Activity of Ruthenium‐Cluster Catalysts for Fuel‐Cell Feed‐Gas Purification: A Gas‐Phase Approach 下载免费PDF全文
Dr. Sandra M. Lang Prof. Dr. Thorsten M. Bernhardt Marjan Krstić Prof. Dr. Vlasta Bonačić‐Koutecký 《Angewandte Chemie (International ed. in English)》2014,53(21):5467-5471
Gas‐phase ruthenium clusters Run+ (n=2–6) are employed as model systems to discover the origin of the outstanding performance of supported sub‐nanometer ruthenium particles in the catalytic CO methanation reaction with relevance to the hydrogen feed‐gas purification for advanced fuel‐cell applications. Using ion‐trap mass spectrometry in conjunction with first‐principles density functional theory calculations three fundamental properties of these clusters are identified which determine the selectivity and catalytic activity: high reactivity toward CO in contrast to inertness in the reaction with CO2; promotion of cooperatively enhanced H2 coadsorption and dissociation on pre‐formed ruthenium carbonyl clusters, that is, no CO poisoning occurs; and the presence of Ru‐atom sites with a low number of metal–metal bonds, which are particularly active for H2 coadsorption and activation. Furthermore, comprehensive theoretical investigations provide mechanistic insight into the CO methanation reaction and discover a reaction route involving the formation of a formyl‐type intermediate. 相似文献
56.
Oxidizing Elemental Platinum with Oleum under Harsh Conditions: The Unique Tris(disulfato)platinate(IV) [Pt(S2O7)3]2− Anion 下载免费PDF全文
Jörn Bruns Prof. Dr. Thorsten Klüner Prof. Dr. Mathias S. Wickleder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(24):7222-7227
For the first time, direct oxidation of elemental platinum by a mineral acid to its tetravalent state was observed in course of the reaction of platinum with oleum (65 % SO3) in the presence of barium carbonate. The reaction has been carried out in torch‐sealed glass ampoules at 160 °C and gave yellow single crystals of Ba[Pt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 (triclinic, P$\bar 1$ , Z=2, a=992.05(2), b=1069.07(3), c=1114.22(3) pm, α=69.49(7), β=72.96(2), γ=72.93(1)°, V=1033.95(5) Å3). The structure of Ba[Pt(S2O7)3](H2SO4)0.5(H2S2O7)0.5 exhibits the unique tris‐(disulfato)‐platinate anion [Pt(S2O7)3]2? with three chelating disulfate groups coordinated to the platinum atom. Charge balance is achieved by the Ba2+ ions, which are coordinated by (S2O7)2? groups from the platinate complex and by disordered sulfuric acids and disulfuric acid molecules. Thermal decomposition of the bulk material revealed elemental platinum and barium sulfate as decomposition residual. 相似文献
57.
Dipl.‐Chem. Alexander Rupp Dr. Nataliya Roznyatovskaya Dr. Harald Scherer Dr. Witali Beichel Petra Klose Carola Sturm Dr. Anke Hoffmann Dr. Jens Tübke Prof. Dr. Thorsten Koslowski Prof. Dr. Ingo Krossing 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(31):9794-9804
Several, partly new, ionic liquids (ILs) containing imidazolium and ammonium cations as well as the medium‐sized [NTf2]? (0.230 nm3; Tf=CF3SO3?) and the large [Al(hfip)4]? (0.581 nm3; hfip=OC(H)(CF3)2) anions were synthesized and characterized. Their temperature‐dependent viscosities and conductivities between 25 and 80 °C showed typical Vogel–Fulcher–Tammann (VFT) behavior. Ion‐specific self‐diffusion constants were measured at room temperature by pulsed‐gradient stimulated‐echo (PGSTE) NMR experiments. In general, self‐diffusion constants of both cations and anions in [Al(hfip)4]?‐based ILs were higher than in [NTf2]?‐based ILs. Ionicities were calculated from self‐diffusion constants and measured bulk conductivities, and showed that [Al(hfip)4]?‐based ILs yield higher ionicities than their [NTf2]? analogues, the former of which reach values of virtually 100 % in some cases.From these observations it was concluded that [Al(hfip)4]?‐based ILs come close to systems without any interactions, and this hypothesis is underlined with a Hirshfeld analysis. Additionally, a robust, modified Marcus theory quantitatively accounted for the differences between the two anions and yielded a minimum of the activation energy for ion movement at an anion diameter of slightly greater than 1 nm, which fits almost perfectly the size of [Al(hfip)4]?. Shallow Coulomb potential wells are responsible for the high mobility of ILs with such anions. 相似文献
58.
Improving Site‐Directed RNA Editing In Vitro and in Cell Culture by Chemical Modification of the GuideRNA 下载免费PDF全文
Paul Vogel Marius F. Schneider Jacqueline Wettengel Dr. Thorsten Stafforst 《Angewandte Chemie (International ed. in English)》2014,53(24):6267-6271
Adenosine‐to‐inosine deamination can be re‐addressed to user‐defined mRNAs by applying phosphothioate/2′‐methoxy‐modified guideRNAs. Dense chemical modification of the guideRNA clearly improves performance of the covalent conjugates inside the living cell. Furthermore, careful positioning of a few modifications controls editing selectivity in vitro and was exploited for the challenging repair of the Factor 5 Leiden missense mutation. 相似文献
59.
Dr. José I. Urgel Dr. Marco Di Giovannantonio Kristjan Eimre Thorsten G. Lohr Dr. Junzhi Liu Shantanu Mishra Dr. Qiang Sun Amogh Kinikar Dr. Roland Widmer Samuel Stolz Max Bommert Dr. Reinhard Berger Dr. Pascal Ruffieux Dr. Carlo A. Pignedoli Prof. Dr. Klaus Müllen Prof. Dr. Xinliang Feng Prof. Dr. Roman Fasel 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(32):13383-13389
Cumulene compounds are notoriously difficult to prepare and study because their reactivity increases dramatically with the increasing number of consecutive double bonds. In this respect, the emerging field of on-surface synthesis provides exceptional opportunities because it relies on reactions on clean metal substrates under well-controlled ultrahigh-vacuum conditions. Here we report the on-surface synthesis of a polymer linked by cumulene-like bonds on a Au(111) surface via sequential thermally activated dehalogenative C−C coupling of a tribenzoazulene precursor equipped with two dibromomethylene groups. The structure and electronic properties of the resulting polymer with cumulene-like pentagon–pentagon and heptagon–heptagon connections have been investigated by means of scanning probe microscopy and spectroscopy methods and X-ray photoelectron spectroscopy, complemented by density functional theory calculations. Our results provide perspectives for the on-surface synthesis of cumulene-containing compounds, as well as protocols relevant to the stepwise fabrication of carbon–carbon bonds on surfaces. 相似文献
60.
Thorsten Bies Dr. Rudolf C. Hoffmann Dr. Matthias Stöter Dr. Adalbert Huber Prof. Dr. Jörg J. Schneider 《ChemistryOpen》2020,9(12):1251-1263
Aluminum pigments were coated with Fe2O3 and CuO by solution-based thermal decomposition of the urea nitrate compounds hexakisureairon(III)nitrate and tetrakisureacopper(II)nitrate. The deposition process was optimized to obtain homogeneously coated aluminum pigments. The growth of the surface coatings was controlled by investigation with scanning electron microscopy, energy dispersive X-ray spectroscopy and static light scattering as well as infrared, X-ray diffraction and thermogravimetric analysis. The iron precursor showed an incomplete decomposition in solution, incorporating traces of urea molecules inside the coatings while the copper precursor showed complete dissociation accompanied by in situ formation of amine complexes. The amount of organic residues resulting from ligand fragments in the final oxide coatings could be reduced to 22 % for the iron oxide and 12 % for the copper oxide by further temperature treatment in solution (259 °C). Colorimetric investigations of the obtained pigments revealed an excellent hiding power, outperforming the pigments used in current state-of-the-art formulations. 相似文献