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The first total synthesis of the marine steroid alkaloid plakinamine B (1) was accomplished in seven steps starting from known aldehyde 3. Key steps in this synthesis are the attachment of a vinylpyridine side chain by an aldol reaction, a chemoselective reduction of a pyridinium salt to a vinyl tetrahydropyridine, and the introduction of the 3α-methylamino group under Mitsunobu conditions. Plakinamine B and some of its precursors with amino or pyridinium side chains show significant antimicrobial activities. 相似文献
224.
Chang Jong Kim Markus Mazurowski Katrin Sondergeld Markus Gallei Matthias Rehahn 《Soft Materials》2014,12(4):S41-S48
We previously reported that grafted polystyrene (PS) chains on silica nanoparticles at a low grafting density show similar conformations to free PS chains in the same solvent, THF (diameter ?50 nm, Colloid.poly.Sci. (2013), 291, 9, 2087–2099). As an extension of our previous study we choose an organic nanoparticle (deuterated polystyrene, dPS) instead of inorganic nanoparticle to see the impact of the substrate material on chain conformation. Additionally, a wider range of molecular weights were prepared to investigate the conformation feature of grafted PS chains more in detail. Small angle neutron scattering (SANS) experiments were performed to characterize PS grafted dPS particles in good solvent condition, with deuterated toluene and deuterated THF as solvent. To get insight into the conformation of the grafted PS layer we apply a scaling law describing the dimension of free PS polymer in good solvent condition to the obtained thickness of the grafted PS layer. We find an overall agreement with the scaling law where the thickness of the grafted PS layer is slightly larger than 2Rg of the free polymer chains in the respective solvent giving hint for semi dilute polymer brush (SDPB) situation. 相似文献
225.
Markus R. Meyer Carina Lindauer Jessica Welter Hans H. Maurer 《Analytical and bioanalytical chemistry》2014,406(7):1845-1854
Dimethocaine (DMC, larocaine), a synthetic derivative of cocaine, is a widely distributed “legal high” consumed as a “new psychoactive substance” (NPS) without any safety testing, for example studies of metabolism. Therefore, the purpose of this work was to study its in-vivo and in-vitro metabolism by use of liquid chromatography–(high resolution) mass spectrometry (LC–HRMS n ). DMC was administered to male Wistar rats (20 mg kg?1) and their urine was extracted either by solid-phase extraction after enzymatic cleavage of conjugates or by use of protein precipitation (PP). The metabolites were separated and identified by LC–HRMS n . The main phase I reactions were ester hydrolysis, deethylation, hydroxylation of the aromatic system, and a combination of these. The main phase II reaction was N-acetylation of the p-aminobenzoic acid part of the unchanged parent compound and of several phase I metabolites. The metabolites identified were then used for identification of DMC in rat urine after application of a common user’s dose. By use of GC–MS and LC–MS n standard urine-screening approaches (SUSAs), DMC and its metabolites could be detected in the urine samples. 相似文献
226.
Jessica Welter Markus R. Meyer Pierce Kavanagh Hans H. Maurer 《Analytical and bioanalytical chemistry》2014,406(7):1957-1974
4-Methyl-amphetamine (1-(4-methylphenyl)propane-2-amine; 4-MA) and its isomers 2-methyl-amphetamine (2-MA) and 3-methyl-amphetamine (3-MA) belong to the group of amphetamine-type stimulants and of new psychoactive substances. Several studies showed similar potencies in releasing noradrenalin and dopamine, but higher potencies in releasing serotonin than amphetamine. In March 2013, the EU Council decided on an EU-wide control based on the European Monitoring Centre for Drugs and Drug Addiction risk assessment report documenting that 4-MA was sold as amphetamine on the illicit market and detected in several fatal cases. Therefore, 4-MA and its isomers should be covered by drug testing in clinical and forensic toxicology. The aims of the presented work were to study the metabolism and detectability of each isomer in urine samples. For metabolism studies, rat urine samples were isolated by solid-phase extraction without and after enzymatic cleavage of conjugates. The phase I metabolites were separated and identified after acetylation by gas chromatography–mass spectrometry (GC-MS) and/or liquid chromatography–high resolution-linear ion trap mass spectrometry (LC-HR-MS n ) and the phase II metabolites by LC-HR-MS n . From the identified phase I and II metabolites, the following main metabolic pathways were deduced: aromatic hydroxylation, hydroxylation of the phenylmethyl group followed by oxidation to the corresponding carboxylic acid, hydroxylation of the side chain, and glucuronidation and/or sulfation of the hydroxy and carboxy groups. CYP2D6 was involved in the aromatic hydroxylation. Finally, the intake of a commonly used dose of the MAs could be confirmed in rat urine using the authors’ GC-MS and the LC-MS n standard urine screening approaches. Differentiation of the isomers to confirm the intake of a specific isomer was possible with an additional workup in rat urine. 相似文献
227.
Bhaskar R. Aluri Mohammed Ghalib Markus K. Kindermann Peter G. Jones Joachim W. Heinicke 《Heteroatom Chemistry》2015,26(6):426-435
The reactivity of tBuLi (pentane) toward the N‐neopentyl‐substituted π‐excess P=CH–N heterocycle 1 depends on the solvent (tetrahydrofuran, diethyl ether, hexane, and toluene) and reaction conditions. Trapping of the resulting organolithium compounds with CO2/ClSiMe3, ClSiMe3, or EtI led to various products indicating CH lithiation ( 1a , b ), normal addition of tBuLi at the P=C bond (E/Z ‐2a , b ), inverse addition of the primary addition product 2Li at the P=C bond of a second molecule 1 , affording 3‐tert‐butyl‐2,2’‐bis(1,3‐benzazaphospholines) 3 , or inverse addition of tBuLi ( 4b,c ). The formation of 3 demonstrates a novel route to asymmetric heterocyclic 1,2‐diphosphine ligands. The structure elucidation of the new compounds is based on their 31P and 13C NMR data with conclusive chemical shifts and P–C coupling constants, that of the isolated PH‐functionalized diphosphine 3 on crystal structure analysis. 相似文献
228.
Andreas Braeuer Robert Fabian Hankel Markus Konstantin Mehnert Julian Jonathan Schuster Stefan Will 《Journal of Raman spectroscopy : JRS》2015,46(11):1145-1149
We report a Raman technique applicable for the in situ analysis of the development of hydrogen bonds in the liquid water‐rich phase just before the onset of gas hydrate formation. Herewith, the phase transition as well as the working principle of hydrate formation inhibitors and promoters can be analyzed. © 2015 The Authors. Journal of Raman Spectroscopy published by John Wiley & Sons Ltd. 相似文献
229.
The self-reproduction ability of mitotic cells results in an increase of the number of cells with the same characteristics in living bodies. While cells grow in volume and divide themselves, the living body consequently grows in mass and volume. Further, if the factors which regulate the growth process are inhomogeneously distributed, growth takes place at different rates and directions. In this work we aim to provide a new continuum model for growing tissues. More specifically, the model considers the reorientation of the cell-division plane in mitotic cells depending on the stress field of the growing body. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
230.
The complexity of technical products increases significantly, due to an increasing number of interacting design variables of many components and subsystems. At the same time, the need for separated development processes is increasing due to specialization and outsourcing. Solution space methods are designed to solve this conflict. The requirements from an upper level, e.g. performance measures of the whole system, can be cascaded down to requirements on a lower level, e.g. performance measures of the subsystems or components, as it is done in the V-model approach. The method does not only take the numerous interactions into account but also guarantees the resulting intervals of different parameters to be independent of each other. Unfortunately, the computational cost of the state-of-the-art stochastic approach is high. The approach in this paper shows that the computational effort can be reduced considerably using a gradient based optimization approach for constraint problems. We demonstrate that the approach reduces the required number of function evaluations for a chassis design problem by a factor of 30, but more important, the CPU time for solving the problem by a factor of 20. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献