排序方式: 共有17条查询结果,搜索用时 9 毫秒
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Strong cation exchange (SCX)-type chiral stationary phases (CSPs) based on beta-amino sulfonic acid-terminated dipeptide derivatives as chiral selectors, immobilized on thiol-modified silica particles (3.5 microm), were synthesized and applied to enantiomer separations of chiral bases by nonaqueous capillary electrochromatography (CEC). The effect of structural variations of the sulfodipeptide selectors on the separation factors alpha was investigated. These studies included variation of the acid-terminal amino sulfonic acid residue, variation of the configurations, i.e., comparison of the diastereomeric (S,S)- and (R,S)-configurations of the sulfodipeptides, and finally comparison of sulfodipeptide selectors with corresponding beta-amino sulfonic acid analogs. In general, the capillary columns (100 microm ID) packed with the new SCX-type CSPs showed enantioselectivity for an elaborated set of chiral basic drugs in CEC acting by an enantioselective cation-exchange retention mechanism. N-[N-(4-Allyloxy-3,5-dichlorobenzoyl)-leucyl]-2-amino-3,3-dimethylbutane sulfonic acid, in particular with (R,S)-configuration, turned out to be a more effective SCX-type selector than a more rigid analog based on N-[N-(4-Allyloxy-3,5-dichlorobenzoyl)-leucyl]-2-pyrrolidinemethane sulfonic acid. Both of the former diastereomers were capable to baseline-resolve the enantiomers of ca. 40% of the tested basic chiral solutes including sympathomimetics and beta-blockers, while for the latter SCX-type CSPs only 10-20% of the selected solutes afforded resolutions > 1.5. 相似文献
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Nonperturbative electron-positron pair creation (the Schwinger effect) is studied based on the Dirac-Heisenberg-Wigner formalism in 1+1 dimensions. An ab initio calculation of the Schwinger effect in the presence of a simple space- and time-dependent electric field pulse is performed for the first time, allowing for the calculation of the time evolution of observable quantities such as the charge density, the particle number density or the total number of created particles. We predict a new self-bunching effect of charges in phase space due to the spatial and temporal structure of the pulse. 相似文献
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Hebenstreit W Schmid M Redinger J Podloucky R Varga P 《Physical review letters》2000,85(25):5376-5379
Atomically resolved scanning tunneling microscopy reveals the existence of triangular (111) bulk terminated NaCl islands. The islands can be grown by subsequent adsorption of Na and Cl2 on Al(111) and Al(100) or by conversion of stoichiometric NaCl(100) islands to NaCl(111) via additional Na adsorption. The NaCl(111) islands have Na-Cl-Na sandwich structure. Ab initio calculations of the electronic structure of these islands show that each of the Na atoms carries half a positive elementary charge, leaving the islands neutral and explaining the existence of an otherwise unstable surface. 相似文献
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Ketteler G Ogletree DF Bluhm H Liu H Hebenstreit EL Salmeron M 《Journal of the American Chemical Society》2005,127(51):18269-18273
Using a photoemission spectroscometer that operates close to ambient conditions of pressure and temperature we have determined the Pd-O phase diagram and the kinetic parameters of phase transformations. We found that on the (111) surface oxidation proceeds by formation of stable and metastable structures. As the chemical potential of O2 increases chemisorbed oxygen forms followed by a thin surface oxide. Bulk oxidation is a two-step process that starts with the metastable growth of the surface oxide into the bulk, followed by a first-order transformation to PdO. 相似文献
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This study reports on the development and preliminary validation of a capillary electrochromatographic (CEC) method for the enantioselective impurity profiling of D-ephedrine. As chiral selector a novel low-molecular-weight strong chiral cation exchanger, based on penicillamine sulfonic acid, immobilized on thiol-modified silica particles (3.5 microm) was employed. Under optimized conditions, the ephedrine enantiomers were separated on this chiral stationary phase (CSP) with an enantioselectivity of 1.11, an average efficiency of 321 550 plates per meter, and a resolution value of 4.77. A preliminary method validation was carried out to demonstrate the applicability of CEC for enantiomeric excess (ee) determination. Run-to-run repeatabilities (n = 5) reached relative standard deviation values (RSD) of 0.18 and 0.19% for the migration times of L- and D-enantiomer, respectively, 0.3% for the resolution, and about 0.9% for the peak efficiencies. An approach called self-internal standard method was utilized to measure a standard calibration curve. Excellent linearity with a correlation coefficient of R(2) = 0.9998 was found for samples with concentrations in the range between 0.03 and 5 mg.mL(-1) D-ephedrine spiked with L-ephedrine at a constant concentration of 0.2 mg.mL(-1). The high loadability of the investigated CSP and good peak sensitivity allowed us to determine less than 0.1% enantiomeric impurity with good accuracy. The limit of detection (LOD) for the L-enantiomer in a 3 mg.mL(-1) D-ephedrine solution was found to be 0.035% (S/N = 3) and the limit of quantitation (LOQ) 0.058% (S/N = 5). For L-ephedrine samples the strong cation-exchange (SCX)-type CSP with opposite configuration was utilized so that the enantiomeric impurity eluted before the main component peak yielding similar results in terms of separation and validation. Based on these results, the presented nonaqueous CEC methods are assessed as principally suitable for ee determination of ephedrine in terms of repeatability and method sensitivity. 相似文献
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Klein C Eichler A Hebenstreit EL Pauer G Koller R Winkler A Schmid M Varga P 《Physical review letters》2003,90(17):176101
At low tunneling resistance, scanning tunneling microscopy (STM) images of a Rh(100) surface with adsorbed hydrogen reproducibly show protrusions in all bridge sites of the surface, leading to a naive interpretation of all bridge sites being occupied with H atoms. Using quantitative low-energy electron diffraction and temperature programmed desorption we find a much lower H coverage, with most H atoms in fourfold hollow sites. Density functional theory calculations show that the STM result is due to the influence of the tip, attracting the mobile H atoms into bridge sites. This demonstrates that STM images of highly mobile adsorbates can be strongly misleading and underlines the importance of additional analysis techniques. 相似文献
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Scanning tunnelling microscopy (STM) was used to study the (1 1 0) surface of a VC0.8 sample. The surface shows a missing-row reconstruction, i.e., a grating structure with ridges and valleys oriented along the [0 0 1] direction and (1 0 0) and (0 1 0) facets. We did not find unreconstructed (1 1 0) terraces. The regular spacing of the ridges corresponds to a periodicity of (3 × 1) or (4 × 1), depending on preparation, presumably related to different concentrations of carbon vacancies. In the STM images, we can also observe apparent pairing of atoms in the rows, leading to the larger c(6 × 2) and (4 × 2) superstructure cells, which also show up in LEED. We attribute these additional periodicities to ordering of carbon vacancies in the surface rows. 相似文献