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71.
72.
Rainer Koeck Martin Fischnaller Rania Bakry Richard Tessadri Guenther K. Bonn 《Analytical and bioanalytical chemistry》2014,406(24):5897-5907
Short-term polymerization or the so-called low-conversion polymerization was applied for the preparation of N-vinylcarbazole (NVC) and 1,4-divinylbenzene (DVB) monolithic capillary columns. The synthesis was carried out by thermally initiated free radical copolymerization under the influence of inert micro- (toluene) and macroporogen (1-decanol) and α,α′-azoisobutyronitrile (AIBN) as radical initiator. The morphological and porous properties were studied by scanning electron microscopy (SEM), nitrogen adsorption, and mercury intrusion porosimetry (MIP). The copolymerization process was studied by monomer conversion measurements. This approach led to increased porosity and specific surface area. A specific surface area above 400 m2/g of the monolith and a distinct bimodal pore size distribution were obtained. The chromatographic performance was determined in terms of theoretical plate heights and number of theoretical plates. The lowest plate height value was found to be 3.9 μm (corresponding to ≈256,000 plates per meter) applying methylparaben utilizing an 80 mm?×?0.2 mm i.d. monolithic capillary. The developed NVC/DVB monolithic supports showed high separation efficiency towards small molecules, which was exemplified applying reversed-phase (RP) separation of alkylbenzenes, beta-blockers, flavanoids, parabens, and phenones. The loading capacity was analyzed for isocratic separation of seven alkylbenzenes and was found to be up to 77 ng total mass of alkylbenzenes. Furthermore, a long-term stability test of 1,000 consecutive runs was performed and resulted in a maximum variance of 0.97, 0.85, and 0.16 % RSD for resolution, peak width at half height, and retention times, respectively. The material was proven to have a high permeability of 1.11E?14 m2, applying water as a mobile phase. 相似文献
73.
Shah Hussain Cornelia Pezzei Yüksel Güzel Matthias Rainer Christian W. Huck Günther K. Bonn 《Analytica chimica acta》2014
An efficient blood plasma clean-up method was developed, where methanol protein precipitation was applied, followed by zirconium silicate assisted exclusion of residual proteins. A strong binding of zirconium (IV) silicate to the proteins enabled the elimination of remaining proteins after solvent deproteinization through a rapid solid-phase extraction (SPE) procedure. Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI/TOF MS) was used for monitoring the proteins during clean-up practice applied to human plasma samples. The proteins were quantified by colorimetric detection using the bicinchoninic acid (BCA) assay. The presented analytical strategy resulted in the depletion of >99.6% proteins from human plasma samples. Furthermore, high-performance liquid chromatography hyphenated to diode-array and electrospray ionization mass spectrometric detection (HPLC–DAD/ESI MS) was applied for qualitative and quantitative analysis of the caffeoylquinic acids (CQAs) and their metabolites in human plasma. The procedure demonstrated high recoveries for the standard compounds spiked at different concentrations. Cynarin and chlorogenic acid were recovered in the range of 81–86% and 78–83%, respectively. Caffeic acid was extracted in the excess of 89–92%, while ferulic acid and dihydroxyhydrocinnamic acid showed a recovery of 87–91% and 92–95%, respectively. The method was partially validated in accordance with FDA-Industry Guidelines for Bioanalytical Method Validation (2001). The presented scheme improves the clean-up efficacy of the methanol deproteinization, significantly reduces the matrix effects and provides a great analytical tool for the isolation of small molecules from human plasma. 相似文献
74.
We study a classical stochastic optimal control problem with constraints and discounted payoff in an infinite horizon setting.
The main result of the present paper lies in the fact that this optimal control problem is shown to have the same value as
a linear optimization problem stated on some appropriate space of probability measures. This enables one to derive a dual
formulation that appears to be strongly connected to the notion of (viscosity sub) solution to a suitable Hamilton-Jacobi-Bellman
equation. We also discuss relation with long-time average problems. 相似文献
75.
This is a reprinting of a paper by Jerome Kristian and Rainer K. Sachs, first published in 1966, in which they proposed a
power-series scheme for reading out various parameters of the Universe directly from observations in a model-independent way.
The paper has been selected by the Editors of General Relativity and Gravitation for re-publication in the Golden Oldies series
of the journal. This republication is accompanied by an editorial note written by George Ellis and by a brief biography of
J. Kristian, compiled by A. Krasiński from internet sources. 相似文献
76.
This article presents a mathematical model describing flow of two fluid phases in a heterogeneous porous medium. The medium
contains disconnected inclusions embedded in the background material. The background material is characterized by higher value
of the non-wetting-phase entry pressure than the inclusions, which causes non-standard behavior of the medium at the macroscopic
scale. During the displacement of the non-wetting fluid by the wetting one, some portions of the non-wetting fluid become
trapped in the inclusions. On the other hand, if the medium is initially saturated with the wetting phase, it starts to drain
only after the capillary pressure exceeds the entry pressure of the background material. These effects cannot be represented
by standard upscaling approaches based on the assumption of local equilibrium of the capillary pressure. We propose a relevant
modification of the upscaled model obtained by asymptotic homogenization. The modification concerns the form of flow equations
and the calculation of the effective hydraulic functions. This approach is illustrated with two numerical examples concerning
oil–water and CO2–brine flow, respectively. 相似文献
77.
William P. Clark Andreas Khn Rainer Niewa 《Angewandte Chemie (International ed. in English)》2020,59(1):339-342
The first quasi‐binary acetonitriletriide Sr3[C2N]2 has been synthesised and characterised. The nearly colourless crystals were obtained from the reaction of Sr metal, graphite, and elemental N2, generated by decomposition of Sr(N3)2, in a sealed Ni ampoule with the aid of an alkali metal flux. The structure of this compound was analysed via single‐crystal X‐ray diffraction and the identity of the [C2N]3? anion was confirmed by Raman spectroscopy and further investigated by quantum‐chemical methods. Computed interatomic distances within the [C2N]3? anion strikingly match the obtained experimental data. 相似文献
78.
79.
80.
Elisabeth Schmoeger Eva Berger Alexandru Trefilov Alois Jungbauer Rainer Hahn 《Journal of chromatography. A》2009,1216(48):8460-8469
Refolding of proteins must be performed under very dilute conditions to overcome the competing aggregation reaction, which has a high reaction order. Refolding on a chromatography column partially prevents formation of the intermediate form prone to aggregation. A chromatographic refolding procedure was developed using an autoprotease fusion protein with the mutant EDDIE from the Npro autoprotease of pestivirus. Upon refolding, self-cleavage generates a target peptide with an authentic N-terminus. The refolding process was developed using the basic 1.8-kDa peptide sSNEVi-C fused to the autoprotease EDDIE or the acidic peptide pep6His, applying cation and anion exchange chromatography, respectively. Dissolved inclusion bodies were loaded on cation exchange chromatographic resins (Capto S, POROS HS, Fractogel EMD SO3−, UNOsphere S, SP Sepharose FF, CM Sepharose FF, S Ceramic HyperD F, Toyopearl SP-650, and Toyopearl MegaCap II SP-550EC). A conditioning step was introduced in order to reduce the urea concentration prior to the refolding step. Refolding was initiated by applying an elution buffer containing a high concentration of Tris–HCl plus common refolding additives. The actual refolding process occurred concurrently with the elution step and was completed in the collected fraction. With Capto S, POROS HS, and Fractogel SO3−, refolding could be performed at column loadings of 50 mg fusion protein/ml gel, resulting in a final eluate concentration of around 10–15 mg/ml, with refolding and cleavage step yields of around 75%. The overall yield of recovered peptide reached 50%. Similar yields were obtained using the anion exchange system and the pep6His fusion peptide. This chromatographic refolding process allows processing of fusion peptides at a concentration range 10- to 100-fold higher than that observed for common refolding systems. 相似文献