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排序方式: 共有314条查询结果,搜索用时 9 毫秒
111.
Bron M Teschner D Knop-Gericke A Jentoft FC Kröhnert J Hohmeyer J Volckmar C Steinhauer B Schlögl R Claus P 《Physical chemistry chemical physics : PCCP》2007,9(27):3559-3569
The hydrogenation of acrolein over pure and supported silver has been investigated with a focus on the influence of catalyst structure and reaction pressure (mbar to 20 bar range) on activity and selectivity. An onset of formation of allyl alcohol beyond 100 mbar reaction pressure (at 250 degrees C) is ascribed to a change in adsorption geometry upon increasing coverage. Smaller silver particles (in the nanometer range), the proximity of a reducible oxide component as well as high pressure lead to enhanced allyl alcohol formation; the selectivity to the other main product propionaldehyde is reduced. The silver dispersion changed depending on the reaction pressure. Moreover, the presence of oxygen, most likely as subsurface oxygen, and the presence of defects are of paramount importance for the catalytic behaviour. The considerable changes of the silver catalysts under reaction conditions and the pressure dependence call for in situ measurements to establish true structure-activity/selectivity relationships for this system. 相似文献
112.
We briefly review recent theoretical and simulation studies of charged colloidal dispersions in alternating electric fields (AC fields). The response of single colloid to an external field can be characterized by a complex polarizability, which describes the dielectric properties of the colloid and its surrounding electrical double layer. We present computer simulation studies of single spherical colloid, using a coarse-grained mesoscale approach that accounts in full for hydrodynamic and electrostatic interactions as well as for thermal fluctuations. We investigate systematically a number of controlling parameters, such as the amplitude and frequency of the AC-fields. The results are in good agreement with recent theoretical predictions. 相似文献
113.
Silvers R Sziegat F Tachibana H Segawa S Whittaker S Günther UL Gabel F Huang JR Blackledge M Wirmer-Bartoschek J Schwalbe H 《Journal of the American Chemical Society》2012,134(15):6846-6854
During oxidative folding, the formation of disulfide bonds has profound effects on guiding the protein folding pathway. Until now, comparatively little is known about the changes in the conformational dynamics in folding intermediates of proteins that contain only a subset of their native disulfide bonds. In this comprehensive study, we probe the conformational landscape of non-native states of lysozyme containing a single native disulfide bond utilizing nuclear magnetic resonance (NMR) spectroscopy, small-angle X-ray scattering (SAXS), circular dichroism (CD) data, and modeling approaches. The impact on conformational dynamics varies widely depending on the loop size of the single disulfide variants and deviates significantly from random coil predictions for both NMR and SAXS data. From these experiments, we conclude that the introduction of single disulfides spanning a large portion of the polypeptide chain shifts the structure and dynamics of hydrophobic core residues of the protein so that these regions exhibit levels of order comparable to the native state on the nanosecond time scale. 相似文献
114.
M. Fehr A. Schnegg B. Rech K. Lips O. Astakhov F. Finger C. Freysoldt R. Bittl C. Teutloff 《Journal of Non》2012,358(17):2067-2070
Paramagnetic coordination defects in undoped hydrogenated amorphous silicon (a-Si:H) are studied using multifrequency pulsed electron-paramagnetic resonance (EPR) spectroscopy at S-, X-, Q- and W-band microwave frequencies (3.6, 9.7, 34, and 94 GHz, respectively). The improved spectral information extractable from a multifrequency fitting procedure allows us to conclude that the g tensor exhibits a rhombic splitting instead of axial symmetry. Our methods allow for precise and accurate determination of the g tensor principal values gx = 2.0079(2), gy = 2.0061(2) and gz = 2.0034(2) and their distribution parameters (g strain). 相似文献
115.
Friederike Fehr André Nadler Florian Brodhun Ivo Feussner Ulf Diederichsen 《ChemistryOpen》2012,1(1):26-32
Total synthesis of proteins can be challenging despite assembling techniques, such as native chemical ligation (NCL) and expressed protein ligation (EPL). Especially, the combination of recombinant protein expression and chemically addressable solid-phase peptide synthesis (SPPS) is well suited for the redesign of native protein structures. Incorporation of analytical probes and artificial amino acids into full-length natural protein domains, such as the sequence-specific DNA binding zinc-finger motifs, are of interest combining selective DNA recognition and artificial function. The semi-synthesis of the natural 90 amino acid long sequence of the zinc-finger domain of Zif268 is described including various chemically modified constructs. Our approach offers the possibility to exchange any amino acid within the third zinc finger. The realized modifications of the natural sequence include point mutations, attachment of a fluorophore, and the exchange of amino acids at different positions in the zinc finger by artificial amino acids to create additional metal binding sites. The individual constructs were analyzed by circular dichroism (CD) spectroscopy with respect to the integrity of the zinc-finger fold and DNA binding. 相似文献
116.
117.
Jrg Doege Max Fehr Juri Hinz Hans-Jakob Lüthi Martina Wilhelm 《European Journal of Operational Research》2009,199(3):936-943
Since the 1990s power markets are being restructured worldwide and nowadays electrical power is traded as a commodity. The liberalization and with it the uncertainty in gas, fuel and electrical power prices requires an effective management of production facilities and financial contracts. Thereby derivatives build essential instruments to exchange volume as well as price risks. The challenge for participants in the newly competitive market environment is how to design, price and hedge derivative contracts in particular combination with the flexibility embedded in dispatch strategies of production assets. Accordingly, an adequate basis for management and investment decisions is needed which responds to the highly complex market situation. 相似文献
118.
Friederike M. Wunsch Bernhard Wünsch Freddy A. Bernal Thomas J. Schmidt 《Molecules (Basel, Switzerland)》2021,26(17)
On the basis of the finding that various aminoalkyl-substituted chromene and chromane derivatives possess strong and highly selective in vitro bioactivity against Plasmodium falciparum, the pathogen responsible for tropical malaria, we performed a structure–activity relationship study for such compounds. With structures and activity data of 52 congeneric compounds from our recent studies, we performed a three-dimensional quantitative structure–activity relationship (3D-QSAR) study using the comparative molecular field analysis (CoMFA) approach as implemented in the Open3DQSAR software. The resulting model displayed excellent internal and good external predictive power as well as good robustness. Besides insights into the molecular interactions and structural features influencing the antiplasmodial activity, this model now provides the possibility to predict the activity of further untested compounds to guide our further synthetic efforts to develop even more potent antiplasmodial chromenes/chromanes. 相似文献
119.
We present a simple model which allows us to investigate the equilibrium aspects of molecular recognition between rigid biomolecules on a generic level. Using a two-stage approach, which consists of a design and a testing step, the role of cooperativity and of varying bond strength in molecular recognition is investigated. Cooperativity is found to enhance selectivity. In complexes which require a high binding flexibility, a small number of strong bonds seems to be favored compared to a situation with many but weak bonds. 相似文献
120.
Regula Theurillat Friederike A. Sandbaumhüter Claudia Gittel M. Paula Larenza Menzies Christina Braun Wolfgang Thormann 《Electrophoresis》2019,40(15):1959-1965
An enantioselective assay for the determination of methadone and its main metabolite 2‐ethylidene‐1,5‐dimethyl‐3,3‐diphenylpyrrolidine in equine plasma based on capillary electrophoresis with highly sulfated γ‐cyclodextrin as chiral selector and electrokinetic analyte injection is described. The assay is based on liquid/liquid extraction of the analytes at alkaline pH from 0.1 mL plasma followed by electrokinetic sample injection of the analytes from the extract across a buffer plug without chiral selector. Separation occurs cationically at normal polarity in a pH 3 phosphate buffer containing 0.16% (w/v) of highly sulfated γ‐cyclodextrin. The developed assay is precise (intra‐ and interday RSD < 4% and < 7%, respectively), is capable to determine enantiomer levels of methadone and 2‐ethylidene‐1,5‐dimethyl‐3,3‐diphenylpyrrolidine in plasma down to 2.5 ng/mL, and was successfully applied to monitor enantiomer drug and metabolite levels in plasma of a pony that was anesthetized with racemic ketamine and isoflurane and received a bolus of racemic methadone and a bolus followed by constant rate infusion of racemic methadone. The data suggest that the assay is well suited for pharmacokinetic purposes. 相似文献