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161.
162.
Influence of P‐Bonded Bulky Substituents on Electronic Interactions in Ferrocenyl‐Substituted Phospholes
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Dominique Miesel Dr. Alexander Hildebrandt Marcus Korb Prof. Dr. Heinrich Lang 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(32):11545-11559
2,5‐Diferrocenyl‐1‐Ar‐1H‐phospholes 3 a – e (Ar=phenyl ( a ), ferrocenyl ( b ), mesityl ( c ), 2,4,6‐triphenylphenyl ( d ), and 2,4,6‐tri‐tert‐butylphenyl ( e )) have been prepared by reactions of ArPH2 ( 1 a – e ) with 1,4‐diferrocenyl butadiyne. Compounds 3 b – e have been structurally characterized by single‐crystal XRD analysis. Application of the sterically demanding 2,4,6‐tri‐tert‐butylphenyl group led to an increased flattening of the pyramidal phosphorus environment. The ferrocenyl units could be oxidized separately, with redox separations of 265 ( 3 b ), 295 ( 3 c ), 340 ( 3 d ), and 315 mV ( 3 e ) in [NnBu4][B(C6F5)4]; these values indicate substantial thermodynamic stability of the mixed‐valence radical cations. Monocationic [ 3 b ]+–[ 3 e ]+ show intervalence charge‐transfer absorptions between 4650 and 5050 cm?1 of moderate intensity and half‐height bandwidth. Compounds 3 c – e with bulky, electron‐rich substituents reveal a significant increase in electronic interactions compared with less demanding groups in 3 a and 3 b . 相似文献
163.
Topics that attract public attention can originate from current events or developments, might be influenced by situations in the past, and often continue to be of interest in the future. When respective information is made available textually, one possibility of detecting such topics of public importance consists in scrutinizing, e.g., appropriate press articles using—given the continual growth of information—text processing techniques enriched by computer routines which examine present-day textual material, check historical publications, find newly emerging topics, and are able to track topic trends over time. Information clustering based on content-(dis)similarity of the underlying textual material and graph-theoretical considerations to deal with the network of relationships between content-similar topics are described and combined in a new approach. Explanatory examples of topic detection and tracking in online news articles illustrate the usefulness of the approach in different situations. 相似文献
164.
Dr. Samuel M. Meier M. Sc. Dominique Kreutz Dr. Lilli Winter M. Sc. Matthias H. M. Klose M. Sc. Klaudia Cseh M. Sc. Tamara Weiss Dr. Andrea Bileck M. Sc. Beatrix Alte Dr. Johanna C. Mader M. Sc. Samir Jana Dr. Annesha Chatterjee Dr. Arindam Bhattacharyya Michaela Hejl Dr. Michael A. Jakupec Priv.-Doz. Dr. Petra Heffeter Prof. Dr. Walter Berger Prof. Dr. Christian G. Hartinger Prof. Dr. Bernhard K. Keppler Prof. Dr. Gerhard Wiche Prof. Dr. Christopher Gerner 《Angewandte Chemie (International ed. in English)》2017,56(28):8267-8271
Organometallic metal(arene) anticancer agents require ligand exchange for their anticancer activity and this is generally believed to confer low selectivity for potential cellular targets. However, using an integrated proteomics-based target-response profiling approach as a potent hypothesis-generating procedure, we found an unexpected target selectivity of a ruthenium(arene) pyridinecarbothioamide (plecstatin) for plectin, a scaffold protein and cytolinker, which was validated in a plectin knock-out model in vitro. Plectin targeting shows potential as a strategy to inhibit tumor invasiveness as shown in cultured tumor spheroids while oral administration of plecstatin-1 to mice reduces tumor growth more efficiently in the invasive B16 melanoma than in the CT26 colon tumor model. 相似文献
165.
Olivier Gicque Dominique Thévenin Nasser Darabiha 《Flow, Turbulence and Combustion》2005,73(3-4):307-321
In this paper we wish to investigate the occurrence of super-equilibrium temperature values, observed in many experimental
configurations. We would like to understand the origin of this phenomenon. Previous authors have already shown that differential
diffusion can lead to considerable changes in the temperature field and we would like to build on top of this observation.
We investigate numerically super-equilibrium combustion by considering both laminar counter-flow and turbulent diluted hydrogen/air
diffusion flames. These turbulent flames are computed using direct numerical simulations (DNS). A detailed reaction mechanism
is employed and the transport properties are modeled using multicomponent diffusion velocities, including the Soret effect.
Analyzing these results we introduce three complementary parameters (dilution-free mixture fraction, dilution excess and local
enthalpy) to describe the local combustion conditions. Introducing a measure of dilution separately from the mixture fraction
is necessary for a proper analysis. Using this set of parameters it becomes possible to explain super-equilibrium temperature
levels as a consequence of differential diffusion. 相似文献
166.
The gelation kinetics of aqueous solutions of acrylamideacrylic acid copolymers in the presence of chromium ions was studied with different rheometers. The gel time is found to vary with the principle of the apparatus because of a low shear dependence of the elongation of the macromolecules. The variations of the gel time with the experimental conditions of the gel preparation were investigated and we conclude that the gelation is governed by the oligornerization kinetics of the chromium ions which are instantaneously, complexated by the carboxylate groups of the polymer. The variation laws of the gel time and of the elastic modulus with chromium and polymer concentrations, temperature and ionic strength are in qualitative agreement with the structure of the temporary network of the semi-dilute solutions of these copolymers. 相似文献
167.
168.
Phan-Xuan T Durand D Nicolai T Donato L Schmitt C Bovetto L 《Langmuir : the ACS journal of surfaces and colloids》2011,27(24):15092-15101
Stable suspensions of protein microgels are formed by heating salt-free β-lactoglobulin solutions at concentrations up to about C = 50 g·L(-1) if the pH is set within a narrow range between 5.75 and 6.1. The internal protein concentration of these spherical particles is about 150 g·L(-1) and the average hydrodynamic radius decreases with increasing pH from 200 to 75 nm. The formation of the microgels leads to an increase of the pH, which is a necessary condition to obtain stable suspensions. The spontaneous increase of the pH during microgel formation leads to an increase of their surface charge density and inhibits secondary aggregation. This self-stabilization mechanism is not sufficient if the initial pH is below 5.75 in which case secondary aggregation leads to precipitation. Microgels are no longer formed above a critical initial pH, but instead short, curved protein strands are obtained with a hydrodynamic radius of about 15-20 nm. 相似文献
169.
Ropartz D Bodet PE Przybylski C Gonnet F Daniel R Fer M Helbert W Bertrand D Rogniaux H 《Rapid communications in mass spectrometry : RCM》2011,25(14):2059-2070
Compared to other analytical methods, matrix-assisted laser desorption ionization mass spectrometry (MALDI-MS) presents several unique advantages for the structural characterization of degradation products of carbohydrates. Our final goal is to implement this technique as a high-throughput platform, with the aim of exploring natural bio-diversity to discover new carbohydrate depolymerizing enzymes. In this approach, a variety of carbohydrates will be used as enzymes substrates and MALDI-MS will be employed to monitor the oligosaccharides produced. One drawback of MALDI, however, is that the choice of the matrix is largely dependent on the chemical properties of the analyte. In this context, our objective in the present work was to find the smallest set of MALDI matrices able to detect chemically heterogeneous oligosaccharides. This was done through the performance evaluation of more than 40 MALDI matrices preparations. Homogeneity of analyte-matrix deposits was considered as a critical feature, especially since the final objective is to fully automate the analyses. Evaluation of the matrices was done by means of a rigorous statistical approach. Amongst all tested compounds, our work proposes the use of the DHB/DMA ionic matrix as the most generic matrix, for rapid detection of a variety of polysaccharides including neutral, anionic, methylated, sulfated, and acetylated compounds. The selected matrices were then used to screen crude bacterial incubation media for the detection of enzymatic degradation products. 相似文献
170.
Knyazev A Louise L Veber M Langevin D Filoramo A Prina-Mello A Campidelli S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(51):14663-14671
The dispersion of highly hydrophobic carbon materials such as carbon nanotubes in biological media is a challenging issue. Indeed, the nonspecific adsorption of proteins occurs readily when the nanotubes are introduced in biological media; therefore, a methodology to control adsorption is in high demand. To address this issue, we developed a bifunctional linker derived from pyrene that selectively enables or prevents the adsorption of proteins on single-wall carbon nanotubes (SWNTs). We demonstrated that it is possible to decrease or completely suppress the adsorption of proteins on the nanotube sidewall by using proper functionalization (either covalent or noncovalent). By subsequently activating the functional groups on the nanotube derivatives, protein adsorption can be recovered and, therefore, controlled. Our approach is simple, straightforward, and potentially suitable for other biomolecules that contain thio or amino groups available for coupling. 相似文献