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Hubertus Appler Lutz W. Gross Bernd Mayer Wilhelm P. Neumann 《Journal of organometallic chemistry》1985,291(1):9-23
Factors governing the ease and mechanism of 7-silabicyclo[2.2.1]heptadienes thermolysis in order to generate free silylenes and the corresponding benzene derivatives are investigated. For this purpose, 29 new compounds of the types VII–X have been prepared. No indications for a polar mechanism or an intermediate biradical could be found. The degradation is exactly of first order in all cases investigated sofar, and is enhanced by phenyl groups at the bridgehead C atoms, if a conformation coplanar with the basic ring is allowed by the neighbouring substituents, but is not enhanced by phenyl groups at the Si. The X-ray structure of two typical derivatives is discussed with this respect. A special mechanism is operating in the easy thermolysis of carbomethoxy-substituted compounds leading to cyclic sila enolether intermediates. 相似文献
3.
Gyula Záray Tibor Kántor Gerhard Wolff Zdravka Zadgorska Hubertus Nickel 《Mikrochimica acta》1992,107(3-6):345-358
The analytical capability of high-temperature halogenation with carbon tetrachloride vapour in a graphite furnace was investigated for silicon carbide powder with known chemical composition and particle size. Intensity vs heating time curves were determined for analytical lines of Al, B, Ba, Ca, Cr, Cu, Fe, Mg, Mn, Ti, V and Si constituents, volatilized with and without the presence of CCl4 vapour in the furnace atmosphere. Igniting 10 mg SiC at 2100 °C for 60 s in chlorinating atmosphere, the evaporated fraction of most of the constituents was higher than 90% (for Al about 50%). The line intensity vs sample mass (4–26 mg) relationships were linear for all impurities studied, while the intensity of silicon line showed a relatively small change with the sample mass. BEC (background equivalent concentration) values for this solid sampling technique (10 mg loaded sample) were 2–20 fold lower than those calculated for the conventional solution sample introduction method. 相似文献
4.
This review provides an overview of direct and indirect technologies to screen protein–ligand interactions with mass spectrometry.
These technologies have as a key feature the selection or affinity purification of ligands in mixtures prior to detection.
Specific fields of interest for these technologies are metabolic profiling of bioactive metabolites, natural extract screening,
and the screening of libraries for bioactives, such as parallel synthesis libraries and small combichem libraries. The review
addresses the principles of each of the methods discussed, with a focus on developments in recent years, and the applicability
of the methods to lead generation and development in drug discovery. 相似文献
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Coverage‐ and Temperature‐Dependent Metalation and Dehydrogenation of Tetraphenylporphyrin on Cu(111) 下载免费PDF全文
Michael Röckert Matthias Franke Quratulain Tariq Stefanie Ditze Michael Stark Patrick Uffinger Daniel Wechsler Upendra Singh Dr. Jie Xiao Dr. Hubertus Marbach Prof. Dr. Hans‐Peter Steinrück Dr. Ole Lytken 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(29):8948-8953
Using temperature‐programmed desorption, supported by X‐ray photoelectron spectroscopy and scanning tunneling microscopy, a comprehensive overview of the main reactions of 5,10,15,20‐tetraphenyl‐21H,23H‐porphyrin (2HTPP) on Cu(111) as a function of coverage and temperature is obtained. Three reactions were identified: metalation with Cu substrate atoms, stepwise partial dehydrogenation, and finally complete dehydrogenation. At low coverage the reactions are independent of coverage, but at higher coverage metalation becomes faster and partial dehydrogenation slower. This behavior is explained by a weaker interaction between the iminic nitrogen atoms and the Cu(111) surface in the high‐coverage checkerboard structure, leading to faster metalation, and the stabilizing effect of T‐type interactions in the CuTPP islands formed at high coverage after metalation, leading to slower dehydrogenation. Based on the amount of hydrogen released and the appearance in STM, a structure of the partially dehydrogenated molecule is suggested. 相似文献
8.
The heats of solution of alcohols in hexane can be considered as the energy necessary to break hydrogen bonds (H-bond). The amount of non H-bonded OH groups estimated from caloric data, are in good agreement with IR-spectroscopic data. Comparison of calorimetric and IR-spectroscopically determined H-bond energies permit the separation of intermolecular van der Waals effects from H-bond interactions. This separation shows that van der Waals interactions of alcohols or water should not be underestimated. 相似文献
9.
Morfill GE Rubin-Zuzic M Rothermel H Ivlev AV Klumov BA Thomas HM Konopka U Steinberg V 《Physical review letters》2004,92(17):175004
Fluid flow around an obstacle was observed at the kinetic (individual particle) level using "complex (dusty) plasmas" in their liquid state. These "liquid plasmas" have bulk properties similar to water (e.g., viscosity), and a comparison in terms of similarity parameters suggests that they can provide a unique tool to model classical fluids. This allows us to study "nanofluidics" at the most elementary-the particle-level, including the transition from fluid behavior to purely kinetic transport. In this (first) experimental investigation we describe the kinetic flow topology, discuss our observations in terms of fluid theories, and follow this up with numerical simulations. 相似文献
10.
Frederic Y. M. Wan Hubertus J. Weinitschke 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1987,38(1):79-91
Summary The method of matched asymptotic expansions is used to describe finite axisymmetric deformations of two thin elastic membrane problems: a circular membrane with a small radial traction at the edge, an annular membrane with a small circular hole at the center. In both problems, the surface load is assumed to be an axial pressure. There is a boundary layer at the outer edge in the first problem, and at the hole in the second problem.
Zusammenfassung Mit Hilfe der in der singulären Störungsrechnung benutzten Methode einer inneren und äußeren asymptotischen Entwicklung werden endliche, axialsymmetrische Deformationen bei zwei Membranproblemen beschrieben: eine dünne elastische Kreismembran mit kleiner radialer Zugspannung am Rande, und eine Kreisringmembran mit einem kleinen konzentrischen Loch. In beiden Problemen wird die Belastung als ein axial gerichteter Oberflächendruck angenommen. Im ersten Problem zeigt die Lösung am äußeren Rand Grenzschichtverhalten, welches im zweiten Problem am Lochrand vorliegt.相似文献