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Derivatives of N-pyrrolobenzene with a para-donor and a para-acceptor substituent on the benzene ring are compared. It is shown that by a suitable increase of the donor strength of the pyrrolo group, CT fluorescence can be achieved even for donor–donor-substituted benzenes. The ICT emission for sterically hindered compounds is more forbidden than that of unhindered phenyl pyrroles. This suggests conformational effects which induce a narrower twist angle distribution around a perpendicular minimum in the excited state. 相似文献
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Sven Tombrink Saskia Müller Richard Heming Antje Michels Peter Lampen Joachim Franzke 《Analytical and bioanalytical chemistry》2010,397(7):2917-2922
In this study a simple micro-tube-based system for analysis of metal-containing liquids is introduced and its analytical performance
is evaluated. It is based on a miniaturised dielectric barrier discharge driven at atmospheric pressure. The emission lines
of various elements are observed. The system is developed for quantitative measurements and the limits of detection are determined.
Because of very low flow rates of just μL min−1 the approach requires extremely low sample volumes. 相似文献
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This paper estimates the price for restructuring risk in the US corporate bond market during 1999–2005. Comparing quotes from default swap (CDS) contracts with a restructuring event and without, we find that the average premium for restructuring risk represents 6%–8% of the swap rate without restructuring. We show that the restructuring premium depends on firm-specific balance-sheet and macroeconomic variables. And, when default swap rates without a restructuring event increase, the increase in restructuring premia is higher for low-credit-quality firms than for high-credit-quality firms. We propose a reduced-form arbitrage-free model for pricing default swaps that explicitly incorporates the distinction between restructuring and default events. A case study illustrating the model’s implementation is provided. 相似文献
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Banert K Köhler F Melzer A Scharf I Rheinwald G Rüffer T Lang H Herges R Hess K Ghavtadze N Würthwein EU 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(36):10071-10080
1,4‐Diazidobuta‐1,3‐dienes (Z,Z)‐ 10 , 17 , and 21 were photolyzed and thermolyzed to yield the pyridazines 13 , 20 , and 23 , respectively. To explain these aromatic final products, the generation of highly strained bi‐2H‐azirin‐2‐yls 12 , 19 , and 22 and their valence isomerization were postulated. In the case of meso‐ and rac‐ 22 , nearly quantitative formation from diazide 21 , isolation as stable solids, and complete characterization were possible. On the thermolysis of 22 , aromatization to 23 was only a side reaction, whereas equilibration of meso‐ and rac‐ 22 and fragmentation, which led to alkyne 24 and acetonitrile, dominated. Prolonged irradiation of 22 gave mainly the pyrimidine 25 . The change of the configuration at C‐2 of the 2H‐azirine unit was observed not only in the case of bi‐2H‐azirin‐2‐yls 22 but also for simple spirocyclic 2H‐azirines 29 at a relatively low temperature (75 °C). The fragmentation of rac‐ 22 to give alkyne 24 and two molecules of acetonitrile was also studied by high‐level quantum chemical calculations. For a related model system 30 (methyl instead of phenyl groups), two transition states TS‐ 30 – 31 of comparable energy with multiconfigurational electronic states could be localized on the energy hypersurface for this one‐step conversion. The symmetrical transition state complies with the definition of a coarctate mechanism. 相似文献