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191.
Uroš Grošelj Dieter Seebach D. Michael Badine W. Bernd Schweizer Albert K. Beck Ingo Krossing Petra Klose Yujiro Hayashi Tadafumi Uchimaru 《Helvetica chimica acta》2009,92(7):1225-1259
Structures of the reactive intermediates (enamines and iminium ions) of organocatalysis with diarylprolinol derivatives have been determined. To this end, diarylprolinol methyl and silyl ethers, 1 , and aldehydes, Ph? CH2? CHO, tBu? CH2? CHO, Ph? CH=CH? CHO, are condensed to the corresponding enamines, A and 3 (Scheme 2), and cinnamoylidene iminium salts, B and 4 (Scheme 3). These are isolated and fully characterized by melting/decomposition points, [α]D, elemental analysis, IR and NMR spectroscopy, and high‐resolution mass spectrometry (HR‐MS). Salts with BF4, PF6, SbF6, and the weakly coordinating Al[OC(CF3)3]4 anion were prepared. X‐Ray crystal structures of an enamine and of six iminium salts have been obtained and are described herein (Figs. 2 and 4–8, and Tables 2 and 7) and in a previous preliminary communication (Helv. Chim. Acta 2008 , 91, 1999). According to the NMR spectra (in CDCl3, (D6)DMSO, (D6)acetone, or CD3OD; Table 1), the major isomers 4 of the iminium salts have (E)‐configuration of the exocyclic N?C(1′) bond, but there are up to 11% of the (Z)‐isomer present in these solutions (Fig. 1). In all crystal structures, the iminium ions have (E)‐configuration, and the conformation around the exocyclic N‐C? C‐O bond is synclinal‐exo (cf. C and L ), with one of the phenyl groups over the pyrrolidine ring, and the RO group over the π‐system. One of the meta‐substituents (Me in 4b , CF3 in 4c and 4e ) on a 3,5‐disubstituted phenyl group is also located in the space above the π‐system. DFT Calculations at various levels of theory (Tables 3–6) confirm that the experimentally determined structures (cf. Fig. 10) are by far (up to 8.3 kcal/mol) the most stable ones. Implications of the results with respect to the mechanism of organocatalysis by diarylprolinol derivatives are discussed. 相似文献
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We have made theoretical studies on the limitation of the open-circuit voltageV
oc of a hydrogenated amorphous silicon (a-Si:H) p-i-n type solar cell. The effects of the tail states in the a-Si:H i layer and of the interface recombination are discussed in detail. The opencircuit voltage increases when the distribution of the tail states is sharp and/or the capture cross sections of these states are small. This is because the recombination rate of photogenerated carriers and/or the density of space charge due to trapped carriers in these states become low in these conditions. These effects of the tail states on the value ofV
oc become pronounced when the built-in potential of the p-i-n junction is high. The decrease in the effective recombination velocity of carriers at the p/i and n/i interfaces results in an increase ofV
oc. This increase becomes remarkable when the effects of the tail states on the value ofV
oc are small. Both the sharp distribution of tail states and the small value of the interface recombination velocity are necessary to increase considerably the value ofV
oc. We show the conditions of the material parameters necessary to obtain an open-circuit voltage of 1.0 V. 相似文献
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Summary The analytical roles of chromatographic variables (column length, etc.) can be soundly comprehended and compared in terms
of the precision (Φ) of measurements and efficiency (ϑ) of analysis which are described as Shannon information and information
flow, respectively. The φϑ plots of the optimization process and the information Φ transmitted by a single peak are useful
to understand the analytical structure of optimization. Variables treated here are mobile phase composition (X), column length
(L), mobile phase velocity rate (u), detection wavelength (λ) and plate number (N). 相似文献
197.
Shuhei Hayashi 《Bulletin of the Brazilian Mathematical Society》2000,31(3):337-350
Mañé suggested the following question: Consider aC r flow on a compact manifold without boundary and suppose that the ω-limit set of a pointp intersets the α-limit set ofq, i.e. ω(p)∩α(q)≠Ø. Can the flow beC r-perturbed so that either (a)p is connected toq (p andq in the same orbit) or (b) ω(p)∩α(q)=Ø for the new flow? Here we solve positively a stronger version of this problem forC 1 small perturbations of the original flow. 相似文献
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