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101.
In this paper, we generalize earlier work dealing with maxima of discrete random variables. We show that row-wise stationary block maxima of a triangular array of integer valued random variables converge to a Gumbel extreme value distribution if row-wise variances grow sufficiently fast as the row-size increases. As a by-product, we derive analytical expressions of normalising constants for most classical unbounded discrete distributions. A brief simulation illustrates our theoretical result. Also, we highlight its usefulness in practice with a real risk assessment problem, namely the evaluation of extreme avalanche occurrence numbers in the French Alps. 相似文献
102.
The steady-state laminar mixed convection of a binary gas mixture in a parallel-plate channel is investigated. The channel walls are subjected to different combinations of first-type thermal and solutal boundary conditions and different wall inclinations have been considered. A second-order accurate control-volume based numerical scheme is used for the resolution. In parallel with the numerical investigation, the governing conservation equations are also simplified for fully developed conditions and are shown to be controlled by a single parameter. An exact analytical solution is obtained for the main flow variables and transfer rates and serves as a validation tool for the numerical model. In addition, it establishes a criterion based on the two Grashof numbers, the Reynolds number and the channel inclination for the existence of a reversed flow. 相似文献
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Laura Febvay Erwann Hamon Raphaël Recht Nicolas Andres Mathilde Vincent Dalal Aoudé-Werner Hervé This 《Magnetic resonance in chemistry : MRC》2019,57(9):589-602
Roasting of Coffea arabica L. seeds gives rise to chemical reactions that produce more than 800 compounds, some being responsible for the desired organoleptic properties for which the beverage called “coffee” is known. In the industry, the “roasting profile,” that is, the times and temperatures applied, is key to influence the composition of roasted coffee beans and the flavour of the beverage made from them. The impact of roasting on the chemical composition of coffee has been the subject of numerous studies, including by nuclear magnetic resonance (NMR) spectroscopy. However, the roasting equipment and profiles applied in these studies are often far from real industrial conditions. In this work, the effects of two critical technological parameters of the roasting process, namely, the “development time” (the period of time after the “first crack,” a characteristic noise due to seed disruption) and the final roasting temperature on coffee extracts, were investigated. Seeds were roasted at pilot scale according to 13 industrial roasting profiles and extracted in D2O. The extracts were analysed by 1H NMR experiments. The NMR spectra were compared using (a) quantitative analysis of main signals by successive orders of magnitude and (b) chemometric tools (principal component analysis, partial least squares and sparse-orthogonal partial least squares analysis). This allowed to identify compounds, which may serve as markers of roasting and showed that changes in chemical composition can be detected even for slight change in final temperature (~1°C) or in total roasting time (~25 s). 相似文献
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Dr. Massimo Rigo Evi R. M. Habraken Dr. Koyel Bhattacharyya Manuela Weber Dr. Andreas W. Ehlers Dr. Nicolas Mézailles Dr. J. Chris Slootweg Prof. Dr. Christian Müller 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(37):8769-8779
A series of substituted phosphinines, 1-phosphabarrelenes and 5-phosphasemibullvalenes were synthesized and evaluated for their potential application as ligands in homogeneous catalytic reactions. While their buried volume (%Vbur) was calculated to get insight into the steric properties, [LNi(CO)3] complexes were prepared in order to determine the corresponding Tolman electronic parameter. ETS-NOCV (extended-transition-state natural orbital for chemical valence) calculations on [LAuCl] complexes further allowed an estimation of the σ- and π-contributions to the L− M interaction. AuI coordination compounds of selected examples were prepared and characterized by single crystal X-ray diffraction. Finally, the three classes of PIII compounds were successfully used in the AuI-catalyzed cycloisomerization of N-2-propyn-1-ylbenzamide, showing very good activities and selectivities, which are comparable with the reported data of cationic phosphorus-based gold catalysts. 相似文献
109.
Dr. Ting Liang Dr. Dominique Collin Melodie Galerne Dr. Gad Fuks Dr. Andreas Vargas Jentzsch Prof. Dr. Mounir Maaloum Alain Carvalho Prof. Dr. Nicolas Giuseppone Dr. Emilie Moulin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(63):14341-14348
C3-Symmetric triarylamine trisamides (TATAs), decorated with three norbornene end groups, undergo supramolecular polymerization and further gelation by π–π stacking and hydrogen bonding of their TATA cores. By using subsequent ring-opening metathesis polymerization, these physical gels are permanently crosslinked into chemical gels. Detailed comparisons of the supramolecular stacks in solution, in the physical gel, and in the chemical gel states, are performed by optical spectroscopies, electronic spectroscopies, atomic force microscopy, electronic paramagnetic resonance spectroscopy, X-ray scattering, electronic transport measurements, and rheology. The results presented here clearly evidence that the core structure of the functional supramolecular polymers can be precisely retained during the covalent capture whereas the mechanical properties of the gels are concomitantly improved, with an increase of their storage modulus by two orders of magnitude. 相似文献
110.
We study the mechanical response, and tearing features of crêpe paper, a two-dimensional, very anisotropic material, with one direction much less stiff than the other one. Depending on how the soft direction has been pre-stretched or not, the apparent Young modulus of the material can be varied over a broad range, while its fracture energy remains unaltered. The classical tearing concertina problem shows that a macroscopic measurement (the shape of the teared region) provides a direct access to the fracture properties of the material (effective Young's modulus, and fracture energy). The overall discussion is conducted in the frame of Griffith's theory of fracture. 相似文献