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971.
Javier Catalán 《Journal of Physical Organic Chemistry》2015,28(7):497-503
Molecular structures possessing atomic sites that contribute a non‐bonding electron pair to their π system (e.g. nitrogen atoms with sp2 hybridization in pyrroles and anilines) usually exhibit a first absorption band whose solvatochromism is, surprisingly, sensitive only to the polarizability of the medium even though they are dipolar. As shown here, this solvatochromic behavior is a result of the first electronic transition in these compounds occurring from a substantially localized π orbital to a substantially delocalized π* orbital in the molecular structure. The high electronic delocalization present leads to a marked bathochromic band shift as the polarizability of the medium increases. It is especially relevant that this solvatochromism, which is because of the polarizability of the medium, explains the spectral shift that is only because of the redistribution of the electrons of the solvent molecules. It is important to take into account that this electronic redistribution happens instantaneously in this process. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
972.
《Comptes Rendus Chimie》2015,18(7):713-741
The purpose of this review is to analyze the different reaction mechanisms of the H/D exchange on organic substrates catalyzed by transition metal complexes in homogeneous phase. The metal-catalyzed H/D exchange is a multifaceted reaction whose mechanism depends strongly on the reaction conditions and on the metal complex used as a catalyst. It is possible to group the different mechanisms into three main families depending on the “role” and behavior of the catalyst: (i) Lewis acid–base catalysis; (ii) CH activation (iii) insertion/β-elimination. For each macro-group, several representative examples are discussed and critically evaluated in order to provide the reader with keys to the understanding of how the different catalytic systems act and how their modification may affect their performance in terms of activity and selectivity. This knowledge is fundamental for designing improved organometallic H/D catalysts for labeling organic products in greener conditions with more cost-effective processes. 相似文献
973.
Cross-flow displacements of neutrally buoyant solid spheres under Poiseuille-type flow conditions in narrow channels, at low volume fraction, are described by a phenomenological model within the framework of the Fokker-Planck equation. In this model, the effects of particle-particle and particle-wall interactions are taken into account. In addition to the classical wall effect (depleted layer near the wall), numerical solutions of the derived equations display two opposite lateral migrations towards the wall and the tube axis, and an alignment of the particles in adjacent layers parallel to the flow. These numerical results are then compared with experimental results obtained by Goldsmith and Marlow [18] for erythrocyte suspensions. A good qualitative agreement is observed. 相似文献
974.
Yun-Hu Wang 《Mathematical Methods in the Applied Sciences》2015,38(1):138-144
Under investigation in this paper are the (1+1)-dimensional and (2+1)-dimensional Ito equations. With the help of the Bell polynomials method, Hirota bilinear method and symbolic computation, the bilinear representations, N-soliton solutions, bilinear Bäcklund transformations and Lax pairs of these two equations are obtained, respectively. In particular, we obtain a new bilinear form and N-soliton solutions of the (2+1)-dimensional Ito equation. The bilinear Bäcklund transformation and Lax pair of the (2+1)-dimensional Ito equation are also obtained for the first time. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
975.
976.
977.
Aikaterini M. Gremilogianni Nikolaos C. MegoulasMichael A. Koupparis 《Journal of chromatography. A》2010,1217(43):6646-6651
Streptomycin (STR) and dihydrostreptomycin (DHSTR) are two of the most common aminoglycoside antibiotics used in veterinary medicine. The physicochemical properties of both substances, make their determination challenging. In the present study the development of methods based on ion-pair chromatography (IPC) and on hydrophilic interaction chromatography (HILIC), for the determination of the above mentioned aminoglycosides in the range of 100–1000 μg L−1 is described. The two methods were validated according to EU requirements for residues in food. The recoveries for the IPC method were 69.3% and 56.5% of STR and DHSTR, respectively, and for HILIC method 85.5% and 72.3%, respectively. The intra- and inter-day precision, studied at 100, 200 and 300 μg kg−1 levels in milk samples, gave %RSD ≤ 13 for both methods. LOQs for the HILIC method were 14 μg kg−1 for both analytes and for the IPC method were 109 and 31 μg kg−1, for STR and DHSTR, respectively. The sensitivity of the HILIC method is 80 and 210 times greater than that of the ICP method, for STR and DHSTR, respectively. 相似文献
978.
979.
Jonathan Tennyson Peter F. Bernath Alain Campargue Ludovic Daumont Joseph T. Hodges Oleg L. Polyansky Laurence S. Rothman Ann Carine Vandaele Sophie Fally Tibor Furtenbacher Shui-Ming Hu Boris A. Voronin 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(15):2160-1106
This is the second of a series of articles reporting critically evaluated rotational-vibrational line positions, transition intensities, pressure dependences, and energy levels, with associated critically reviewed assignments and uncertainties, for all the main isotopologues of water. This article presents energy levels and line positions of the following singly deuterated isotopologues of water: HD16O, HD17O, and HD18O. The MARVEL (measured active rotational-vibrational energy levels) procedure is used to determine the levels, the lines, and their self-consistent uncertainties for the spectral regions 0-22 708, 0-1674, and 0-12 105 cm−1 for HD16O, HD17O, and HD18O, respectively. For HD16O, 54 740 transitions were analyzed from 76 sources, the lines come from spectra recorded both at room temperature and from hot samples. These lines correspond to 36 690 distinct assignments and 8818 energy levels. For HD17O, only 485 transitions could be analyzed from three sources; the lines correspond to 162 MARVEL energy levels. For HD18O, 8729 transitions were analyzed from 11 sources and these lines correspond to 1864 energy levels. The energy levels are checked against ones determined from accurate variational nuclear motion computations employing exact kinetic energy operators. This comparison shows that the measured transitions account for about 86% of the anticipated absorbance of HD16O at 296 K and that the transitions predicted by the MARVEL energy levels account for essentially all the remaining absorbance. The extensive list of MARVEL lines and levels obtained are given in the Supplementary Material of this article, as well as in a distributed information system applied to water, W@DIS, where they can easily be retrieved. In addition, the transition and energy level information for H217O and H218O, given in the first paper of this series [Tennyson, et al. J Quant Spectr Rad Transfer 2009;110:573-96], has been updated. 相似文献
980.
J. Suleiman 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(6):857-864
We were able to reproduce the near K edge photoabsorption spectrum of rubidium in the energy range 15,200-15,235 eV. This was done by calculating the transition probabilities for inner shell excitations to singly and doubly excited states. The calculations have been carried out using multi-configuration Dirac-Fock wave functions with the inclusion of the Breit interaction, quantum electrodynamics contributions and finite nuclear size corrections. The transition probabilities were then convoluted into Lorentzian line shapes. A rough estimate of the effect of photoionization was also taken into account. Good overall agreement was attained when the results of the calculation is compared with previous measurements of the K edge photoabsorption spectrum of rubidium. 相似文献