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31.
The combination of a high‐order unstructured spectral difference (SD) spatial discretization scheme with sub‐grid scale (SGS) modeling for large‐eddy simulation is investigated with particular focus on the consistent implementation of a structural mixed model based on the scale similarity hypothesis. The difficult task of deriving a consistent formulation for the discrete filter within the SD element of arbitrary order led to the development of a new class of three‐dimensional constrained discrete filters. The discrete filters satisfy a set of selected criteria and are completely local within the SD element. Their weights can be automatically computed at run time from the number of solution points within each element and the expected filter cutoff length scale. The novel discrete filters can be applied to any SGS model involving explicit filtering and to a broad class of high‐order discontinuous finite element numerical schemes. The code is applied to the computation of turbulent channel flows at three Reynolds numbers, namely Reτ = 180, 395, and 590 (based on the friction velocity uτ and channel half‐width δ). Results from computations with and without the SGS model are compared against results from direct numerical simulation. The numerical experiments suggest that the results are sensitive to the use of the SGS model, even when a high‐order numerical scheme is used, especially when the grid resolution is kept relatively low and mostly in terms of resolved Reynolds stresses. Results obtained using existing filters based on the projection of the solution over lower‐order polynomial bases are also shown and demonstrate that these filters are inadequate for SGS modeling purposes, mostly because of their inability to enforce the selected cutoff length scale with sufficient accuracy. The use of the similarity mixed formulation proved to be particularly accurate in reproducing SGS interactions, confirming that its well‐known potential can be realized in conjunction with state‐of‐the‐art high‐order numerical schemes.Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
32.
33.
Dr. Samuel Oger Damien Schapman Dr. Romain Mougeot Dr. Stéphane Leleu Dr. Noëlle Lascoux Dr. Patrice Baldeck Dr. Magalie Bénard Dr. Thibault Gallavardin Dr. Ludovic Galas Dr. Xavier Franck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(46):10954-10964
Epicocconone 1 is a natural chromophore isolated from the fungus Epicoccum nigrum that has shown applications in proteomics and fluorescent microscopy thanks to its unique pro-fluorescence properties. The modification of the skeleton of the natural product by replacing the triene side chain by a fluorenyl scaffold can noticeably increase the fluorophore's absorption coefficient. The synthesis of the analogues of the natural product has been made possible by the use of a palladium-catalyzed carbonylation reaction, allowing the construction of the β-keto-dioxinone key intermediate. Two-photon absorption cross-section measurements of the fluorenyl epicocconone analogues show a structure dependency with values ranging from 60 to 280 GM and live cell imaging show intense staining of intracellular vesicle-like structures around the nucleus. 相似文献
34.
Dr. Adrien Bourdolle Dr. Mustapha Allali Dr. Anthony D'Aléo Dr. Patrice L. Baldeck Dr. Kenji Kamada Prof. J. A. Gareth Williams Dr. Hubert Le Bozec Dr. Chantal Andraud Dr. Olivier Maury 《Chemphyschem》2013,14(14):3361-3367
The synthesis of tris(2‐thenoyltrifluoroacetonate)lanthanide(III) complexes featuring a diethylaminostyryl‐2,2′‐bipyridine coligand was achieved for lanthanum; the near‐infrared (NIR) emitters neodymium, erbium, and ytterbium; and the transition‐metal yttrium. The photophysical properties were thoroughly studied, and it was demonstrated that the conjugated bipyridine ligand acts as a good antenna for the sensitization of the NIR emitters. The two‐photon absorption (TPA) properties of all five complexes were investigated by using both two‐photon excited fluorescence and the Z‐scan method. We demonstrate that the nature of the rare earth ion has almost no influence on the TPA properties centered on the conjugated bipyridyl ligand. Finally, we show that YbIII is sensitized by a two‐photon antenna effect, and that NdIII is mostly sensitized by a one‐photon process involving direct excitation of forbidden f–f transitions. 相似文献
35.
Armand Gellis Charline Kieffer Nicolas Primas Gilles Lanzada Michel Giorgi Pierre Verhaeghe Patrice Vanelle 《Tetrahedron》2014
We report herein a new methodology for synthesizing quinazoline derivatives bearing a heteroarylamino moiety at position-4 of the quinazoline ring. As an alternative to the Buchwald–Hartwig cross-coupling reaction, which appears, until now, as the only efficient way to react 4-chloroquinazolines with numerous amino nitrogen-containing heterocycles displaying poor nucleophilicity, we developed a DMAP-catalyzed reaction involving microwave irradiation. Optimization of the reaction conditions led to the use of 30 mol % of DMAP in toluene, using a monomode microwave reactor and sealed vials. Moreover, the SNAr reaction intermediate salt was isolated and fully characterized. Finally, the procedure was extended to two different 2-substituted-quinazoline series and also to various anilines, demonstrating that this approach was a general efficient way to access to such 4-substituted quinazoline scaffolds of high pharmaceutical interest. 相似文献
36.
Hussein Awada Leila Mezzasalma Sylvie Blanc Delphine Flahaut Christine Dagron‐Lartigau Joël Lyskawa Patrice Woisel Antoine Bousquet Laurent Billon 《Macromolecular rapid communications》2015,36(16):1486-1491
The functionalization of zinc oxide (ZnO) nanoparticles by poly(3‐hexylthiophene) (P3HT) brush is completed by the combination of a mussel inspired biomimetic anchoring group and Huisgen cyclo‐addition “click chemistry.” Herein, the direct coupling of an azide modified catechol derivative with an alkyne end‐functionalized P3HT is described. This macromolecular binding agent is used to access core@corona ZnO@P3HT with a stable and homogeneous conjugated organic corona. Preliminary photoluminescence measurement proves an efficient electron transfer from the donor P3HT to the acceptor ZnO nanoparticles upon grafting, thus demonstrating the potential of such a combination in organic electronics.
37.
Léna Sambe Victor R. de La Rosa Khaled Belal Dr. François Stoffelbach Dr. Joel Lyskawa Dr. François Delattre Marc Bria Prof. Graeme Cooke Prof. Richard Hoogenboom Prof. Patrice Woisel 《Angewandte Chemie (International ed. in English)》2014,53(20):5044-5048
A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT4+) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT4+ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences. 相似文献
38.
Sébastien Redon Anne Roly Obah Kosso Julie Broggi Patrice Vanelle 《Tetrahedron letters》2017,58(28):2771-2773
The regioselective selenocyanation of imidazoheterocycles using triselenodicyanide at room temperature is reported. The electrophilic aromatic substitution of a broad range of substrates is promoted by the triselenodicyanide obtained by oxidative coupling of malononitrile and selenium dioxide, under an air atmosphere. The major advantages of the presented method are an easy set-up, excellent yields, short reaction times, use of odorless and inexpensive reagents and easy purification of the final products. 相似文献
39.
Ahlem Bouhlel Christophe Curti Michèle P. Bertrand Patrice Vanelle 《Tetrahedron》2012,68(18):3596-3604
An easily reproducible protocol allowing inter- or intramolecular spirocyclization on β-dicarbonyl structures is described. This methodology could afford a wide variety of spirocyclic pharmacophores. As examples, highly substituted spirobenzophenanthridin-6(5H)-ones and spirolactones were synthesized. These scaffolds could be used for the design of many compounds exhibiting biological activities. 相似文献
40.
Gas-phase behaviour of negative ions produced from thiazidic diuretics under electrospray conditions
Garcia P Popot MA Fournier F Bonnaire Y Tabet JC 《Journal of mass spectrometry : JMS》2002,37(9):940-953
A systematic mass spectrometric study of 10 thiazidic diuretics and related compounds was undertaken by mass spectrometry (MS) with electrospray ionization in the negative ion mode. Collisional dissociation 'in-source' (CID-MS) and in a low-pressure collision cell (CID-MS/MS) were compared in both excitation regions. Spectra obtained by CID-MS and by CID-MS/MS were matched. Using the two methods, loss of HCl and consecutive dissociations from 2HCl losses were exhibited from compounds such as methyclothiazide and trichlormethiazide but not from other thiazidic diuretics that contain chlorine substituents in the aromatic moiety. However, deprotonated dichlorphenamide gave rise to loss of HCl by CID-MS and CID-MS/MS. For other diuretics such as hydroflumethiazide and hydrochlorothiazide, the loss of HCN and [HCN + SO(2)] was relevant. Reaction mechanisms were checked by means of deuterium-hydrogen exchange, which showed that deprotonation took place regioselectively on the heterocyclic moiety. The cleavage pathways require molecular isomerization forming ion-dipole complexes prior to decompositions, allowing long-distance proton transfer for neutral elimination. Identifications of the most specific fragmentations presented in this paper were applied to the screening and unambiguous identification of diuretics for horse doping control. 相似文献