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1.
Ozonolysis of a Series of Methylated Alkenes: Reaction Rate Coefficients and Gas‐Phase Products 下载免费PDF全文
Tristan Braure Véronique Riffault Alexandre Tomas Romeo Iulian Olariu Cecilia Arsene Yuri Bedjanian Patrice Coddeville 《国际化学动力学杂志》2015,47(9):596-605
The gas‐phase ozonolysis of three methylated alkenes, i.e., trans‐2,2‐dimethyl‐3‐hexene (22dM3H), trans‐2,5‐dimethyl‐3‐hexene (25dM3H), and 4‐methyl‐1‐pentene (4M1P), has been investigated in the presence of sufficient hydroxyl radical scavenger in a laminar flow reactor at ambient temperature (296 ± 2 K) and P = 1 atm of dry air (RH ≤ 5%). Ozone levels in the reactor were monitored by an automatic analyzer. Alkene and gas‐phase product concentrations were determined via online sampling either on three‐bed adsorbent cartridges followed by thermodesorption and GC/FID‐MS analysis or on 2,4‐dinitrophenylhydrazine (DNPH) cartridges for subsequent HPLC/UV analysis. Reaction rate coefficients of (3.38 ± 0.12) × 10?17 for 22dM3H and (2.71 ± 0.26) × 10?17 for 25dM3H, both in cm3 molecule?1 s?1 units, have been obtained under pseudo–first‐order conditions. Primary carbonyl products have been identified for the three investigated alkenes, and branching ratios are reported. In the case of 4M1P ozonolysis, the yield of a Criegee intermediate was indirectly determined. Kinetics and product study results are compared to those of literature when available. This work represents the first investigation of reaction products in the ozonolysis of 22dM3H, 25dM3H, and 4M1P in a flow reactor. 相似文献
2.
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
3.
Marie-Ange Lespinasse Dr. Kaiyao Wei Justine Perrin Dr. Matthias Winkler Sieme Hamaidia Alexis Leroy Dr. Zuzana Macek Jilkova Dr. Christian Philouze Dr. Patrice N. Marche Dr. Carlo Petosa Dr. Jérôme Govin Dr. Anouk Emadali Dr. Yung-Sing Wong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(64):e202202293
The pharmaceutical industry has a pervasive need for chiral specific molecules with optimal affinity for their biological targets. However, the mass production of such compounds is currently limited by conventional chemical routes, that are costly and have an environmental impact. Here, we propose an easy access to obtain new tetrahydroquinolines, a motif found in many bioactive compounds, that is rapid and cost effective. Starting from simple raw materials, the procedure uses a proline-catalyzed Mannich reaction followed by the addition of BF3 ⋅ OEt2, which generates a highly electrophilic aza-ortho-quinone methide intermediate capable of reacting with different nucleophiles to form the diversely functionalized tetrahydroquinoline. Moreover, this enantioselective one-pot process provides access for the first time to tetrahydroquinolines with a cis-2,3 and trans-3,4 configuration. As proof of concept, we demonstrate that a three-step reaction sequence, from simple and inexpensive starting compounds and catalysts, can generate a BD2-selective BET bromodomain inhibitor with anti-inflammatory effect. 相似文献
4.
5.
Capillary electrophoresis for rapid identification of monoclonal antibodies for routine application in hospital 下载免费PDF全文
Emmanuel Jaccoulet Claire Smadja Patrice Prognon Myriam Taverna 《Electrophoresis》2015,36(17):2050-2056
mAbs are widely used in cancer therapy. Their compounding, performed just before their administration to patients, is executed in a production unit of the hospital. Identification of these drugs, individually prepared in bags for infusion before patient administration, is of paramount importance to detect potential mistakes during compounding stage. A fast and reliable analytical method based on CZE combined to a cationic capillary coating (hexadimethrine bromide) was developed for identification of the most widely used compounded therapeutic for cancer therapy (bevacizumab, cetuximab, rituximab, and trastuzumab). Considering the high structural and physico‐chemical similarities of these mAbs, an extensive optimization of the BGE composition has been performed. The addition of perchlorate ions and polysorbate in the BGE greatly increased the resolution. To validate the method, an internal standard was used and the relative migration times (RTm) were estimated. Very satisfactory RSDs of the RTm for rituximab (0.76%), cetuximab (0.46%), bevacizumab (0.31%), and trastuzumab (0.60%) were obtained. The intraday and interday RSD of the method were less than 0.32 and 1.3%, respectively for RTm. Significant differences between theses RTms have been demonstrated allowing mAbs identification. Finally, accurate mAbs identification has been demonstrated by a blind test. 相似文献
6.
In squeeze flow rheometry, the main problem is the boundary condition between the squeezed material and the plates. Therefore, the crucial assumption is to know the location and the shape of the sample part where wall slip may or may not occur. This question is investigated from experimental results. For this, squeeze flow experiments are carried out to visualize the flow pattern at the walls. Influence of boundary conditions is particularly studied using different plate surface condition. As a result, with wall slipping conditions, we propose a flow modelling divided into two zones: a circular central zone of the sample sticks on the plates and, beyond that zone, the sample slips at the plates with friction. 相似文献
7.
This paper develops a theoretical analysis of a Bingham fluid in slipping squeeze flow. The flow field decomposition consists
in combining a central extensional flow zone in the plane of symmetry and shear flow zones near the plates. It is also considered
that the slipping zone is located around a central sticking zone as previously shown from experiments. It is assumed that
the shear stress at the plates is constant in the slipping zone and equals a fixed friction yield value. The squeeze force
required to compress a Bingham fluid under the slipping behaviour as well as the radial evolution of the transition point
between both sticking and slipping zones are finally determined. 相似文献
8.
Guido Lodato Patrice Castonguay Antony Jameson 《Flow, Turbulence and Combustion》2014,92(1-2):579-606
The combination of the high-order unstructured Spectral Difference (SD) spatial discretization scheme with Sub-Grid Scale (SGS) modeling for Wall-Modeled Large-Eddy Simulation (WMLES) is investigated. Particular focus is given to the use of wall-function approaches and to the relevant optimal coupling with the numerical scheme and the SGS model, a similarity mixed type model featuring newly designed discrete filters with specified cutoff length scale. To take full advantage of the discontinuous Finite Element (FE) structure which characterizes the SD scheme, wall-modeling is accomplished within the first wall element by using the information from the farthest solution points from the wall. Compared to the customary used first off-wall node, this point provides more accurate information to the wall-function, thus improving the quality of the solution. Two different law-of-the-wall are tested, a classical three-layers wall-function based on the equilibrium assumption and a more general formulation to account for the pressure gradient in more complex configurations. Moreover, the mixed scale-similarity SGS model is used in the entire computational domain without any particular adjustment inside the wall-modeled region. Numerical tests on the classical test case of the turbulent channel flow at different Reynolds numbers and on the channel with periodic constrictions at Re h = 10,595 give evidence that the results are extremely sensitive to the choice of the solution points used to provide the informations to the law-of-the-wall. In particular, it is shown that significant improvements in the results can be attained by solving the wall-function away from the wall, rather than at the first off-wall solution point as customary done. The combination of the selected wall-modeling strategies and the similarity mixed formulation proves to be remarkably accurate, even in the presence of boundary layer separation, thus opening the path to further exploit the high-order SD platform, as well as a broad range of other similar methodologies, for WMLES. Extensions of the methodology are envisaged to include more sophisticated wall-modeling approaches incorporating turbulent sensors to switch to no-slip conditions in laminar regions. 相似文献
9.
10.
We report here the first example of a one-pot synthesis of 2-(alkyl)arylbenzoselenazoles from N-(acetyl)benzoyl-2-iodoanilines. The reaction was carried out in the presence of Woollins’ reagent under microwave irradiation and resulted in moderate to good yields. 相似文献