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171.
Laetitia Souillart Evelyne Parker Nicolai Cramer 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2014,126(11):3045-3049
The selective functionalization of carbon–carbon σ bonds is a synthetic strategy that offers uncommon retrosynthetic disconnections. Despite progress in C C activation and its great importance, the development of asymmetric reactions lags behind. Rhodium(I)‐catalyzed selective oxidative additions into enantiotopic C C bonds in cyclobutanones are reported. Even operating at a reaction temperature of 130 °C, the process is characterized by outstanding enantioselectivity with the e.r. generally greater than 99.5:0.5. The intermediate rhodacycle is shown to react with a wide variety of tethered olefins to deliver complex bicyclic ketones in high yields. 相似文献
172.
A Highly Active and Magnetically Recoverable Tris(triazolyl)–CuI Catalyst for Alkyne–Azide Cycloaddition Reactions
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Dr. Dong Wang Laetitia Etienne María Echeverria Prof. Sergio Moya Prof. Dr. Didier Astruc 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):4047-4054
Nanoparticle‐supported tris(triazolyl)–CuBr, with a diameter of approximately 25 nm measured by TEM spectroscopy, has been easily prepared, and its catalytic activity was evaluated in the copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reaction. In initial experiments, 0.5 mol % loading successfully promoted the CuAAC reaction between benzyl azide and phenylacetylene, in water at room temperature (25 °C). During this process, the iron oxide nanoparticle‐supported tris(triazolyl)–CuBr displayed good monodispersity, excellent recoverability, and outstanding reusability. Indeed, it was simply collected and separated from the reaction medium by using an external magnet, then used for another five catalytic cycles without significant loss of catalytic activity. Inductively coupled plasma (ICP) analysis for the first cycle revealed that the amount of copper leached from the catalyst into the reaction medium is negligible (1.5 ppm). The substrate scope has been examined, and it was found that the procedure can be successfully extended to various organic azides and alkynes and can also be applied to the one‐pot synthesis of triazoles, through a cascade reaction involving benzyl bromides, alkynes, and sodium azide. In addition, the catalyst was shown to be an efficient CuAAC catalyst for the synthesis of allyl‐ and TEG‐ended (TEG=triethylene glycol) 27‐branch dendrimers. 相似文献
173.
Trupia L Dechamps N Flammang R Bouchoux G Nguyen MT Gerbaux P 《Journal of the American Society for Mass Spectrometry》2008,19(1):126-137
The isomerization process between ionized phenol and ionized cyclohexadienone is studied by performing ion/molecule reactions with several alkyl nitrites in a hexapole collision cell inserted in a six-sector mass spectrometer. The distinction between both isomeric species is readily achieved on the basis of the completely different reactivity patterns observed for them in subsequent reactions. When reacting with alkyl nitrite, ionized phenol undergoes two competitive reactions corresponding to the formal radical substitution of the hydroxylic hydrogen atom by respectively (i) the nitrosyl radical (m/z 123) and (ii) an alkoxyl radical (m/z 138 if alkyl=ethyl). Both reactions were theoretically demonstrated by density functional theory calculations [B3LYP/6-311++G(d,p)+ZPE] to involve hydrogen-bridged radical cations as key intermediates. The ion/molecule reaction products detected starting from ionized cyclohexadienone as the mass-selected ions arise from *OAlkyl, *OH, and NO2* radical additions. The occurrence of a spontaneous ring-opening of cyclohexadienone radical ion into a distonic species is suggested to account for the observed ion/molecule reaction products. We also demonstrated that ionized cyclohexadienone is partly isomerized during a proton-transfer catalysis process into ionized phenol inside the Hcell with ethyl nitrite as the base. The molecular ions of phenol generated in such conditions consecutively undergo reactions producing m/z 123 and 138 radical cations. The proposed mechanism is supported by results of quantum chemical calculations. 相似文献
174.
Mouls L Subra G Aubagnac JL Martinez J Enjalbal C 《Journal of mass spectrometry : JMS》2006,41(11):1470-1483
The behavior of C-terminal amidated and carboxylated peptides upon low-energy collision-induced dissociation (CID) was investigated. Two sets of 76 sequences of variable amino acid compositions and lengths were synthesized as model compounds. In most cases, C-terminal amidated peptides were found to produce, upon CID, an abundant loss of ammonia from the protonated molecules. To validate such MS/MS signatures, the studied peptides contained amino acids that can potentially release ammonia from their side chains, such as asparagine, glutamine, tryptophan, lysine and arginine. Arginine, and to a lesser extent lysine, was shown to induce a competitive fragmentation leading to the loss of ammonia from their side chains, thus interfering with the targeted backbone neutral release. However, when arginine or lysine was located at the C-terminal position mimicking a tryptic digest, losses of ammonia from the arginine side chain and from the peptide backbone were completely suppressed. Such results were discussed in the frame of peptidomic or proteomic studies in an attempt to reveal the presence of C-terminal amidated peptides or proteins. 相似文献
175.
Laetitia Bueno-Ravel Ghislaine Gueudet 《International Journal of Computers for Mathematical Learning》2009,14(1):1-20
The study we present here concerns the consequences of integrating online resources into the teaching of mathematics. We focus
on the interaction between teachers and specific online resources they draw on: e-exercise bases. We propose a theoretical
approach to study the associated phenomena, combining instrumental and anthropological perspectives. For given didactical
tasks, we observe teachers’ instrumental geneses, and the didactical techniques they develop. We exemplify our approach with
the analysis of a case study of trigonometry in grade 9.
相似文献
Ghislaine GueudetEmail: |
176.
Damiana Lerose Mikhael Bechelany Laetitia Philippe Johann Michler Silke Christiansen 《Journal of Crystal Growth》2010,312(20):2887-2891
Gold dot arrays on (1 1 1) Si substrates obtained through nanosphere lithography (NSL) combined with sputtering and annealing in Ar at 1000 °C are used to catalyze vapor liquid solid (VLS) epitaxial growth of silicon nanowires (Si NWs) using chemical vapor deposition (CVD) with SiH4 in Ar. The NWs grow primarily epitaxially on the underlying (1 1 1) Si wafer following the four independent 〈1 1 1〉 directions. The diameter distribution of the wires reflects the diameter distribution of the catalyst gold dot arrays and is therefore predictable. The wire length depends on the size of the gold catalyst for the same CVD parameters. The wire position is foreseeable within the limits of the pattern geometrical quality, but one-to-one growth of NWs to gold dots is not always observed, probably due to (very locally) the remaining presence of silicon oxide. Overall, this inexpensive patterning method for obtaining high-quality crystalline VLS Si NWs by CVD fulfills the requirements of many device applications, where patterning control, quality and reproducibility of the nanostructures are crucial. 相似文献
177.
Dr. Baptiste Lecachey Dr. Laetitia Palais Dr. Benoît de Courcy Dr. Samira Bouauli Dr. Muriel Durandetti Prof. Hassan Oulyadi Dr. Anne Harisson-Marchand Dr. Jacques Maddaluno Prof. Hélène Gérard Dr. Emmanuel Vrancken Prof. Jean-Marc Campagne 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(29):7942-7950
The reaction of a silyl dienolate, a Cu(II) salt and TBAT yielding the corresponding copper dienolate is addressed. A combined NMR and cyclic voltammetry analysis first highlight the role of TBAT in the Cu(II) to Cu(I) reduction and the structure of the precatalytic species. From these first results a second set of NMR and theoretical studies enable the determination of the structure and the mechanism of formation of the copper dienolate catalytic species. Finally, we showed that that the copper catalyst promote the E/Z s-cis/s-trans equilibration of the silyl dienolate precursor through a copper dienolate intermediate. All of these results unveil some peculiarities of the catalytic and asymmetric vinylogous Mukaiyama reaction. 相似文献
178.
Oumaima Zidi Nessrine Souai Henda Raies Farhat Ben Ayed Amel Mezlini Sonia Mezrioui Fabrice Tranchida Jean-Marc Sabatier Amor Mosbah Ameur Cherif Laetitia Shintu Soumaya Kouidhi 《Molecules (Basel, Switzerland)》2021,26(8)
Breast cancer (BC) is the most common form of cancer among women worldwide. Despite the huge advancements in its treatment, the exact etiology of breast cancer still remains unresolved. There is an increasing interest in the role of the gut microbiome in modulating the anti-cancer therapeutic response. It seems that alteration of the microbiome-derived metabolome potentially promotes carcinogenesis. Taken together, metabolomics has arisen as a fascinating new omics field to screen promising metabolic biomarkers. In this study, fecal metabolite profiling was performed using NMR spectroscopy, to identify potential biomarker candidates that can predict response to neoadjuvant chemotherapy (NAC) for breast cancer. Metabolic profiles of feces from patients (n = 8) following chemotherapy treatment cycles were studied. Interestingly, amino acids were found to be upregulated, while lactate and fumaric acid were downregulated in patients under the second and third cycles compared with patients before treatment. Furthermore, short-chain fatty acids (SCFAs) were significantly differentiated between the studied groups. These results strongly suggest that chemotherapy treatment plays a key role in modulating the fecal metabolomic profile of BC patients. In conclusion, we demonstrate the feasibility of identifying specific fecal metabolic profiles reflecting biochemical changes that occur during the chemotherapy treatment. These data give an interesting insight that may complement and improve clinical tools for BC monitoring. 相似文献
179.