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971.
Sylvain Antoniotti 《Tetrahedron letters》2009,50(21):2536-4719
In the presence of 5 mol % of tin(IV) triflimidate, a cyclization reaction of epoxyesters to δ-hydroxy-γ-lactones proceeding in 46-98% yields without additives, ligands, or co-catalysts was observed. The cyclization to five-membered rings is greatly favored compared to the possible six-membered rings formation and is probably under the control of a Thorpe-Ingold type effect. 相似文献
972.
Jos Alberto Galicia Aguilar Sylvain Berns 《Acta Crystallographica. Section C, Structural Chemistry》2009,65(4):o176-o178
3,6‐Dinitrodurene (1,2,4,5‐tetramethyl‐3,6‐dinitrobenzene), C10H12N2O4, has been crystallized in two polymorphic forms which may be distinguished by their colours in the solid state. Polymorph I gives clear colourless prismatic crystals, while polymorph II crystallizes in the dark and under an inert atmosphere as irregular purple blocks. Both forms belong to the space group C2/c, with both asymmetric units containing two half‐molecules. One molecule is located on an inversion centre and the other lies on a twofold axis. The polymorphism arises from different orientations of the twofold axis: in form I, this axis passes through the mid‐points of two C—C bonds of the benzene ring and, as a consequence, all atoms in the asymmetric unit are in general positions. In form II, the N atoms of the nitro groups and the Cipso atoms are located on the binary axis. Comparing phases I and II, slightly different conformations are observed for the nitro substituents, while the stacking structures are very similar. 相似文献
973.
Sylvain Ervedoza Jean-Pierre Puel 《Annales de l'Institut Henri Poincaré (C) Analyse Non Linéaire》2009
In this article, we analyze the approximate controllability properties for a system of Schrödinger equations modeling a single trapped ion. The control we use has a special form, which takes its origin from practical limitations. Our approach is based on the controllability of an approximate finite dimensional system for which one can design explicitly exact controls. We then justify the approximations which link up the complete and approximate systems. This yields approximate controllability results in the natural space (L2(R))2 and also in stronger spaces corresponding to the domains of powers of the harmonic operator. 相似文献
974.
Hana Ben Abderrazak Aurélie Fildier Sylvain Marque Damien Prim Hatem Ben Romdhane Hans R. Kricheldorf Saber Chatti 《European Polymer Journal》2011,(11):2097-2110
New polyesters were prepared by polycondensation in solution of 1,4:3,6 dianhydrohexitols with various aliphatic–aromatic acid dichlorides which differ by their chain length (m = 6,8,10). They are obtained with yields in the range of between 89% and 95%. In order to obtain these polymers within optimum conditions, a systematic study was conducted on the effect of the parameters involved in the reaction, such as the alkyl chain length of acid dichlorides and the endo or exo positions of hydroxyl function of diols. The resulting polyesters were characterized by different analytical techniques such as NMR (1H and 13C), FT-IR spectrometry, SEC measurements and MALDI-ToF mass spectrometry. Under optimized conditions a high molar fraction of cyclic polyesters was formed.The differential scanning calorimetry (DSC) measurements revealed an amorphous character with glass transition temperatures in the range of 27–45 °C. The polymers are obtained with inherent viscosities in the range of 0.11–0.25 dL/g with a polydispersity index between 1.75 and 1.99. 相似文献
975.
Agullo J Canesi S Schaper F Morin M Bélanger D 《Langmuir : the ACS journal of surfaces and colloids》2012,28(10):4889-4895
The in situ generation of 3-diazonium cations from 3-aminopyridine and their subsequent stability under experimental conditions used for electrografting of pyridine groups were investigated by spectroscopy and electrochemistry. UV spectroscopy revealed the rapid kinetics for the reaction of 3-aminopyridine with sodium nitrite in HCl to form the 3-diazopyridinium cation with a second-order rate constant of 550 ± 20 L mol(-1) s(-1) at 22 °C. UV spectroscopy showed that the 3-diazopyridinium ion was relatively unstable and its transformation into 3-hydroxypyridine was proven by (1)H NMR. Its hydrolytic decomposition was investigated by NMR and followed first-order kinetics with a rate constant of (53 ± 5) × 10(-3) s(-1) at 22 °C. These results enable us to establish the appropriate conditions for the electrografting of pyridine from the corresponding diazonium cations generated in situ. The electrochemical modification of glassy carbon electrodes with pyridine was characterized by cyclic voltammetry and the resulting grafted layer by electrochemical impedance spectroscopy in the presence of Fe(CN)(6)(3-/4-) as redox probes. The effect of diazotization time before electrochemical reduction on the blocking effect of the grafted layer was investigated and showed that an increase of the diazotization time led to less efficient grafting. The presence of immobilized pyridine on the electrode surface was demonstrated by X-ray photoelectron spectroscopy measurements, and a surface coverage of 8.8 × 10(-10) mol cm(-2) was estimated for the grafted pyridine groups. The significance of these results for researchers using the in situ generation approach for electrochemical and chemical grafting is discussed. 相似文献
976.
Dr. Tariq Mahmood Yilei Wu Domitille Loriot Dr. Marina Kuimova Dr. Sylvain Ladame 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(39):12349-12356
The synthesis of a geometrically constrained and near‐planar hexacyclic acridinium cyanine dye 9 is reported. When compared to its unlocked and non‐fluorescent monomethine cyanine dye analogue 3 , this photostable dye emits in the green area of the spectrum with a remarkable quantum yield close to unity in organic solvents and above 0.5 in water. A detailed steady‐state and time‐resolved spectroscopic study revealed that dye 9 forms emissive aggregates in water, which are responsible for a red‐shifted and broadened emission band and longer emission lifetime, τ≈33 compared to 6.5–7.0 ns for the monomeric dye. Dye 9 also binds strongly to DNA (both duplex and quadruplex) in its monomeric form and is very efficiently taken up by cells, in which it accumulates primarily into the nucleus. 相似文献
977.
Zhu Y Smith DA Herbert DE Gatard S Ozerov OV 《Chemical communications (Cambridge, England)》2012,48(2):218-220
Reactions of a series of phenyl esters with a (PNP)Rh fragment have been studied. PhO(2)CPh only underwent C-H oxidative addition (OA). PhO(2)CCF(3) chiefly underwent acyl-oxygen OA. PhO(2)CBu(t) and PhO(2)CNEt(2) initially underwent OA of an ortho-C-H bond of the phenyl group but continued thermolysis led to the phenyl-oxygen OA products. 相似文献
978.
Elena Bagryanskaya Paul Brmond Mariya Edeleva Sylvain R. A. Marque Dmitriy Parkhomenko Valrie Roubaud Didier Siri 《Macromolecular rapid communications》2012,33(2):152-157
In recent work, a 15‐fold increase in the C–ON bond homolysis rate constant kd of 4‐pyridylethyl‐SG1‐based alkoxyamine was observed upon protonation of the pyridyl moiety in organic solvent. In this report, the pH dependence of kd (pKa = 4.7) is investigated in D2O/CD3OD (v/v 1:1). A 64‐fold increase in kd is observed at acidic pH. Calculations show that the increase in kd upon protonation is due to both an increase in the stabilization of the protonated 4‐pyridylethyl radical and an increase of the destabilization of the starting materials through an increase in the polarity of the alkyl fragment. This new alkoxyamine is applied to NMP of styrene and sodium styrene sulfonate. 相似文献
979.
Ledreux A Sérandour AL Morin B Derick S Lanceleur R Hamlaoui S Furger C Biré R Krys S Fessard V Troussellier M Bernard C 《Analytical and bioanalytical chemistry》2012,403(7):1995-2007
Successive unexplained shellfish toxicity events have been observed in Arcachon Bay (Atlantic coast, France) since 2005. The positive mouse bioassay (MBA) revealing atypical toxicity did not match the phytoplankton observations or the liquid chromatography-tandem mass spectrometry (LC-MS/MS) investigations used to detect some known lipophilic toxins in shellfish. The use of the three cell lines (Caco2, HepG2, and Neuro2a) allows detection of azaspiracid-1 (AZA1), okadaic acid (OA), or pectenotoxin-2 (PTX2). In this study, we proposed the cell-based assays (CBA) as complementary tools for collecting toxicity data about atypical positive MBA shellfish extracts and tracking their chromatographic fractionation in order to identify toxic compound(s). The present study was intended to investigate the responses of these cell lines to shellfish extracts, which were either control or spiked with AZA1, OA, or PTX2 used as positive controls. Digestive glands of control shellfish were extracted using the procedure of the standard MBA for lipophilic toxins and then tested for their cytotoxic effects in CBA. The same screening strategy previously used with pure lipophilic toxins was conducted for determining the intra- and inter-laboratory variabilities of the responses. Cytotoxicity was induced by control shellfish extracts whatever the cell line used and regardless of the geographical origin of the extracts. Even though the control shellfish extracts demonstrated some toxic effects on the selected cell lines, the extracts spiked with the selected lipophilic toxins were significantly more toxic than the control ones. This study is a crucial step for supporting that cell-based assays can contribute to the detection of the toxic compound(s) responsible for the atypical toxicity observed in Arcachon Bay, and which could also occur at other coastal areas. 相似文献
980.
Marie-Anne Pilette Jérôme Marrot Sylvain Duval Fatma Bannani Sébastien Floquet Francis Sécheresse Emmanuel Cadot 《Comptes Rendus Chimie》2012,15(2-3):124-129
Reaction of the [Mo2O2S2(OH2)6]2+ aqua cation and [WO4]2? with the trivacant ion [α-B-AsW9O33]9? in acidic condition (pH = 1.4) leads to the formation of a {Mo2S2O2}-supported polyoxotungstate. The mixed salt NMe4K12[(α–AsW9O33)3(WO(OH2))3(Mo2O2S2(H2O)4)]?20H2O (noted TMAK12–1) has been obtained as single crystals and structurally characterized by X-ray diffraction analysis. The structural analysis of TMAK12-1 reveals a molecular polyoxotungsto-arsenate (III) framework consisting of three α-{AsW9O33} subunits mutually linked by three {O = W-OH2}4+ groups. The resulting triangular arrangement delimits a large “open-space”, lined on the periphery by six terminal oxygen atoms. The central cavity is partially filled by a single {Mo2O2S2(OH2)4}2+ which spans two {AsW9O33} subunits. Furthermore, three potassium ions have been located, one being embedded within the central cavity and the other two, symmetrically distributed at the periphery of the central cavity. In the solid state, two anions 1 interact through hydrogen bonds and ionic contacts to give a large dimeric arrangement bordered by two TMA+ cations. 1 has been characterized in solution (Li+ salt) by its 183W NMR spectrum which contains 16 lines in agreement with the Cs idealized symmetry assumed for the isolated anion 1. Infrared data and elemental analysis are also supplied. 相似文献