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61.
Kerdelhué JL Langenwalter KJ Warmuth R 《Journal of the American Chemical Society》2003,125(4):973-986
Photolysis of p-tolyldiazirine (6) in the inner phase of a hemicarcerand with four butane-1,4-dioxy linker groups (5) in C(6)D(5)CD(3) at 77 K yields the 5-methylcycloheptatetraene hemicarceplex 5 circle 3b in 41% together with innermolecular reaction products resulting from an insertion of transient p-tolylcarbene (1b) into an acetal C-H or linker C-O bond of 5 and from the addition of 1b to an aryl unit of 5. The yield of incarcerated 3b increased up to 67% if 6 is photolyzed inside a hemicarcerand with deuterated spanners and butane-1,4-dioxy linker groups (d(48)-5). Hemicarceplex 5 circle 3b is not formed if the photolysis is carried out in CDCl(3). Incarcerated 3b is stable at room temperature in the absence of oxygen and is characterized by 1D and 2D NMR spectroscopy. In the presence of oxygen, 3b reacts quantitatively to yield toluene and CO(2). Upon heating solutions of d(48)-5 circle 3b in C(6)D(5)CD(3), 3b rearranges to 1b and m-tolylcarbene (18). Both tolylcarbenes immediately react with the surrounding host. From a product analysis and the measured rate constants for the thermal decomposition of d(48)-5 circle 3b in the temperature range 70-102 degrees C, the activation parameters for the 3b to 1b and 3b to 18 rearrangements are calculated (3b to 1b: DeltaG(373)++ = 27.3 +/- 1.4 kcal/mol, DeltaH(373)++ = 26.4 +/- 1.0 kcal/mol, TDeltaS(373)++ = -0.9 +/- 1.0 kcal/mol; 3b to 18: DeltaG(373)++ = 27.8 +/- 1.4 kcal/mol, DeltaH(373)++ = 19.7 +/- 1.0 kcal/mol, TDeltaS(373)++ = 8.1 +/- 1.0 kcal/mol). These values are compared with those calculated by Geise and Hadad at the B3LYP/6-311+G** level of theory (Geise, C. M.; Hadad, C. M. J. Org. Chem. 2002, 67, 2532-2540). The slightly higher inner phase activation free energy of the 3b to 18 rearrangement is explained through steric constraints imposed by the surrounding hemicarcerand on the transition state. The enthalpy-entropy compensation observed for the 3b to 18 rearrangement is discussed and interpreted as a result of a hemicarcerand and solvent reorganization along the reaction coordinate. It is taken as indirect evidence for the intermediacy of 2-methylbicyclo[4.1.0]hepta-2,4,6-triene in the 3b to 18 rearrangement. 相似文献
62.
Guillou C Beunard JL Gras E Thal C 《Angewandte Chemie (International ed. in English)》2001,40(24):4745-4746
63.
64.
Sarah Djabarouti Pierre Duffau Fabien Xuereb Estibaliz Lazaro Carine Greib Jean-Baptiste Gordien Olivier Caubet Marie-Claude Saux Jean-François Viallard Jean-Luc Pellegrin Dominique Breilh 《Chromatographia》2009,70(5-6):939-945
Liquid chromatography coupled with mass spectrometry for the determination of total and unbound mycophenolic acid and its major metabolite in human plasma has been developed. Sample preparations were based on a fully automated solid-phase extraction process and ultrafiltration. Mass spectrometric data were acquired in a single-ion monitoring method. The analytes and nevirapine (internal standard) were well separated in an isocratic mode over 8 min. Validation study exhibited excellent linearity, with intra- and inter-day precision and accuracy of less than 12%. The assay was successfully applied to the pharmacokinetic study of mycophenolic acid in patients with autoimmune diseases. 相似文献
65.
Catalina Gómez Jean-Luc Putaux Iñaki Mondragon Cristina Castro Piedad Gañán 《Composite Interfaces》2013,20(1):29-37
Cellulose microfibrils extracted by various alkaline treatments of vascular bundles from banana rachis were used to elaborate films. The films were comparatively studied to determine changes in polarity induced by various treatments. Atomic force microscopy was used to characterize the surface morphology of the films and transmission electron microscopy was employed to characterize the microfibrils used to elaborate the films. Contact angles were measured to determine surface free energy (SFE) and thermogravimetric analyses were carried out to determine changes in composition of the films. The results showed that the films of cellulose microfibrils prepared by the peroxide alkaline (PA) and peroxide alkaline-hydrochloric acid (PA-HCl) treatments had lower content of non-cellulosic constituents like xylose and had lower SFE than films of microfibrils treated with KOH-5. Furthermore, specimens treated with the most concentrated KOH solution (18 wt%) and sodium chloride presented the highest SFE and polar component. 相似文献
66.
A passive scalar is advected by a velocity field, with a nonuniform spatial source that maintains concentration inhomogeneities. For example, the scalar could be temperature with a source consisting of hot and cold spots, such that the mean temperature is constant. Which source distributions are best mixed by this velocity field? This question has a straightforward yet rich answer that is relevant to real mixing problems. We use a multiscale measure of steady-state enhancement to mixing and optimize it by a variational approach. We then solve the resulting Euler-Lagrange equation for a perturbed uniform flow and for simple cellular flows. The optimal source distributions have many broad features that are as expected: they avoid stagnation points, favour regions of fast flow, and their contours are aligned such that the flow blows hot spots onto cold and vice versa. However, the detailed structure varies widely with diffusivity and other problem parameters. Though these are model problems, the optimization procedure is simple enough to be adapted to more complex situations. 相似文献
67.
Michael Bs Willy P. Burkard Jean-Luc Moreau Peter Schnholzer 《Helvetica chimica acta》1990,73(4):932-939
The synthesis of the title compound 2 and its diastereoisomer 3 was accomplished using tricarbonyl[1-5-n-(4-methoxycyclohexa-2,4-dien-1-yl)]iron tetrafluoroborate ( 4 ) as a precursor to the cyclohexanone ring. The assignments of the relative configurations of 2 and 3 are based on the X-ray analysis of compound 3 . Both compounds 2 and 3 are potent inhibitors of neuronal noradrenaline uptake in rats with similar potencies in vitro as compared to amitriptyline and desipramine. Compounds 2 and 3 are less potent as serotonin-uptake inhibitors, very weak inhibitors of dopamine uptake, and virtually devoid of antinociceptive activity. 相似文献
68.
Yannick Rio Jean-Franois Nicoud Jean-Luc Rehspringer Jean-Franois Nierengarten 《Tetrahedron letters》2000,41(52):10207-10210
Triethylene glycol terminated poly(aryl ether) dendritic branches with an aldehyde function at the focal point have been prepared and attached to C60 by a 1,3-dipolar cycloaddition. 相似文献
69.
Agnès Rivaton Sylvain Chambon Jean-Luc Gardette Stéphane Guillerez 《Polymer Degradation and Stability》2010,95(3):278-2251
Polymer-based organic solar cells are known to offer a poor stability in real use conditions, and the photodegradation of the active organic layer plays an important role in the reduced lifetime of the devices. This paper focuses on the photodegradation of two conjugated polymers used in organic solar cells, namely poly(2-methoxy-5-(3′,7′-dimethyloctyloxy)-1,4-phenylenevinylene (MDMO-PPV) and poly(3-hexyylthiophene) (P3HT), and their blends with [60]PCBM (methano-fullerene[6,6]-phenyl C61-butyric acid methyl ester), a fullerene derivative. MDMO-PPV and P3HT thin films were submitted to photoageing (λ > 300 nm) in the presence and in the absence of oxygen. The mechanisms by which these polymers degrade were elucidated. P3HT, pristine and blended with PCBM, was shown to be much more stable under illumination than MDMO-PPV. The results showed that, if deposited on an inert substrate and well protected from oxygen with a convenient encapsulation, P3HT:PCBM based active layer should be intrinsically stable for several years in use conditions. 相似文献
70.
Candice Grivel Jean-Louis Rocca Davy Guillarme Jean-Luc Veuthey Sabine Heinisch 《Journal of chromatography. A》2010,1217(4):459-472
Reversed phase gradient elution is the method of choice for pharmaceuticals analysis since it allows reducing the analysis time while improving both the quality of the separation and the detection limits. The current trends are towards faster separations which can be achieved thanks to equipments withstanding ultra-high pressures and/or high temperatures. Under such conditions, gradient separations can be carried out within a few minutes or even a few tens of seconds. A long equilibration time in addition to the gradient time can be therefore very detrimental. In this work, we investigated the extent to which the gradient equilibration time can be reduced and which parameters mainly affect the retention variability of ionizable compounds when using volatile buffers. We first found out an excellent repeatability between run-to-run experiments whatever the equilibration time and the operating conditions. We then pointed out the key operating parameters which allow achieving reproducible runs when varying the equilibration time between runs. With a view of reducing the equilibration time, the effects of various conditions were examined. The latter include the type of additive for mobile phase pH adjustment, the initial eluent composition, the type of stationary phase, the temperature and the flow-rate. Although much remains to be understood about the equilibration process, our study allows making progress in the knowledge of this phenomenon. Based on the present results, a beneficial effect of both temperature and flow-rate was highlighted and operating conditions leading to faster column equilibration are suggested. 相似文献