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71.
In this letter we describe an unusual result in terms of regioselectivity with respect to copper-catalyzed conjugate additions of various Grignard reagents to cyclic enynones. The use of Cu(OTf)(2) and NHC ligand L1 as the catalyst combination in CH(2)Cl(2) led to the unique formation of the 1,4 adduct. This selectivity does not follow the general trend previously observed in the literature using extended Michael acceptors. Moreover these reactions allowed for the creation of a quarternary stereogenic center with enantioselectivities up to 97% ee. 相似文献
72.
Pieters G Gaucher A Marrot J Maurel F Naubron JV Jean M Vanthuyne N Crassous J Prim D 《Organic letters》2011,13(16):4450-4453
The synthesis and properties of new chiral polycyclic architectures that display both helicity and a saddle-type shape are described. The enantiomers have been separated, and their absolute configuration was determined by VCD and ECD. The unprecedented molecular architecture is based on a cyclooctatriene core surrounded by an association of benzo[c]fluorene and ortho-phenylene units. 相似文献
73.
Schebb NH Huby M Morisseau C Hwang SH Hammock BD 《Analytical and bioanalytical chemistry》2011,400(5):1359-1366
Soluble epoxide hydrolase (sEH) is a promising therapeutic target for the treatment of hypertension, pain, and inflammation-related diseases. In order to enable the development of sEH inhibitors (sEHIs), assays are needed for determination of their potency. Therefore, we developed a new method utilizing an epoxide of arachidonic acid (14(15)-EpETrE) as substrate. Incubation samples were directly injected without purification into an online solid phase extraction (SPE) liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS-MS) setup allowing a total run time of only 108 s for a full gradient separation. Analytes were extracted from the matrix within 30 s by turbulent flow chromatography. Subsequently, a full gradient separation was carried out on a 50X2.1 mm RP-18 column filled with 1.7 μm core-shell particles. The analytes were detected with high sensitivity by ESI-MS-MS in SRM mode. The substrate 14(15)-EpETrE eluted at a stable retention time of 96 ± 1 s and its sEH hydrolysis product 14,15-DiHETrE at 63 ± 1 s with narrow peak width (full width at half maximum height: 1.5 ± 0.1 s). The analytical performance of the method was excellent, with a limit of detection of 2 fmol on column, a linear range of over three orders of magnitude, and a negligible carry-over of 0.1% for 14,15-DiHETrE. The enzyme assay was carried out in a 96-well plate format, and near perfect sigmoidal dose-response curves were obtained for 12 concentrations of each inhibitor in only 22 min, enabling precise determination of IC(50) values. In contrast with other approaches, this method enables quantitative evaluation of potent sEHIs with picomolar potencies because only 33 pmol L(-1) sEH were used in the reaction vessel. This was demonstrated by ranking ten compounds by their activity; in the fluorescence method all yielded IC(50) ≤ 1 nmol L(-1). Comparison of 13 inhibitors with IC(50) values >1 nmol L(-1) showed a good correlation with the fluorescence method (linear correlation coefficient 0.9, slope 0.95, Spearman's rho 0.9). For individual compounds, however, up to eightfold differences in potencies between this and the fluorescence method were obtained. Therefore, enzyme assays using natural substrate, as described here, are indispensable for reliable determination of structure-activity relationships for sEH inhibition. 相似文献
74.
Hedberg C Dekker FJ Rusch M Renner S Wetzel S Vartak N Gerding-Reimers C Bon RS Bastiaens PI Waldmann H 《Angewandte Chemie (International ed. in English)》2011,50(42):9832-9837
A matter of common sense: A common recognition motif consisting of a negatively charged group five to six bonds away (red) from the (thio)ester functionality (green) and a positively charged tail group ten to twelve bonds away (blue) was identified in two native acyl protein thioesterase?1 (APT1) substrates. This similarity led to the design of potent inhibitors of the Ras-depalmitoylating enzyme APT1. 相似文献
75.
76.
Bauer M Többens DM Mayer E Loerting T 《Physical chemistry chemical physics : PCCP》2011,13(6):2167-2171
A range of techniques has so far been employed for producing amorphous aqueous solutions. In case of aqueous tetrahydrofuran (THF) this comprises hyperquenching of liquid droplets, vapour co-deposition and pressure-induced amorphization of the crystalline cubic structure II clathrate. All of these samples are thermally labile and crystallize at temperatures above 110 K. We here outline a variant of the pressure-amorphization protocol developed by Suzuki [Phys. Rev. B, 2004, 70, 172108], which results in a highly crystallization resistant amorphous THF hydrate. The hydrate produced according to our protocol (annealing to 180 K at 1.8 GPa rather than to 150 K at 1.5 GPa) does not transform to the cubic structure II THF clathrate even at 150 K. We track the reason for this higher stability to the presence of crystalline remnants when following the Suzuki protocol, which are removed when using our protocol involving higher pressures and an annealing step. These crystalline remnants later serve as crystallization seeds lowering the thermal stability of the amorphous sample. Our protocol thus makes a purely amorphous THF hydrate available to the research community. We use powder X-ray diffraction to study the process of nucleation and slow crystal growth in the temperature range 160-200 K and find that the local cage structure and periodicity of the fully crystalline hydrate develops even at the earliest stages of crystallization, when the "clathrate crystal" has a size of about two unit cells. 相似文献
77.
Open shop problems with unit time operations 总被引:2,自引:0,他引:2
Peter Brucker Bernd Jurisch Marion Jurisch 《Mathematical Methods of Operations Research》1993,37(1):59-73
We show that them-machine open shop problem in which all operations have unit processing times can be polynomially transformed to a special preemptive scheduling problem onm identical parallel machines. Many results published recently as well as some new results are derived by using this transformation. The new results include solutions of open problems mentioned in a recent paper by Kubiak et al. p]A similar relationship is derived between no-wait open shop problems with unit time operations andm-machine problems with jobs having unit processing times.This work was supported by Deutsche Forschungsgemeinschaft (Project JoPTAG). 相似文献
78.
79.
Jean-Luc Tissot 《Comptes Rendus Physique》2003,4(10):1083-1088
The emergence of uncooled detectors has opened new opportunities for IR detection for both military and commercial applications. Development of such devices involves a lot of trade-offs between the different parameters that define the technological stack. These trade-offs explain the number of different architectures that are under worldwide development. The key factor is to find a high sensitivity and low noise thermometer material compatible with silicon technology in order to achieve high thermal isolation in the smallest area as possible. Ferroelectric thermometer based hybrid technology and electrical resistive thermometer based (microbolometer) technology are under development. LETI and ULIS have chosen from the very beginning to develop first a monolithic microbolometer technology fully compatible with commercially available CMOS technology and secondly amorphous silicon based thermometer. This silicon approach has the greatest potential for reducing infrared detector manufacturing cost. After the development of the technology, the transfer to industrial facilities has been performed in a short period of time and the production is now ramping up with ULIS team in new facilities. LETI and ULIS are now working to facilitate the IRFPA integration into equipment in order to address a very large market. Achievement of this goal needs the development of smart sensors with on-chip advanced functions and the decrease of manufacturing cost of IRFPA by decreasing the pixel pitch and simplifying the vacuum package. We present in this paper the technology developed by CEA/LETI and its improvement for being able to designs 384×288 and 160×120 arrays with a pitch of 35 μm. Thermographic application needs high stability infrared detector with a precise determination of the amount of absorbed infrared flux. Hence, infrared detector with internal temperature stabilized shield has been developed and characterized. These results will be presented. To cite this article: J.-L. Tissot, C. R. Physique 4 (2003). 相似文献
80.
We present a model of a new paramagnetic defect center which results from the interaction of atomic hydrogen with the MgO(1 0 0) surface. DFT calculations have been performed using periodic supercells and embedded cluster models where long-range polarization effects are included explicitly. The H atom promotes the creation of an oxygen vacancy (F center) by formation of the FS+(OH−) defect where an hydroxyl group is adsorbed near an electron trapped in an oxygen vacancy. This new center has some characteristics similar to those of the classical FS+ centers but a smaller formation energy; furthermore, being globally neutral, it can be treated also with supercell methods. 相似文献