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81.
Kuethe JT Marcoux JF Wong A Wu J Hillier MC Dormer PG Davies IW Hughes DL 《The Journal of organic chemistry》2006,71(19):7378-7390
A highly efficient synthesis of the potent and selective NK-1 receptor antagonist 1 is described. The key transformation involved the etherification reaction between cyclopentanol 12 and chiral imidate 30 which was catalyzed by HBF4 to initially give ether 14 as a 17:1 mixture of diastereomers and in 75% combined yield. The diastereoselectivity was upgraded to 109:1 by crystallization of the triethylamine solvate 44 which was isolated in 54% yield from 12. Mechanistic studies confirmed that the etherification reaction proceeds through an unprecedented S(N)2 reaction pathway under typical S(N)1 reaction conditions. 相似文献
82.
Vronique Sadtler Marianna Rondon‐Gonzalez Audrey Acrement Lionel Choplin Emmanuelle Marie 《Macromolecular rapid communications》2010,31(11):998-1002
This study reports the first PEO‐coated polymer nanoparticles synthesis by miniemulsion polymerization of nano‐emulsions prepared by the low‐energy emulsification method called EIP. The surfactant used was Brij 98, a PEO based non ionic commercial surfactant. The partial phase diagram of the system water/Brij 98/styrene was first determined. The Emulsion Inversion Point technique was then used on the water/Brij 98/styrene system to the formation of styrene‐in‐water nano‐emulsions. After miniemulsion polymerization, particle sizes as low as 36 nm were obtained. To the best of our knowledge, this method had not been used for polymerizable system up to now.
83.
Gourier D Binet L Scrzypczak A Derenne S Robert F 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2004,60(6):1349-1357
The insoluble organic matter (IOM) of three carbonaceous meteorites (Orgueil, Murchison and Tagish Lake meteorites) and three samples of cherts (microcrystalline SiO2 rock) containing microfossils with age ranging between 45 million years and 3.5 billion years is studied by electron paramagnetic resonance (EPR). The age of the meteorites is that of the solar system (4.6 billion years). The purpose of this work was to determine the EPR parameters, which allow us to discriminate between biogenic and extra terrestrial origin for the organic matter. Such indicators should be relevant for the controversy regarding the biogenicity of the organic matter in the oldest cheroot (3.5 billion years) and in Martian meteorites containing microbe-like microstructures. The organic matter of meteorites contains a high concentration of diradicaloid moieties characterised by a diamagnetic ground state S = 0 and a thermally accessible triplet state S = 1. The three meteorites exhibit the same singlet-triplet gap (ST gap) DeltaE approximately 0.1 eV. To the best of our knowledge, such diradicaloids are unknown in insoluble organic matter of terrestrial origin. We have also shown that the EPR linewidth of insoluble organic matter in cherts and coals decrease logarithmically with the age of the organic matter. We conclude from this result that the organic matter in the oldest cherts (3.5 billion years) has the same age as their SiO2 matrix, and is not due to a latter contamination by bacteria, as was recently found in meteoritic samples. 相似文献
84.
Beattie DA Beaussart A Mierczynska-Vasilev A Harmer SL Thierry B Puskar L Tobin M 《Langmuir : the ACS journal of surfaces and colloids》2012,28(3):1683-1688
Synchrotron FTIR microscopy has been used to probe the structure of model boundary lubricant layers confined at the solid-solid interface. The combination of high brightness of the IR source and a novel contact geometry that uses a hemispherical internal reflection element as the means for light delivery has enabled the detection of <2.5 nm thin monolayer lubricant layers in the solid-solid contact, in addition to allowing for spectral acquisition from specific regions of the contact. Spectra of hydration water from within a confined polyelectrolyte multilayer film have also been acquired, highlighting the altered hydrogen bonding environment within the polymer layer. 相似文献
85.
Energetic and spectral properties of triple photon downconversion in a phase-matched KTiOPO4 crystal
Dot A Borne A Boulanger B Segonds P Félix C Bencheikh K Levenson JA 《Optics letters》2012,37(12):2334-2336
We measured the spectrum and energy of infrared triple photons generated in a phase-matched KTiOPO4 crystal pumped by picosecond beams at 532 and 1662 nm. The experimental data are in good agreement with our model, taking into account the spectral linewidths of the incident beams as well as a parasitic Kerr effect. 相似文献
86.
Ab initio molecular dynamics simulations of the liquid-vapor interface are presented for thin slabs of 72 water molecules containing a single molecule of sulfuric acid. Trajectories in the 306-330 K range are calculated for two functionals with double- and triple-ζ quality basis sets. Comparisons are made between BLYP and HCTH/120 results for the slab simulations and for bulk simulations of one H(2)SO(4) in a periodic box with 63 waters. Good agreement is found with the available experimental data and the results of other relevant AIMD studies with respect to ionization of the acid, size of the coordination shells, partitioning of the ions with the hydronium exhibiting a surface preference and the anions in the interior, and the orientational distributions for the hydronium ions and for the surface/subsurface water molecules. The major differences in the performance of the two functionals are attributable to the greater basicity of the anion oxygen atoms with the HCTH functional and the more structured aqueous solution with BLYP. The enhanced basicity results in larger aqueous coordination shells for the anion oxygens. The structuring of the BLYP aqueous solution is observed in the corrugation of the water density profile, the higher first peak in g(OO)(r), and a smaller water self-diffusion constant. This structuring with the BLYP functional yields anion hydrogen bonds that endure longer and where the dissociated ions more rapidly and directly segregate in the slab. The simulations indicate that aqueous surfaces containing ionizable diprotic acids can be modeled with rather modest sized systems and be informative. 相似文献
87.
C Boyère AF Léonard B Grignard A Favrelle JP Pirard M Paquot C Jérôme A Debuigne 《Chemical communications (Cambridge, England)》2012,48(67):8356-8358
Highly porous materials were produced by acrylamide polymerisation templated by supercritical CO(2)-in-water emulsions using new fluorinated glycosurfactants. Properties of the resulting polymer scaffolds were tuned by performing dispersion polymerisations within their cavities filled with supercritical CO(2). 相似文献
88.
Gaulier C Hospital A Legeret B Delmas AF Aucagne V Cisnetti F Gautier A 《Chemical communications (Cambridge, England)》2012,48(33):4005-4007
A reducing agent-free version of CuAAC able to operate under open air conditions is reported. A readily-synthesizable, hydrophilic and highly stable Cu(I)-NHC allows the clean ligations of unprotected peptides comprising sensitive side chains, at millimolar concentrations. 相似文献
89.
Hudson R Rivière A Cirtiu CM Luska KL Moores A 《Chemical communications (Cambridge, England)》2012,48(27):3360-3362
We report for the first time the use of iron-iron oxide core-shell nanoparticles for the hydrogenation of olefins and alkynes under mild conditions in ethanol and in an aqueous medium. This catalyst proves robust towards the presence of oxidants, such as oxygen and water, is magnetically recoverable and shows selectivity towards the less activated double bonds. 相似文献
90.
Using a Cu(II) 2-quinoxalinol salen complex as the catalyst and tert-butyl hydroperoxide (TBHP) as the oxidant, allylic activations of olefin substrates can be converted to the corresponding enones or 1,4-enediones. Excellent yields can be achieved (up to 99%) within a very short reaction time and with great tolerance for additional functional groups. Possible mechanistic pathways have been characterized using Raman spectroscopy, cyclic voltammetry, and theoretical calculations. 相似文献