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31.
Nicolas Bouleau 《Journal of Functional Analysis》2007,251(1):325-345
The error on a real quantity Y due to the graduation of the measuring instrument may be asymptotically represented, when the graduation is regular and fines down, by a Dirichlet form on R whose square field operator does not depend on the probability law of Y as soon as this law possesses a continuous density. This feature is related to the “arbitrary functions principle” (Poincaré, Hopf). We give extensions of this property to Rd and to the Wiener space for some approximations of the Brownian motion. This gives new approximations of the Ornstein-Uhlenbeck gradient. These results apply to the discretization of some stochastic differential equations encountered in mechanics. 相似文献
32.
Peter Friz Nicolas Victoir 《Annales de l'Institut Henri Poincaré (B) Probabilités et Statistiques》2007,43(6):775-785
We study large deviation principles for Gaussian processes lifted to the free nilpotent group of step N. We apply this to a large class of Gaussian processes lifted to geometric rough paths. A large deviation principle for enhanced (fractional) Brownian motion, in Hölder- or modulus topology, appears as special case. 相似文献
33.
A highly flexible method for direct and quantitative determination of surface Br?nsted acidity of solids in terms of number, type and strength of the acid sites based on quantitative H/D exchange kinetics between the acid solid and gaseous D2O has been developed and applied to materials covering the whole range of acidity. 相似文献
34.
Nicolas Le Calvez 《中国化学会会志》2002,49(4):585-592
The aim of this study was to develop an analytical method to determine the organochlorine concentrations in sediments. Combination of Microwave assisted Solvent Extraction (MASE) and capillary gas chromatography with specific detection (electron capture detector) was a viable approach for the determination of pesticides in solid matrixes. In this study, MASE development was focused on the selection of a suitable extraction solvent for all the target analytes. MASE procedure was validated by comparison with conventional methods such as Soxhlet and sonication extraction. The proposed method was then applied to determine the organochlorine insecticides concentrations in samples from Authie Bay (France). Environmental water samples were analysed and five target analytes were detected in concentrations from 0.03 to 0.56 ng/g of dry sediment. These investigations showed the accumulation and the persistency of these products in sediments in spite of the fact they were banned a few decades ago. 相似文献
35.
We present solubility and diffusion data for the gases methane and carbon dioxide in the polymer poly(vinylidene fluoride). The polymer was cut from extruded piping intended for use in offshore oil and gas applications. Measurements were carried out using a purpose-built high-pressure microbalance. These properties were determined in the temperature range 80-120 °C and in the pressure range 50-150 bar for methane and 20-40 bar for carbon dioxide. In general, good agreement was obtained for similar measurements reported in the literature. Solubility follows a Henry’s law (linear) dependence with pressure. Diffusion coefficients for each of the gases in the polymer were also measured using the balance. Activation energies for diffusion and heats of solution for the two gases in the polymer were also determined. 相似文献
36.
Clément JL Ferré N Siri D Karoui H Rockenbauer A Tordo P 《The Journal of organic chemistry》2005,70(4):1198-1203
[structure: see text] Spin trapping consists of using a nitrone or a nitroso compound to "trap" an unstable free radical as a long-lived nitroxide that can be characterized by electron paramagnetic resonance (EPR) spectroscopy. The formation of DMPO-OOH, the spin adduct resulting from trapping superoxide (O(2)(*)(-)) with 5,5-dimethyl-1-pyrroline N-oxide (DMPO), has been exploited to detect the generation of superoxide in a wide variety of biological and chemical systems. The 12-line EPR spectrum of DMPO-OOH has been either reported or mentioned in more than a thousand papers. It has been interpreted as resulting from the following couplings: A(N) approximately 1.42 mT, A(H)beta approximately 1.134 mT, and A(H)gamma(1H) approximately 0.125 mT. However, the DMPO-OOH EPR spectrum has an asymmetry that cannot be reproduced when the spectrum is calculated considering a single species. Recently, it was proposed that the 0.125 mT splitting was misassigned and actually results from the superimposition of two individual EPR spectra associated with different conformers of DMPO-OOH. We have prepared 5,5-dimethyl-[3,3-(2)H(2)]-1-pyrroline N-oxide (DMPO-d(2)), and we showed that the EPR spectrum of the corresponding superoxide spin adduct is composed of only six lines, in agreement with the assignment of the 0.125 mT splitting to a gamma-splitting from a hydrogen atom bonded to carbon 3 of DMPO. This result was supported by DFT calculations including water solvation, and the asymmetry of the DMPO-OOH EPR spectrum was nicely reproduced assuming a chemical exchange between two conformers. 相似文献
37.
Aude-Emmanuelle Navarro Corinne Moustrou Nicolas Spinelli Bernard Mandrand 《Tetrahedron》2005,61(16):3947-3952
In previous works we have described a fully automated synthesis of new ferrocene labelled oligonucleotides (Fc-ODNs) probes with one or more electroactive markers at different position in the chain. These Fc-ODNs have shown good properties to detect ODN target in solution. Here we describe the post-functionalization of a conducting co-polymer based on ethylenedioxythiophene (EDOT) derivatives by a series of Fc-ODNs. The grafting of the Fc-ODNs probes resulted in the appearance of the ferrocene redox couple which directly confirm the effectiveness of the ODN anchoring compared to traditional approach based on IR spectroscopy and X-ray fluorescence of the films. Moreover, the electrochemical response of the modified electrodes analysed in organic media before and after hybridization with ODN target confirm that properties obtain in solution for Fc-ODNs already exist in the film. The changes in the current intensity were found to be dependant on the structure of the grafted ODN that validate our strategy to synthesize an optimal Fc-ODNs. 相似文献
38.
Three types of resins, related to the spacer, environmental and microenvironmental models were prepared by grafting commercial AMP polymer with 2-[2-(2-aminoethylamino)-2-oxoethoxy]acetic acid. All resins were highly loaded and functionalized with Rink-amide linker. A comparative synthesis of the classic difficult sequence ACP (65-74) on the prepared resins by Fmoc/t-Bu chemistry is presented. The ‘microenviromental’ model resin afforded the crude peptide in the highest purity (98%). 相似文献
39.
We describe an efficient protocol for the Suzuki-Miyaura synthesis of ortho-biphenyltetrazoles from non-protected 2-bromophenyltetrazole and arylboronic acids. The optimised conditions were achieved using [1,1′-bis(diphenylphosphino)ferrocene]dichloropalladium(II) as catalyst and Na2CO3 as base. A panel of structurally diverse arylboronic acids was used to demonstrate the scope of the coupling procedure. 相似文献
40.
Claude Lavalle Alain Leborgne Nicolas Spassky Robert E. Prud'homme 《Journal of polymer science. Part A, Polymer chemistry》1987,25(5):1315-1328
β-(trichloromethyl)-β-propiolactone (CCl3-PL), β-(trifluoromethyl,methyl)-β-propiolactone (CF3, Me-PL) and β-(trifluoromethyl,ethyl)-β-propiolactone (CF3,Et-PL) have been obtained by the reaction of ketene with chloral, 1,1,1-trifluoroacetone and 1,1,1-trifluorobutanone, respectively. Chiral catalysis lead to optically active monomers. The enantiomeric excess of the lactones has been measured by 1H-NMR spectroscopy, in the presence of 2,2,2-trifluoro-1-(9-anthryl)ethanol or an europium chiral shift reagent. Polymerizations have been carried out in bulk or in toluene, at 60°C or 80°C, using mainly organometallic initiators. The Polymers become insoluble and crystalline at enantiomeric excesses over 80% for CCl3-PL and 70% for CF3,Me-PL. Melting temperatures were recorded from 238 to 268°C for poly(CCl3-PL) and from 78 to 100°C for poly(CF3,Me-PL), depending upon the molecular weight and the enantiomeric excess. The 13C-NMR specroscopy of poly(CCL3-PL) indicates that the polymerization of the corresponding lactone leads to polymers of increasing degrees of isotacticity with the enantiomeric excess of the monomer. 相似文献