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51.
A more realistic estimation of the scattering and hemispheric backscattering coefficients, σsp and σbsp, and their respective optical cross section, Csca and Cbk, of aerosol particles is presented on the basis of the exact resolution of the width of the size bins of the particle counter instruments when size distribution measurements are used, and, with the exact optical detector instruments ability. The scattering and hemispheric backscattering cross sections, Csca and Cbk, of the particles are averaged over the full size bins of the particle counter instrument, while these quantities are usually estimated only on the value of the mean geometric diameter of each size bin. Six instruments, the APS, ASASP-X, DMPS, FSSP-100, ELPI, and SMPS frequently used in particle size distribution measurements are reviewed, for spherical sea-salt particles at a wavelength λ=0.55 μm. The comparison using the conventional geometric mean diameter versus the use of the full size bin leads to large amount of errors for the optical cross section with non-negligible effects on their respective optical coefficients. The maximal accuracy expected for these optical quantities depend on the particle diameter as well as on the channel width of the instruments, and are also function of the angular detector probe used to measure them.  相似文献   
52.
A convenient synthesis of 4'-aminopantetheine from commercial D-pantethine is reported. The amino group was introduced by reductive amination in order to avoid substitution at a sterically congested position. Derivatives of 4'-aminopantetheine were also prepared to evaluate the effect of O-to-N substitution on inhibitors of the resistance-causing enzyme aminoglycoside N-6'-acetyltransferase. The biological results combined with docking studies indicate that in spite of its reported unusual flexibility and ability to adopt different folds, this enzyme is highly specific for AcCoA.  相似文献   
53.
We consider a linear wave equation, on the interval (0,1), with bilinear control and Neumann boundary conditions. We study the controllability of this nonlinear control system, locally around a constant reference trajectory. We prove that the following results hold generically.
For every T>2, this system is locally controllable in H3×H2, in time T, with controls in L2((0,T),R).
For T=2, this system is locally controllable up to codimension one in H3×H2, in time T, with controls in L2((0,T),R): the reachable set is (locally) a non-flat submanifold of H3×H2 with codimension one.
For every T<2, this system is not locally controllable, more precisely, the reachable set, with controls in L2((0,T),R), is contained in a non-flat submanifold of H3×H2, with infinite codimension.
The proof of these results relies on the inverse mapping theorem and second order expansions.  相似文献   
54.
Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface.  相似文献   
55.
56.
Two 2,2'-bipyridines, substituted at the 4,4'-positions by p-dialkylaminophenylazostyryl moieties p-R2N-C6H4-N=N-C6H4-CH=CH-[6 a, R2N=nBu2N; 6 b, R2N=(nBu)(C4H8OTHP)N; 6 c, R2N=(nBu)(C4H8OH)N], were successfully synthesized by using Wadworth-Emmons reactions. The X-ray structure of 6 a has been determined. Esterification of 6 c with 2-bromoisobutyroylbromide afforded 6 d. This ligand was used as an initiator for the living radical polymerization of methylmethacrylate (MMA) and gave rise to macroligand 6 e. Thin films of good optical quality were obtained by the spin-coating technique. Photoisomerization experiments were carried out on 6 a in solution and on 6 e in both solution and film, and the kinetics of photochemical (E/Z) and thermal (Z/E) isomerization were investigated. They were found to show Z-E back isomerization typical of aminoazobenzene-type rather than of push-pull-type molecules. Density functional theoretical (TD-DFT) calculations were performed on model compound 6 a' (R2N=Me2N) to understand the structural and electronic transitions of the corresponding E-E, E-Z and Z-Z isomers. It was found that the E-E isomer is almost planar as observed experimentally by X-ray diffraction, whereas the Z-Z isomer, which is 35.4 kcal mol(-1) less stable than the E-E isomer, is nonplanar. The theoretical studies also reveal that several transitions of pi-pi*, n-pi* and charge-transfer (CT) types, are involved in the long-wavelength transition of 6 a (E-E). The same observations can be made for the (Z-Z) isomer, and the TD-DFT simulated spectrum fits quite nicely to the experimental, reproducing and explaining the apparition of a blue-shifted charge-transfer band at 390 nm.  相似文献   
57.
An automated multi-pumping flow system is proposed for the simultaneous chemiluminometric determination of benserazide and levodopa using multivariate calibration methods. The developed methodology is based on chemiluminescence (CL) emission generated by the reaction of benserazide with luminol, and on a concurrent inhibiting effect of levodopa on this reaction. A multi-pumping flow system comprising multiple solenoid micro-pumps as the only active components was developed to implement a stopped-flow approach for signal acquisition and processing. Artificial neural networks were used to establish a relationship between the CL emission profile and the concentration of both drugs. The concentration values used to establish the experimental calibration samples were varied between 5 and 30 mg l(-1) for levodopa and between 2.5 and 20 mg l(-1) for benserazide. The proposed method was successfully applied to the simultaneous determination of levodopa and benserazide in pharmaceutical formulations combining both drugs.  相似文献   
58.
We propose a test procedure which compares the extreme value indices of two samples with heavy tail distributions. On a theoretical point of view, we adopt the minimax nonparametric point of view. We exhibit the separating rate between the null hypothesis and the alternative of our procedure. Next, we present a data driven test methodology and we evaluate its performance thanks to an extensive simulation study. As a practical real-life application, we compare the risk behaviors of a panel of different financial data.  相似文献   
59.
The instant controlled pressure drop (DIC) technology enabled both the extraction of essential oil and the expansion of the matrix itself which improved solvent extraction. The sequential use of DIC and Ultrasound Assisted Extraction (UAE) triggered complementary actions materialized by supplementary effects. We visualized these combination impacts by comparing them to standard techniques: Hydrodistillation (HD) and Solvent Extraction (SE). First, the extraction of orange peel Essential Oils (EO) was achieved by HD during 4 h and DIC process (after optimization) during 2 min; EO yields was 1.97 mg/g dry material (dm) with HD compared to 16.57 mg/g dm with DIC. Second, the solid residue was recovered to extract antioxidant compounds (naringin and hesperidin) by SE and UAE. Scanning electron microscope showed that after HD the recovered solid shriveled as opposite to DIC treatment which expanded the product structure. HPLC analyses showed that the best kinetics and yields of naringin and hesperidin extraction was when DIC and UAE are combined. Indeed, after 1 h of extraction, DIC treated orange peels with UAE were 0.825 ± 1.6 × 10?2 g/g of dry material (dm) for hesperidin and 6.45 × 10?2 ± 2.3 × 10?4 g/g dm for naringin compared to 0.64 ± 2.7 × 10?2 g/g of dry material (dm) and 5.7 × 10?2 ± 1.6 × 10?3 g/g dm, respectively with SE. By combining DIC to UAE, it was possible to enhance kinetics and yields of antioxidant extraction.  相似文献   
60.
Dirubidium divanadyl phyllooctasilicate, Rb2(VO)2[Si8O19], is the first known anhydrous diphyllosilicate containing VIV. The structure consists of silicate double layers which are separated by [V2O8]8− dimers and is related to that of the compounds A2Cu2[Si8O19] (A = Rb or Cs), although the title compound crystallizes in a noncentrosymmetric orthorhombic space group. The silicate double layers contain four tetrahedrally coordinated Si sites in general positions and 12 O sites, nine in general positions and the other three on mirror planes. The vanadyl dimers have two square‐pyramidally coordinated V sites (site symmetry m). There are two different 10‐ and 12‐fold coordinated Rb sites with site symmetry m, one of which is a split position located between the dimers in the interlayer space, while the other is in a channel within the silicate layer.  相似文献   
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