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1.
Carmen Gal Remus Nutiu 《International journal of environmental analytical chemistry》2013,93(7):447-460
An extraction device has been investigated for the separation and preconcentration of a series of volatile organic compounds (CHCl3, CHCl2Br, CHClBr2 and CHBr3) in aqueous matrices. The device consisted of a microporous membrane system utilising a hollow fibre tube filled with organic solvent directly immersed into the sample solution. The hollow fibre containing 160 µL organic solvent was immersed in a glass vial with 10 mL capacity, and the extraction took place through diffusive transport between the aqueous sample and the small amount of solvent. For validation of the method, some operational conditions, such as extraction solvent, temperature, stirring rate and separation time, were optimised. Limit of detection was at low ppb levels, with GC-MS analysis under selected ion monitoring (SIM), whereas enrichment factors between 22 and 35 were obtained. Good reproducibility with RSDs between 7.2% and 9.8% and large linear dynamic ranges with R 2 between 0.996 and 0.998 were also achieved. In addition, the performance of the membrane assisted solvent extraction (MASE) system was compared with two existing configurations: a non-porous membrane separation device, as well as with a comparable microporous configuration. The comparison considered the extraction mechanism and the underlying transport processes. The application to real samples showed a good concordance with classical analytical methods. 相似文献
2.
Dr. Andrey Y. Khalimon Prof. Dr. Stanislav K. Ignatov Andrey I. Okhapkin Dipl.‐Ing. Razvan Simionescu Prof. Dr. Lyudmila G. Kuzmina Prof. Dr. Judith A. K. Howard Dr. Georgii I. Nikonov 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(26):8573-8590
The reactions of bis(borohydride) complexes [(RN?)Mo(BH4)2(PMe3)2] ( 4 : R=2,6‐Me2C6H3; 5 : R=2,6‐iPr2C6H3) with hydrosilanes afford new silyl hydride derivatives [(RN?)Mo(H)(SiR′3)(PMe3)3] ( 3 : R=Ar, R′3=H2Ph; 8 : R=Ar′, R′3=H2Ph; 9 : R=Ar, R′3=(OEt)3; 10 : R=Ar, R′3=HMePh). These compounds can also be conveniently prepared by reacting [(RN?)Mo(H)(Cl)(PMe3)3] with one equivalent of LiBH4 in the presence of a silane. Complex 3 undergoes intramolecular and intermolecular phosphine exchange, as well as exchange between the silyl ligand and the free silane. Kinetic and DFT studies show that the intermolecular phosphine exchange occurs through the predissociation of a PMe3 group, which, surprisingly, is facilitated by the silane. The intramolecular exchange proceeds through a new non‐Bailar‐twist pathway. The silyl/silane exchange proceeds through an unusual MoVI intermediate, [(ArN?)Mo(H)2(SiH2Ph)2(PMe3)2] ( 19 ). Complex 3 was found to be the catalyst of a variety of hydrosilylation reactions of carbonyl compounds (aldehydes and ketones) and nitriles, as well as of silane alcoholysis. Stoichiometric mechanistic studies of the hydrosilylation of acetone, supported by DFT calculations, suggest the operation of an unexpected mechanism, in that the silyl ligand of compound 3 plays an unusual role as a spectator ligand. The addition of acetone to compound 3 leads to the formation of [trans‐(ArN)Mo(OiPr)(SiH2Ph)(PMe3)2] ( 18 ). This latter species does not undergo the elimination of a Si? O group (which corresponds to the conventional Ojima′s mechanism of hydrosilylation). Rather, complex 18 undergoes unusual reversible β‐CH activation of the isopropoxy ligand. In the hydrosilylation of benzaldehyde, the reaction proceeds through the formation of a new intermediate bis(benzaldehyde) adduct, [(ArN?)Mo(η2‐PhC(O)H)2(PMe3)], which reacts further with hydrosilane through a η1‐silane complex, as studied by DFT calculations. 相似文献
3.
Razvan Gurau 《Communications in Mathematical Physics》2011,304(1):69-93
Random matrix models generalize to Group Field Theories (GFT) whose Feynman graphs are dual to higher dimensional topological
spaces. The perturbative development of the usual GFT’s is rather involved combinatorially and plagued by topological singularities
(which we discuss in great detail in this paper), thus very difficult to control and unsatisfactory. 相似文献
4.
In this article we continue with the study of smooth Gauss–Weierstrass singular integral operators over the real line regarding their simultaneous global smoothness preservation property with respect to the Lp norm, 1≤p≤∞, by involving higher order moduli of smoothness. Also we study their simultaneous approximation to the unit operator with rates involving the modulus of continuity with respect to the uniform norm. The produced Jackson type inequalities are almost sharp containing elegant constants, and they reflect the high order of differentiability of the engaged function. 相似文献
5.
Razvan Gabriel Iagar Ariel Sánchez Juan Luis Vázquez 《Journal de Mathématiques Pures et Appliquées》2008,89(1):1-24
In this paper we prove that there exists an explicit correspondence between the radially symmetric solutions of two well-known models of nonlinear diffusion, the porous medium equation and the p-Laplacian equation. We establish exact correspondence formulas between these solutions. We also study in detail the application of the results in the important case of self-similar solutions. In particular, we derive the existence of new self-similar solutions for the evolution p-Laplacian equation. 相似文献
6.
7.
We derive high-order corrections to a modulation theory for the propagation of internal gravity waves in a density-stratified fluid with coupling to the mean flow. The methodology we use allows for strong modulations of wavenumber and mean flow, extending previous approaches developed for the quasi-monochromatic regime. The wave mean flow modulation equations consist of a system of nonlinear conservation laws that may be hyperbolic, elliptic or of mixed type. We investigate the regularizing properties of the asymptotic correction terms in the case when the system becomes unstable and ill-posed due to a change of type (loss of hyperbolicity). A linear analysis reveals that the regularization by the added correction terms does so by introducing a short-wave cut-off of the unstable wavenumbers. We perform various numerical experiments that confirm the regularizing properties of the correction terms, and show that the growth of unstable modes is tempered by nonlinearity. We also find an excellent agreement between the solution of the corrected modulation system and the modulation variables extracted from the numerical solution of the nonlinear Boussinesq equations. 相似文献
8.
In this paper, we employ a technique combining the Euler Maclaurin formula with the saddle point approximation method to obtain
the asymptotic behavior (in the limit of large representation index J) of generic Wigner matrix elements DJMM¢(g){D^{J}_{MM'}(g)} . We use this result to derive asymptotic formulae for the character χ
J
(g) of an SU(2) group element and for Wigner’s 3j symbol. Surprisingly, given that we perform five successive layers of approximations, the asymptotic formula we obtain for
χ
J
(g) is in fact exact. The result hints at a “Duistermaat-Heckman like” localization property for discrete sums. 相似文献
9.
10.
Lu Q Keskar G Ciocan R Rao R Mathur RB Rao AM Larcom LL 《The journal of physical chemistry. B》2006,110(48):24371-24376
Density gradient centrifugation is a high-resolution technique for the separation and characterization of large molecules and stable complexes. We have analyzed various nanotube structures by preparative centrifugation in sodium metatungstate-water solutions. Bundled, isolated and acid-treated single-walled nanotubes (SWNTs) and multiwall nanotubes (MWNTs) formed sharp bands at well-defined densities. The structure of the material in each band was confirmed by transmission electron microscopy and Raman spectroscopy. Our data suggest respective densities of 1.87, 2.13, 1.74, and 2.1 g/cm(3) for bundled, isolated, and acid-treated SWNTs and MWNTs. These measured results compare well with their calculated densities. 相似文献