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81.
A practical access to alkyl- and aryl-substituted (E)-2-(azidomethyl)alkenoates and related azido compounds from the corresponding allylic bromides in aqueous acetone is described. An alternative method to obtain the starting bromides based on heterogeneous catalysis under mild conditions was also investigated. 相似文献
82.
In this article, a new methodology for developing discrete geometric conservation law (DGCL) compliant formulations is presented. It is carried out in the context of the finite element method for general advective–diffusive systems on moving domains using an ALE scheme. There is an extensive literature about the impact of DGCL compliance on the stability and precision of time integration methods. In those articles, it has been proved that satisfying the DGCL is a necessary and sufficient condition for any ALE scheme to maintain on moving grids the nonlinear stability properties of its fixed‐grid counterpart. However, only a few works proposed a methodology for obtaining a compliant scheme. In this work, a DGCL compliant scheme based on an averaged ALE Jacobians formulation is obtained. This new formulation is applied to the θ family of time integration methods. In addition, an extension to the three‐point backward difference formula is given. With the aim to validate the averaged ALE Jacobians formulation, a set of numerical tests are performed. These tests include 2D and 3D diffusion problems with different mesh movements and the 2D compressible Navier–Stokes equations. Copyright © 2011 John Wiley & Sons, Ltd. 相似文献
83.
Jasquer A. Sehnem Priscila Milani Vanessa Nascimento Leandro H. Andrade Luciano Dorneles Antonio L. Braga 《Tetrahedron: Asymmetry》2010,21(8):997-1003
N-Trifluoracyl β-chalcogeno amides and N-perfluoracyl β-thio amide ligands were prepared by a simple and efficient reaction sequence. These new ligands were evaluated in palladium-catalyzed alkylation of rac-(E)-1,3-diphenyl-2-propenyl acetate in the presence of dimethyl malonate and an enantioselectivity of up to 99% was obtained. After catalysis, the fluorous ligand can be easily recovered by liquid–liquid extraction and reused without loss in the activity. 相似文献
84.
85.
Summary A method is developed for the computation of the steady solution of the shallow water equations with quasi periodic boundary
conditions. Because of dissipation the influence of the initial conditions becomes negligible with increasing time and the
solution finally depends on the boundary conditions.
The unknowns variables (velocity and surface elevation) and the boundary conditions are developed in power series of a small
perturbation parameter. The problem is then transformed in a sequence of linear problems which have the same associated homogeneous
problem.
By separating the time and space variables in the homogeneous problem we obtain an homogeneous elliptic problem of which we
compute the first eigenvalues and eigensolutions. These are related to the characteristic oscillations of the water in the
basin.
The solution of each linear problem is then obtained as an eigensolution expansion with time dependent coefficients. These
coefficients are solutions of ordinary differential equations which can be solved directly without proceeding step by step
in time.
In this way we are reduced to a stationary problem i.e. the determination of the eigenvalues and eigensolutions of the elliptic
problem and to the computation of several integrals needed for the determination of the time dependent coefficients.
A first test of the method has been carried out for a one-dimensional problem i.e. the tidal wave in a canal of finite length
and constant depth. In this case the various steps of the procedure outlined above can be performed analitically.
The results have been compared with those obtained by a step by step numerical integration of the shallow water equations.
The agreement between these sets of results is good for the range of values of the parameters currently used in the applications.
Work sponsored by the CNR (National Research Council) in the framework of Project ?Conservazione del suolo? Subproject ?Dinamica dei Litorali? Publ. n° 46. 相似文献
Sommario Viene presentato un metodo per il calcolo della soluzione a regime delle equazioni delle onde lunghe, dipendente dalle sole condizioni al contorno quasi-periodiche, dopo aver mostrato che l'influenza delle condizioni iniziali diventa col tempo trascurabile a causa del termine di resistenza. Il metodo si basa sullo sviluppo in serie di potenze di un piccolo parametro sia delle incognite (velocità ed elevazioni del pelo libero) sia delle condizioni al contorno al fine di trasformare il problema non lineare in una serie di problemi lineari aventi lo stesso problema omogeneo associato. Con la separazione delle variabili spazio, tempo quest'ultimo problema viene ricondotto ad un problema ellittico omogeneo di cui si calcolano i primi autovalori ed autosoluzioni. Da ultimo la soluzione di ciascun problema lineare è ottenuta come sviluppo in serie di autosoluzioni a coefficienti dipendenti dal tempo: questi si ricavano risolvendo analiticamente delle equazioni differenziali ordinarie. Si elimina cosi la necessità di procedere passo passo nel tempo analogamente ai classici metodi armonici di soluzione di sistemi lineari. Riassumendo, l'applicazione del metodo riconduce alla soluzione di un problema stazionario (determinazione di autovalori ed autosoluzione del problema ellittico) e quindi al calcolo dei vari integrali necessari per la determinazione dei coefficienti temporali. Il metodo è stato provato nel caso semplice della propagazione di onde di marea in un canale di lunghezza finita e sezione costante. Per questo esempio i vari passi di calcolo possono essere svolti analiticamente. I risultati sono stati confrontati con quelli ottenuti dalla integrazione numerica delle equazioni col metodo delle caratteristiche, ottenendo un buon accordo.
Work sponsored by the CNR (National Research Council) in the framework of Project ?Conservazione del suolo? Subproject ?Dinamica dei Litorali? Publ. n° 46. 相似文献
86.
87.
Luciano Lepori Paolo Gianni Andrea Spanedda Enrico Matteoli 《The Journal of chemical thermodynamics》2011,43(10):1453-1462
Excess molar volumes VE at 298.15 K were determined by means of a vibrating tube densimeter for binary mixtures of {heptane + open chain secondary (diethyl to dibutyl) and tertiary (triethyl to tripentyl) amines} as well as for cyclic imines (C2, C3, C4, C6, and C7) and primary cycloalkylamines (C5, C6, C7, and C12). The VE values were found positive for mixtures involving small size amines, with VE decreasing as the size increases. Negative VE’s were found for tributyl- and tripentylamine, heptamethylenimine, and cyclododecylamine. Mixtures of heptane with cycloheptylamine showed an s-shaped curve.Partial molar volumes of amines at infinite dilution in heptane were obtained from VE and compared with of hydrocarbons and other classes of organic compounds taken from literature. An additivity scheme, based on the intrinsic volume approach, was applied to estimate group (CH3, CH2, CH, C, NH2, NH, N, OH, O, CO, and COO) contributions to . These contributions, the effect of cyclization on , and the limiting slope of the apparent excess molar volumes were discussed in terms of solute–solvent and solute–solute interactions. 相似文献
88.
Nagy EM Nardon C Giovagnini L Marchiò L Trevisan A Fregona D 《Dalton transactions (Cambridge, England : 2003)》2011,40(44):11885-11895
During the last decade, our research group has prepared a number of metal dithiocarbamato derivatives of Pt, Pd and Au that were expected to resemble the main features of cisplatin together with higher activity, improved selectivity and bioavailability, and lower side-effects. Furthermore, we have already published the synthesis, characterization and in vitro cytotoxicity studies of novel ruthenium(III) dithiocarbamato complexes such as [RuL(3)] monomers (11) and α-[Ru(2)L(5)]Cl dimers (12) with five different dithiocarbamate ligands. As both the monomer and the dinuclear complexes have shown significant antitumor activity in different human tumor cell lines, we decided to widen the characterization studies and to analyse thoroughly their behavior in physiological-like medium by UV-visible and CD spectroscopy. In the present paper we report on the crystal structure of [Ru(DMDT)(3)], [Ru(PDT)(3)] and [Ru(ESDT)(3)] complexes and we determine the spin state of the paramagnetic Ru(III) by means of Evans' method. Then, we discuss in detail the UV-visible spectral data of the complexes in different medium. All the studied complexes are stable in dimethyl sulfoxide, and show low solubility in phosphate buffered saline solution, particularly the monomer species, even at low concentration, while increased solubility for both types of complexes have been found in the presence of bovine serum albumin (BSA). Moreover, no changes on the coordination sphere of the metal, as well as no direct interaction between the BSA protein and the complex have been identified by UV-visible spectroscopy. However, some conformational changes on the BSA structure, induced by the ruthenium(III) complexes have been confirmed by CD spectroscopy, indicating a probable secondary electrostatic interaction between the metal complex and the peptide. In addition, no significant interaction has been demonstrated with the components of Dulbecco's Modified Eagle's Medium, used for the in vitro assays. 相似文献
89.
Boga C Forlani L Calienni R Hindley T Hochkoeppler A Tozzi S Zanna N 《Natural product research》2011,25(4):417-421
A decoction of Capparis spinosa L. roots, widely used in the traditional folk medicine of southern Italy, was prepared and submitted to antibacterial activity tests, which showed an interesting bacteriostatic activity on the growth of Deinococcus radiophilus. Heterocyclic compounds were also recovered from the chloroformic extract of the roots. 相似文献
90.
The aim of this study was to develop a fast CE separation method by using multiple short-end injections in a capillary coated with quaternary ammonium chitosan (HACC), in order to determine the iodide content of pharmaceutical formulations. The BGE was composed of 20 mM tris(hydroxymethyl)aminomethane and 11 mM hydrochloric acid, at pH 8. The internal standard used was thiocyanate. Separations were performed in a fused silica capillary (32 cm total length, 8.5 cm effective length and 50 μm i.d.) coated with HACC and direct UV detection at 220 nm. EOF was modified by flushing the capillary with polymeric solution, resulting in a semi-permanent coating of controlled and stable EOF. The EOF was anodic at pH 8. Different strategies, using single and multiple injection short-end configurations, were studied to develop a CE method that resulted in a maximum number of iodide samples analyzed per hour: one plug and flush (Sflush) 35 samples/h, one plug without flush (SWflush) 76 samples/h, four plugs and flush (Mflush) 61 samples/h, and four plugs without flush (MWflush) 80 samples/h. Using the multiple injection configuration, it was possible to inject up to four plugs using spacer electrolytes with good separation efficiency and selectivity. The voltage application time needed to separate the eight peaks (iodide and thiocyanate) with MWflush was only 12s. The method was validated and samples were analyzed using MWflush. Good linearity (R(2)>0.999); a limit of detection 0.4 mg L(-1); intermediate precision better than 3.8% (peak area) and recovery in the range of 99-102% were obtained. 相似文献