Chlorination of aromatic substrates catalyzed by the phthalocyanine complexes

The chlorination of benzene, toluene, and o-xylene with molecular chlorine in the presence of the phthalocyanine complexes of different structures was studied. The transformations of the catalysts during the reaction were investigated. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1644–1647, August, 2008.     

4-Functionally-substituted 3-heterylpyrazoles: XIX. 3-aryl-4-(5-isoxazolyl)pyrazoles

Oximes of 4-(4-pyrazolyl)-3-buten-2-onees obtained by successive reaction of 3-aryl-4-formylpyrazoles with acetone and hydroxylamine at the treatment with iodine suffered an oxidative cyclization yielding 3-aryl-4-(5-isoxazolyl)pyrazoles.     

Influence of the composition of the polymer matrix on the electrooptical properties of films with a dispersed liquid crystal

Polymer films with a dispersed liquid crystal were prepared by photopolymerization of (meth)acrylic monomers. The electrooptical properties of these films were studied. The influence exerted by the composition of the monomer mixture, cross-linking agents, and chain-transfer agent on the liquid crystal drop size and on the transmission of the polymer-liquid crystal films was examined.     

Study of the dynamic structure factor of strong glasses

The dynamic structure factors (DSFs) of several strong glasses (SF6, SF10, BK7, SUPRASIL) measured by Brillouin light scattering spectroscopy are reported. Spectra have been collected, at and above room temperature, at two scattering angles, θ=90° and θ=180° corresponding to exchanged wavevector q values ranging from 0.0256 to 0.0448 nm⁻¹. In particular we find that the isotropic spectral lineshapes are in all cases well described by the simple hydrodynamic theory of an amorphous solid. The width of the Brillouin peaks are found to be consistent with the predicted q² dependence at both investigated temperatures. This damping is however found to account only partially for the strong asymmetry of the Brillouin line clearly visible on a logarithmic intensity scale. As a matter of fact there is an excess intensity in the very low frequency plateau underlying the central component. The height of this plateau and hence the entire lineshape is well reproduced if a relaxation process is taken into account in the hydrodynamic equations. Owing to the intense elastic scattering we are able to determine unambiguously only the ratio between amplitude and characteristic time of this process which quantifies the sound dispersion to be of the order of a few percent in all samples. The temperature dependence of the parameters indicates that this relaxation cannot be attributed to thermally activated relaxation phenomena. These general findings favorably compare with molecular dynamics simulation results on similar systems.     

Closed-form solutions for a rectangular layer with central crack under anti-plane shear stress

We consider the problem of determining the stress distributionin a finite rectangular elastic layer containing a Griffithcrack which is opened by internal shear stress acting alongthe length of the crack. The mode III crack is assumed to belocated in the middle plane of the rectangular layer. The followingtwo problems are considered: (A) the central crack is perpendicularto the two fixed lateral surfaces and parallel to the othertwo stress-free surfaces; (B) all the lateral surfaces of therectangular layer are clamped and the central crack is parallelto the two lateral surfaces. By using Fourier transformations,we reduce the solution of each problem to the solution of dualintegral equations with sine kernels and a weight function whichare solved exactly. Finally, we derive closed-form expressionsfor the stress intensity factor at the tip of the crack andthe numerical values for the stress intensity factor at theedges of the cracks are presented in the form of tables.     

Combined supercritical-fluid chromatography/mass spectrometry in the analysis of diuron in plasma using on-line phase-system switching

On-line sample pretreatment by means of the phase-system switching approach is an interesting technique for the analysis of aqueous samples, e.g., plasma, by means of supercritical-fluid chromatography. In order to analyse plasma samples the following analytical procedure is used. The plasma sample is injected on to a short precolumn, which is washed with water and subsequently dried with nitrogen. Next, the solutes are desorbed with the supercritical mobile phase, analysed with packed-column supercritical-fluid chromatography and detected with either a UV detector or a mass spectrometer, equipped with a moving-belt interface. The herbicide diuron is selected as a test compound to study the feasibility of this approach. Using a selective detector the procedure is sufficiently sensitive to detect diuron in plasma, but not appropriate to detect the diuron metabolites in a post-mortem plasma sample. These have been identified with liquid chromatography/mass spectrometry. The detection limit of diuron in plasma using the procedure described is about 30 ng/mL.     

Banana-shaped mesogens: a new homologous series of compounds exhibiting the B7 mesophase

The synthesis and characterization of a new homologous series of compounds, the 2-cyano-1,3-phenylene bis[4-(4-n-alkoxyphenyliminomethyl)benzoates] derived from 2-cyanoresorcinol is reported. All the compounds are enantiotropic mesogens and exhibit the fascinating B₇ mesophase. The characterization of the mesophase was performed using polarizing optical microscopy, differential scanning calorimetry, X-ray diffraction and electro-optical studies.     

A parallel cell‐based DSMC method on unstructured adaptive meshes

A parallel DSMC method based on a cell‐based data structure is developed for the efficient simulation of rarefied gas flows on PC‐clusters. Parallel computation is made by decomposing the computational domain into several subdomains. Dynamic load balancing between processors is achieved based on the number of simulation particles and the number of cells allocated in each subdomain. Adjustment of cell size is also made through mesh adaptation for the improvement of solution accuracy and the efficient usage of meshes. Applications were made for a two‐dimensional supersonic leading‐edge flow, the axi‐symmetric Rothe's nozzle, and the open hollow cylinder flare flow for validation. It was found that the present method is an efficient tool for the simulation of rarefied gas flows on PC‐based parallel machines. Copyright © 2004 John Wiley & Sons, Ltd.     

A numerical and experimental investigation of the interactions between a non‐uniform planar array of incompressible free jets

The interaction between multiple incompressible air jets has been studied numerically and experimentally. The numerical predictions have been first validated using experimental data for a single jet configuration. The spreading features of five unequal jets in the configuration of one larger central jet surrounded by four smaller equi‐distant jets, have been studied, for different lateral spacing ratios of 1.5, 2.0 and 2.5 and a central jet Reynolds number of 1.24×105 (corresponding to a Mach number of 0.16). Flow of five equal jets has also been simulated, for the sake of comparison. The jet interactions commence at an axial distance of about 3–4 diameters and complete by an axial distance of about 10 diameters for the lowest spacing ratio of 1.5. For larger spacing ratios, the length required for the start and completion of jet interaction increase. Peripheral jets bend more towards the central jet and merge at a smaller distance, when their sizes are smaller than that of the central jet. The entrainment ratio for multiple jets is higher than that for a single jet. Excellent agreement is observed between the experimental data and theoretical predictions for both mean flow field and turbulent quantities, at regions away from the jet inlet. The potential core length and initial jet development, however, are not predicted very accurately due to differences in the assumed and actual velocity profiles at the jet inlet. Copyright © 2004 John Wiley & Sons, Ltd.     

An improved numerical simulator for multiphase flow in porous media

In basin modelling the thermodynamics of a multicomponent multiphase fluid flux are computationally too expensive when derived from an equation of state and the Gibbs equality constraints. In this article we present a novel implicit molar mass formulation technique using binary mixture thermodynamics. The two proposed solution methods, with and without cross derivative terms between components, are based on a preconditioned Newton‐GMRES scheme for each time‐step with analytical computation of the derivatives. These new algorithms reduce significantly the numerical effort for the computation of the molar masses, and we illustrate the behavior of these methods with numerical computations. Copyright © 2004 John Wiley & Sons Ltd.