Experimental and Theoretical Mechanistic Study on the Thermal Decomposition of 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline

The present paper is a continuation of comprehensive study regarding to synthesis and properties of pyrazoles and their derivatives. In its framework an experimental and theoretical studies of thermal decomposition of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline were performed. It was found, that the decompositions of the mentioned pyrazoline system in the solution and at the melted state proceed via completely different molecular mechanisms. These mechanisms have been explained in the framework of the Molecular Electron Density Theory (MEDT) with the computational level of B3LYP/6-31G(d). A Bonding Evolution Theory (BET) examination of dehydrochlorination of the 3,3-diphenyl-4-(trichloromethyl)-5-nitropyrazoline permits elucidation of the molecular mechanism. It was found, that on the contrary for most known HCl extrusion processes in solution, this reaction is realised via single-step mechanism.     

On one generalization of a DiPerna and Majda theorem

The weak limits of sequences {f(u^ν)}_ν∈? where u^ν's are vector‐valued µ‐measurable functions defined on a compact set Ω and f is (possibly) discontinuous are investigated. As shown by the author (J. Conv. Anal. (to appear)), they are described in terms of integral formulae involving parametrized measures independent of f, similarly as in the classical theorem by Young and its generalization due to DiPerna and Majda. In the present paper we describe the supports of the involved parametrized measures. Copyright © 2006 John Wiley & Sons, Ltd.     

Efficient microwave induced direct α-halogenation of carbonyl compounds

A novel and direct method for the synthesis of α-halocarbonyl compounds using sequential treatment of carbonyl compounds with [hydroxy(tosyloxy)iodo]benzene followed by magnesium halides under solvent-free microwave irradiation conditions is described.     

EPR and XPS measurements of polymeric catalysts doped with hereopolyacids in oxygen adsorption studies

The goal of our studies was to determine the nature of interactions between catalytic active samples, such as polypyrrole (PPy) doped with: chloride anions, heteropolyacids such as H₅PMo₁₀V₂O₄₀, or H₄SiW₁₂O₄₀, and oxygen particles. In order to reveal the mechanism of the linkage between the catalysts and oxygen we provided the electron paramagnetic resonance (EPR) measurements of synthesized samples in O₂ and N₂ flow. Moreover, the X-ray photoelectron spectroscopy (XPS) measurements were performed to show the properties of doped heteropolyacids and the state of nitrogen in polypyrrole matrix. The results of EPR studies of PPy(Cl), PPy(H₄SiW₁₂O₄₀), PPy(H₅PMo₁₀V₂O₄₀) samples, show that the polypyrrole doped with chloride anions interacts much easier with oxygen than polypyrrole doped with heteropolyacids (in the above given order, of preference with the most active polypyrrole system first). It correlates with XPS results, which show that a molybdenium-vanadium anion is more reduced than a silicon-tungsten one. The redox reactions of heteropolyacids involve the oxidation-reduction of the conjugated polymer chain, leaving no or little place for interactions with oxygen. Polypyrrole doped with H₄SiW₁₂O₄₀ shows some oxygen sensitivity as observed in the EPR studies, as opposed to polypyrrole doped with H₅PMo₁₀V₂O₄₀, which is in line with the XPS results.     

Development in Synthesis,Electrochemistry, LB Moieties of Phenothiazine Based Units

A convenient and higher yielding synthetic route to N‐alkyl‐bis(thiophene)phenothiazine derivatives is reported and their aggregation, electrochemical properties and polymerization are characterized. The key step in the synthesis of this group of compounds has been the Stille type coupling reaction between the N‐alkyldibromophenothiazine and tin derivatives of thiophene as the best way for preparation of conjugated N‐alkylphenothiazine derivatives. For this group of compounds we also present an electrochemical polymerization effect and widely adopted approach to prepare structurally ordered thin, electroconducting films by Langmuir–Blodgett technique.     

Temperature coefficient of NH chemical shifts of thioamides and amides in relation to structure

NH chemical shift temperature coefficients have been measured in a large series of N-substituted-3-piperidinethiopropionamides in which the NN distances are short but of varied length, as well as in a couple of the corresponding amides and in some simpler amides and thioamides. Geometries are calculated by means of ab initio DFT methods. The N-substituted-3-piperidinethiopropionamides show in most cases strong intramolecular N–HN hydrogen bonds according to IR spectra and ab initio calculations. For compounds with rather short NN distances the S=C–N–H moiety is non-planar. Dihedral angles as small as 160° are found. The NH chemical shift coefficients measured in non-polar solvents in all the N-substituted-3-piperidinethiopropionamides are more negative (−8 to −17 ppb/K) than in non-hydrogen bonded thioamides. For the latter in non-polar solvents like CDCl₃ and toluene the temperature coefficients are as small as −1 to −4 ppb/K. The large negative effects can be related not only to the non-planarity of the thioamide group in a way that the more pronounced the non-planarity the more negative the temperature coefficients, but also to strong hydrogen bonding and the fact that the acceptor is a nitrogen. For similar amides with non-planar amide groups and nitrogen acceptor large negative temperature coefficients are likewise seen. In polar solvents like DMF the effects in simple thioamides are uniform and close to −6 ppb/K, whereas in the more complex compound like 4p(t) the temperature coefficient is close to 0. An essential feature of measuring temperature coefficients of compounds without strong intramolecular hydrogen bonds in non-polar solvents and at low temperatures is to keep the concentration low enough to avoid dimerisation.     

Nonlocality of Reaction-Diffusion Equations Induced by Delay: Biological Modeling and Nonlinear Dynamics

We present a short survey on the biological modeling, dynamics analysis, and numerical simulation of nonlocal spatial effects, induced by time delays, in diffusion models for a single species confined to either a finite or an infinite domain. The nonlocality, a weighted average in space, arises when account is taken of the fact that individuals have been at different points in space at previous times. We discuss and compare two existing approaches to correctly derive the spatial averaging kernels, and we summarize some of the recent developments in both qualitative and numerical analysis of the nonlinear dynamics, including the existence, uniqueness (up to a translation), and stability of traveling wave fronts and periodic spatio-temporal patterns of the model equations in unbounded domains and the linear stability, boundedness, global convergence of solutions and bifurcations of the model equations in finite domains.     

Grid‐free surface vorticity method applied to flow induced vibration of flexible cylinders

In order to study cross flow induced vibration of heat exchanger tube bundles, a new fluid–structure interaction model based on surface vorticity method is proposed. With this model, the vibration of a flexible cylinder is simulated at Re=2.67 × 10⁴, the computational results of the cylinder response, the fluid force, the vibration frequency, and the vorticity map are presented. The numerical results reproduce the amplitude‐limiting and non‐linear (lock‐in) characteristics of flow‐induced vibration. The maximum vibration amplitude as well as its corresponding lock‐in frequency is in good agreement with experimental results. The amplitude of vibration can be as high as 0.88D for the case investigated. As vibration amplitude increases, the amplitude of the lift force also increases. With enhancement of vibration amplitude, the vortex pattern in the near wake changes significantly. This fluid–structure interaction model is further applied to simulate flow‐induced vibration of two tandem cylinders and two side‐by‐side cylinders at similar Reynolds number. Promising and reasonable results and predictions are obtained. It is hopeful that with this relatively simple and computer time saving method, flow induced vibration of a large number of flexible tube bundles can be successfully simulated. Copyright © 2004 John Wiley & Sons, Ltd.     

Polysiloxanol condensation and disproportionation in the presence of a superacid

Kinetics studies of the condensation of model hydroxyl-terminated oligosiloxanes, pentamethyldisiloxane-1-ol (MDH) and heptamethyltrisiloxane-1-ol (MD₂H), catalysed by protic complex of tetrakis(pentafluorophenyl)borate in the toluene solution were performed. The dominating reaction was condensation, which was accompanied by disproportionation of oligosiloxanols. Water released in the condensation forms separate dispersed phase, but the phase separation and the presence of water does not affect the rate of the polycondensation. Both processes, condensation and disproportionation, show analogous kinetic laws being first order in silanol and half order in catalyst. They exhibit also similar values of activation parameters. The kinetics are explained by the formation of a reactive protic complex of silanol with borate being in fast preequilibrium with an unreactive complex including two borate molecules and the silanol molecules. The equilibrium lies to the side of the unreactive borate complex.