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.     

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.     

Comparison of detection efficiencies of negatively charged gold-alkanethiolate-, gold-sulfur- and gold-clusters in ToF-SIMS

In order to improve quantification of high mass ions, the influence of cluster composition on detection efficiencies has been studied using a TOF-SIMS IV with the extended capability of postaccelerating ions up to 20 keV. In this experimental study, we focus on the comparison of detection efficiencies for three types of negatively charged secondary cluster ions: gold-alkanethiolate-clusters (Au_xM_y), gold-sulfur-clusters (Au_xS_y) and gold-clusters (Au_x). The clusters were sputtered from self-assembled monolayers of hexadecanethiols on gold substrates using 10 keV Ar⁺ primary ions. The detection efficiencies were derived on the basis of a function for the secondary electron yield and a fourth-order approximated Poisson probability distribution for electron propagation and amplification within the microchannel plate.In addition to the well-known dependence of detection efficiencies on ion mass and energy, which has already been studied for positively charged ions, we were able to show a similar behaviour for the investigated negatively charged secondary ions. We have observed major variations among the three types of clusters at similar mass and energy as predicted in a theoretical approach. The observed differences are due to the different composition of the investigated clusters which has a major influence on the kinetic ion induced electron emission within the microchannel plate. For the first time it was possible to experimentally verify these predictions for detection efficiencies.     

Numerical flow visualization of first cycle and cyclic motion of a rigid fling-clapping wing

A flow visualization of the two-dimensional rigid fling-clap motions of the flat-plate wing is performed to get the knowledge of fling-clapping mechanism that might be employed by insects during flight. In this numerical visualization, the time-dependent Navier-Stokes equations are solved for two types of wing motion; ‘fling followed by clap and pause motion’ and ‘cyclic fling-clapping motion’. The result is observed regarding the main flow features such as the sequential development of the two families of separation vortex pairs and their movement. For the ‘fling followed by clap and pause motion’, a strong separation vortex pair of counterrotation develops in the opening between the wings in the fling phase and they then move out from the opening in the following clap phase. For ‘the cyclic fling-clapping motion’, the separation vortex pair developed in the outside space in the clap phase move into the opening in the following fling phase. The separation vortex pair in the opening developed in the fling phase of the cyclic motion is observed to be stronger than those of the ‘fling followed by clap and pause motion’. Regarding the strong fling separation vortex and the weak clap separation vortex above it in the opening, the flow pattern of the fling phase of the cyclic fling and clap motion is different to that of the fling phase of the first cycle. The flow pattern of the third cycle of the cyclic fling-clapping motion is observed to be almost same as that of the second cycle. Therefore, a periodicity of the flow pattern is established after the second cycle.     

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.     

Perfect information two-person zero-sum markov games with imprecise transition probabilities

Based on an extension of the controlled Markov set-chain model by Kurano et al. (in J Appl Prob 35:293–302, 1998) into competitive two-player game setting, we provide a model of perfect information two-person zero-sum Markov games with imprecise transition probabilities. We define an equilibrium value for the games formulated with the model in terms of a partial order and then establish the existence of an equilibrium policy pair that achieves the equilibrium value. We further analyze finite-approximation error bounds obtained from a value iteration-type algorithm and discuss some applications of the model.     

Singlewall carbon nanotubes covered with polystyrene nanoparticles by in‐situ miniemulsion polymerization

This work is to make carbon nanotubes dispersible in both water and organic solvents without oxidation and cutting nanotube threads. Polystyrene‐singlewall carbon nanotube (PS‐SWNT) composites were prepared with three different methods: miniemulsion polymerization, conventional emulsion polymerization, and mixing SWNT with PS latex. The two factors, crosslinking and surface coverage of PS are important factors for the mechanical and electrical properties, including dispersion states of SWNT in various solvents. The PS‐SWNT composite prepared via a conventional emulsion polymerization showed SWNT bundles entirely covered with PS, whereas the PS‐SWNT composite prepared via a miniemulsion polymerization showed SWNT partially covered with crosslinked PS nanoparticles. The method of mixing SWNTs with PS latex did not show the well dispersed state of carbon nanotubes because PS was not crosslinked and was dissolved in a solvent, and nanotubes separated from PS precipitated. So the PS nanoparticle‐SWNT composite had lower electrical resistance, and higher mechanical strength than the other composites made by the latter two methods. As the amount of SWNT increases, the bare surface area of SWNT increases and the electrical conductivity increases in the composite made by the miniemulsion polymerization. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 573–584, 2006