Stereoselectivity and kinetics of [4 + 2] cycloaddition reaction of cyclopentadiene to para‐substituted E‐2‐arylnitroethenes

In spite of diversified electrophilicity of E‐2‐arylnitroethenes, their [4 + 2] cycloaddition reactions with cyclopentadiene leads to the corresponding 6‐endo‐aryl‐5‐exo‐nitronorbornenes and 6‐exo‐aryl‐5‐endo‐nitronorbornenes as the only reaction products. Stereoselectivity, substituent and solvent effects, and activation parameters, suggest that these reactions occur via a synchronous concerted mechanism on both competing pathways. The experimental results obtained are consistent with the data from B3LYP/6‐31G(d) calculations. Due to high electrophilicity of E‐2‐arylnitroethenes, the reactions studied should be considered as polar [4 + 2] cycloadditions. Copyright © 2011 John Wiley & Sons, Ltd.     

Surface‐enhanced Raman scattering study of monolayers formed from mixtures of 4–mercaptobenzoic acid and various aromatic mercapto‐derivative bases

Monolayers formed from aromatic compounds have many potential applications, for example in construction of bioelectronic elements having high efficiency of electron transfer. In this paper, the composition of monolayers formed on silver surfaces from mixtures of 4‐mercaptobenzoic acid (MBA) and four model (stable and easily available) aromatic thiols with strong base properties: 4,6‐diamino‐2‐mercaptopyrimidine (APY), 1H‐1,2,4‐triazole‐3‐thiol (HTR), 4‐methyl‐4H‐1,2,4‐triazole‐3‐thiol (MTR) and 3‐amino‐1,2,4‐triazole‐5‐thiol (ATR), were determined from surface‐enhanced Raman scattering (SERS) measurements. Our investigations showed that among studied aromatic bases, APY is the most promising candidate for the formation of mixed monolayers with MBA. In the whole pH range studied (2–12.5), mixed MBA + APY monolayers with similar surface concentration of both components are formed during the adsorption from the 0.5 mM MBA + 0.5 mM APY aqueous solution. Desorption of MBA and APY from the mixed monolayer is, however, significantly different. During immersion in water, surface concentration of APY decreases significantly faster than MBA (a significant part of the adsorbed MBA molecules is present on the silver surface even after 2 h of soaking in water). Presence of chlorides, bovine serum albumin or laccase in the surrounding solution does not observably influence the structure of MBA + APY monolayers. The properties of monolayers formed from MBA and substituted triazoles were found to be significantly different than those of MBA + APY monolayers. Copyright © 2009 John Wiley & Sons, Ltd.     

On numerical realizability of thermal convection

Astounded at the regularity of convective structures observed in simulations of mesoscale flow past realistic topography, we investigate the computational aspects of a classical problem of flow over a heated plane. We find that the numerical solutions are sensitive to viscosity, either incorporated a priori or effectively realized in computational models. In particular, anisotropic viscosity can lead to regular convective structures that mimic naturally realizable Rayleigh–Bénard cells, which are unphysical for the specified external parameter range. Details of the viscosity appear to play a secondary role; that is, similar structures can occur for prescribed constant viscosities, explicit subgrid-scale turbulence models, ad-hoc numerical filters, or implicit dissipation of numerical schemes. This implies the need for a careful selection of numerical tools suitable for convection-resolving simulations of atmospheric circulations. The implicit large-eddy-simulation (ILES) approach using non-oscillatory schemes is especially attractive, as for under-resolved calculations it reproduces well the coarsened results of finely-resolved boundary layer convection.     

Bump time-frequency toolbox: a toolbox for time-frequency oscillatory bursts extraction in electrophysiological signals

Background  

oscillatory activity, which can be separated in background and oscillatory burst pattern activities, is supposed to be representative of local synchronies of neural assemblies. Oscillatory burst events should consequently play a specific functional role, distinct from background EEG activity – especially for cognitive tasks (e.g. working memory tasks), binding mechanisms and perceptual dynamics (e.g. visual binding), or in clinical contexts (e.g. effects of brain disorders). However extracting oscillatory events in single trials, with a reliable and consistent method, is not a simple task.     

Semi-empirical bone model for determination of trabecular structure properties from backscattered ultrasound

A novel semi-empirical scattering model of trabecular bone facilitating its characterization and allowing optimization of the interrogating pulse-echo transducer performance was developed. The model accounts for spatial density distribution of the trabeculae and includes measurement conditions such as pressure–time waveform of the probing ultrasound wave, the emitted field structure, and the transfer function and limited bandwidth of the acoustic source operating in pulse-echo mode. These measurement conditions are of importance as they modify the scattered echoes, which in turn are linked to the micro-architecture of the bone. The bone was modeled by a random distribution of long and thin cylindrical scatterers having randomly varying diameters and mechanical properties, and oriented perpendicularly to the ultrasound beam axis. To mimic clinically encountered conditions the relevant empirical data obtained at 1 MHz were input to the model. The data included pulse-echo source pressure field distribution in the focal zone and the above mentioned transfer function. With these data the model allowed frequency dependent backscattering coefficient of the simulated bone structure and its statistical properties to be determined. The results obtained indicated that the computer simulation is of particular relevance in studying scattering properties of the cancellous bone and holds promise as a tool to determine the relationship between the physical dimensions and shape of the scatterers and for monitoring of osteoporosis. The results of simulations also indicated that the new bone model proposed is well suited to mimic clinically relevant conditions. In contrast to the existing bone models, which usually assume scatterers to be randomly distributed as infinitely long identical cylinders with a cross-section much smaller than the probing ultrasound wave, the new model includes two populations of scatterers having different physical dimensions and also allows the mechanical properties of the scatterers to be varied.     

3D MR imaging of dental cavities-an in vitro study

A 3D spin-echo (3D SE) pulse sequence was used on a 4.7 T research MRI system to produce images of extracted human first molar tooth placed in CuSO4 water solution. The maximal resolution achieved was 35 x 63 x 300 microm3 in read and two phase directions, respectively. The high-intensity signal from water in solution together with the lack of signal from mineralized tooth tissue produce very good contrast allowing to visualize topography of outer and inner surfaces of the tooth. The 3D MR data were median filtered, binarized and then divided into separate segments corresponding to the inner tooth cavities and the hard tooth tissue. The topography of the root canals was visualized and the canals volume was calculated. The presented technique may be used for quantitative analysis of the root canal cavities shape and volume. The results of such an analysis may be applied for estimation of the quality of the impressional mapping methods in restorative dentistry or as an alternative non-impressional 3D mapping method.     

Quantization of Alternative Hamiltonians

We investigate quantum mechanical implications of canonically inequivalent Hamilton formulations of the Newtonian dynamics. Generated alternative quantizations, being noncanonical, are consistent with the same equations of motion, i.e., they satisfy E.Wigner's principle of quantization. As illustration we consider a noncanonical one-dimensional harmonic oscillator.     

Heavy-to-light-quark decays with two-loop accuracy

We present a determination of a new class of three-loop Feynman diagrams describing heavy-to-light transitions. We apply it to find the O(alpha2(s)) corrections to the top quark decay t --> bW and to the distribution of lepton invariant mass in the semileptonic b quark decay b --> ulnu. We also confirm the previously determined total rate of that process as well as the O(alpha2) corrections to the muon lifetime.     

Evolution of density perturbations in a realistic universe

Prompted by the recent more precise determination of the basic cosmological parameters and growing evidence that the matter-energy content of the universe is now dominated by dark energy and dark matter we present the general solution of the equation that describes the evolution of density perturbations in the linear approximation. It turns out that as in the standard CDM model the density perturbations grow very slowly during the radiation dominated epoch and their amplitude increases by a factor of about 4000 in the matter and later dark energy dominated epoch of expansion of the universe.     

Crystal growth, structure and electrical properties of thorium phosphorosulfide

Single crystals of thorium phosphorosulfide have been grown by the chemical vapour transport method. The X-ray diffraction examination showed that the unit cell of the crystals belongs to a tetragonal system of the PbFCl-type structure. The basal plane resistivity ρ(300 K)=64 μΩ cm and thermoelectric power S(300 K)=−7.7 μV/K, examined between 0.4 and 315 K, show metallic behaviour.