Selective Propargylation of Carbonyl Compounds and Imines with Barium Reagents

A Barbier‐type regioselective propargylation of aldehydes and ketones with (3‐bromobut‐1‐ynyl)trimethylsilane has been achieved using reactive barium as a low‐valent metal in THF. Especially in the case of ketones, the corresponding homopropargylic alcohols form almost exclusively. In the reaction of α,β‐unsaturated carbonyl compounds, only 1,2‐adducts have been observed. This method is also applicable to propargylation of imines, and the corresponding homopropargylic amines are obtained regiospecifically in good yields with diastereomeric ratios of up to 87:13.     

A case of concomitant polymorphism and spontaneous resolution: the tetragonal phase of 5‐hydroxymethyl‐7,7,N‐trimethyl‐6‐oxabicyclo[3.2.1]octane‐1‐carboxamide

The title compound, C₁₂H₂₁NO₃, crystallizes in two polymorphic forms, viz. the tetragonal form described here and the monoclinic form described previously [Foces‐Foces, López‐Rodríguez, Pérez, Martín & Pérez‐Hernández (2007). Cryst. Growth Des. 7 , 905–911]. The differences in the conformations of the hydroxymethyl and methylaminocarbonyl substituents have important consequences in the hydrogen‐bond interaction motifs and, therefore, in the packing arrangements. These forms are concomitant polymorphs with melting points differing by 3 K.     

The kinetics of the light-induced defect creation in hydrogenated amorphous silicon – Stretched exponential relaxation

Our model for light-induced defect creation in hydrogenated amorphous silicon is applied to its kinetics, i.e., the growing curve of light-induced dangling bond density as a function of illumination time, which is fitted to a stretched exponential function. Two parameters β and τ involved in the function are estimated as functions of saturated dangling bond density in terms of our model. These are compared with two experimental results, i.e., our results obtained from ESR measurements and Shimakawa et al.’s results obtained from photoconductivity measurements. The saturated dangling bond density is also measured as a function of the generation rate of free carriers. The experimental results are compared with calculated results and discussed.     

Buckling of a stiff thin film on a compliant substrate in large deformation

A finite-deformation theory is developed to study the mechanics of thin buckled films on compliant substrates. Perturbation analysis is performed for this highly nonlinear system to obtain the analytical solution. The results agree well with experiments and finite element analysis in wavelength and amplitude. In particular, it is found that the wavelength depends on the strain. Based on the accurate wavelength and amplitude, the membrane and peak strains in thin films, and stretchability and compressibility of the system are also obtained analytically.     

Application of the wavelet transform for a channel flow in a mixed convection phenomenon

The aim of this paper is to investigate laminar-turbulent transition in a mixed convection phenomenon occurring in a horizontal rectangular duct. Indeed, laminar-turbulent transition is well known in the case of forced convection but the presence of secondary flow induced by natural convection on this transition is not well highlighted. In this study, we will not be concerned by determining a critical threshold value of a Reynolds number of transition but only to estimate the degree of turbulence in the transition regime, i.e. weak turbulence in the case of a mixed convection phenomenon. This is possible thanks to the application of the wavelet transform. The calculation of the Hölder exponent, associated with the maximum value of the singularity spectrum for various experimental conditions allows the degree of turbulence to be measured. The variation of the Hölder exponent versus heat flux and Reynolds number enables us to show that there are two ways to go towards turbulence: thermal by increasing heat flux and hydrodynamic by increasing fluid velocity.     

Numerical simulations of a filament in a flowing soap film

Experiments concerning the properties of soap films have recently been carried out and these systems have been proposed as experimental versions of theoretical two‐dimensional liquids. A silk filament introduced into a flowing soap film, was seen to demonstrate various stable modes, and these were, namely, a mode in which the filament oscillates and one in which the filament is stationary and aligns with the flow of the liquid. The system could be forced from the oscillatory mode into the non‐ oscillatory mode by varying the length of the filament. In this article we use numerical and computational techniques in order to simulate the strongly coupled behaviour of the filament and the fluid. Preliminary results are presented for the specific case in which the filament is seen to oscillate continuously for the duration of our simulation. We also find that the filament oscillations are strongly suppressed when we reduce the effective length of the filament. We believe that these results are reminiscent of the different oscillatory and non‐oscillatory modes observed in experiment. The numerical solutions show that, in contrast to experiment, vortices are created at the leading edge of the filament and are preferentially grown in the curvature of the filament and are eventually released from the trailing edge of the filament. In a similar manner to oscillating hydrofoils, it seems that the oscillating filaments are in a minimal energy state, extracting sufficient energy from the fluid to oscillate. In comparing numerical and experimental results it is possible that the soap film does have an effect on the fluid flow especially in the boundary layer where surface tension forces are large. 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.     

A time‐accurate pseudo‐compressibility approach based on an unstructured hybrid finite volume technique applied to unsteady turbulent premixed flame propagation

A preconditioning approach based on the artificial compressibility formulation is extended to solve the governing equations for unsteady turbulent reactive flows with heat release, at low Mach numbers, on an unstructured hybrid grid context. Premixed reactants are considered and a flamelet approach for combustion modelling is adopted using a continuous quenched mean reaction rate. An overlapped cell‐vertex finite volume method is adopted as a discretisation scheme. Artificial dissipation terms for hybrid grids are explicitly added to ensure a stable, discretised set of equations. A second‐order, explicit, hybrid Runge–Kutta scheme is applied for the time marching in pseudo‐time. A time derivative of the dependent variable is added to recover the time accuracy of the preconditioned set of equations. This derivative is discretised by an implicit, second‐order scheme. The resulting scheme is applied to the calculation of an infinite planar (one‐dimensional) turbulent premixed flame propagating freely in reactants whose turbulence is supposed to be frozen, homogeneous and isotropic. The accuracy of the results obtained with the proposed method proves to be excellent when compared to the data available in the literature. Copyright © 2004 John Wiley & Sons, Ltd.