A novel method for bromodecarboxylation of α,β-unsaturated carboxylic acids using catalytic sodium nitrite

A first novel synthetic utility of catalytic sodium nitrite in combination with aqueous HBr, for bromo decarboxylation of α,β-unsaturated carboxylic acid is described. α,β-Unsaturated carboxylic acid compounds successfully converted into corresponding bromo compounds. The advantages of this protocol are shorter reaction time and moderate to good yields.     

Effect of Compressive Straining on Nanoindentation Elastic Modulus of Trabecular Bone

Trabecular bone with its porous structure is an important compressive load bearing member. Different structural factors such as porosity, non-homogeneous deformation, varying trabeculae thickness, connectivity, and nanoscale (10 nm to 1 μm) to macroscale (~0.1 mm to 10 mm) composition hierarchy determine the failure properties of trabecular bone. While the above factors have important bearing on bone properties, an understanding of how the local nanoscale properties change at different macroscale compressive strain levels can be important to develop an understanding of how bone fails. In the present work, such analyses are performed on bovine femoral trabecular bone samples derived from a single animal. Analyses focus on measuring nanoindentation elastic moduli at three distinct levels of compressive strains in the bone samples: (1) when the samples are not loaded; (2) after the samples have been loaded to a strain level just before apparent yielding and the macroscale compression test is stopped; and (3) after the samples have been compressed to a strain level after apparent yielding and the macroscale compression test is stopped. Nanoindentation elastic modulus values are two orders of magnitude higher than the macroscale compressive elastic modulus values of all samples. A high variability in macroscale compressive elastic modulus values is observed because of porous architecture and small sample size. Nanoindentation elastic modulus values show a progressive reduction with increase in the extent of macroscale compressive deformation. Apparent yielding has a significant effect on this trend. The decrease in nanoindentation modulus value for all samples accelerates from approximately 20% before yielding to approximately 60% after yielding in comparison to the nanoindentation modulus values at 0% strain level. The level of variation in the predicted nanoindentation modulus values is the lowest for uncompressed samples (~16–18%). However, with increase in the extent of compression, the level of variation increases. It varied between 50% and 90% for the samples tested after yielding showing a widespread heterogeneity in local nanoscale structural order after apparent yielding. Scanning electron microscope (SEM) observations suggest that apparent yielding significantly destroys local nanoscale structural order. However, quantitative results suggest that a significant residual nanoscale stiffness varying from 5 GPa to 8 GPa among different samples still remains for possible repair facilitation.     

Axisymmetric vibrations of an isotropic elastic non-homogeneous circular plate of linearly varying thickness

Free axisymmetric vibrations of an isotropic, elastic, non-homogeneous circular plate of linearly varying thickness have been studied on the classical theory of plates. The non-homogeneity of the material of the plate is assumed to arise due to the variation of Young's modulus and density with the radius vector whereas Poisson's ratio is assumed to remain constant. The governing differential equation of motion is solved by the method of Frobenius. The transverse displacement of the plate has been expressed as a power series in terms of the radial co-ordinate. The frequency parameters corresponding to the first two modes of vibration have been computed for different values of the non-homogeneity parameter and taper constant and for clamped and simply supported edge conditions of the plate. A comparison between the numerical results for homogeneous and non-homogeneous material of the plate is also made.     

Jet produced by collapse of conical free surface of a metal by plane shock wave

Theoretical and experimental investigations of metal-jets, produced by interaction of a plane shock wave with a conical cavity at free surface of metals like aluminium, copper and mild steel, have been carried out and an attempt has been made to correlate the jet velocity with shock parameters. The velocity of the jet, obtained from the cavity of different half angles have been mostly measured with oscillographic technique. The experimental results agree with theory within experimental variations. The velocity of the jet increases monotonically with the particle velocity but decreases with increase in the angle of the cavity.     

Two-phase electrohydrodynamic simulations using a volume-of-fluid approach

A numerical methodology to simulate two-phase electrohydrodynamic flows under the volume-of-fluid paradigm is proposed. The electric force in such systems acts only at the interface and is zero elsewhere in the two fluids. Continuum surface force representations are derived for the electric field force in a system of dielectric–dielectric and conducting–conducting fluids. On the basis of analytical calculations for simple flow problems we propose a weighted harmonic mean interpolation scheme to smoothen the electric properties in the diffused transition region (interface). It is shown that a wrong choice of interpolation scheme (weighted arithmetic mean) may lead to a transition region thickness dependent electric field in the bulk. We simulate a set of problems with exact or approximate analytical solutions to validate the numerical model proposed. A coupled level set and volume-of-fluid (CLSVOF) algorithm has been used for simulations presented here.     

High strain-rate behavior of ice under uniaxial compression

In the present study, a modified split Hopkinson pressure bar (SHPB) is employed to investigate the dynamic response of ice under uniaxial compression in the range of strain rates from 60 to 1400 s^?1 and at initial test temperatures of ?10 and ?30 °C. The compressive strength of ice shows positive strain-rate sensitivity over the range of strain rates employed; a slight influence of ice microstructure is observed, but it is much less than that reported previously for ice deformation under quasi-static loading conditions [Schulson, E.M., IIiescu, D., Frott, A., 2005. Characterization of ice for return-to-flight of the space shuttle. Part 1 – Hard ice. NASA CR-2005-213643-Part 1]. Specimen thickness, within the range studied, was found to have little or no effect on the peak (failure) strength of ice, while lowering the test temperature from ?10 to ?30 °C had a considerable effect, with ice behaving stronger at the lower test temperature. Moreover, unlike in the case of uniaxial quasi-static compression of ice, the effect of specimen end-constraint during the high rate compression was found to be negligible. One important result of these experiments, which may have important implications in modeling ice impacts, involves the post “peak-stress” behavior of the ice in that the ice samples do not catastrophically lose their load carrying capacity even after the attainment of peak stress during dynamic compression. This residual (tail) strength of the damaged/fragmented ice is sizable, and in some cases is larger than the quasi-static compression strength reported for ice. Moreover, this residual strength is observed to be dependent on sample thickness and the strain rate, being higher for thinner samples and at higher strain-rates during dynamic compression.     

Studies on the hydrolysis of {Cu[Al(OPri)4]2}, a single source precursor for CuAl2O4 spinel

Controlled hydrolysis experiments of the heterobimetallic alkoxide {Cu[Al(OPrⁱ)₄]₂}, were investigated. The progress of hydrolysis was monitored by the FT-IR and NMR spectroscopy. A blue colored gel appeared after four days of hydrolysis and the hydrolysis experiments were continued up to ten days. The elemental analysis and FT-IR spectrum revealed the presence of isopropoxy group in the gel obtained even after ten days of hydrolysis. The presence of carbon was further confirmed from the presence of a weak signal at 3.351 ppm in the ¹³C CP-NMR spectrum. The thermal analysis of the hydrolyzed gels in air also suggested that they were not simple hydroxides of copper and aluminum. The gels on one time heat treatment at 900 °C in air yielded inverse spinel CuAl₂O₄ as shown by the PXRD patterns. CuO was observed along with CuAl₂O₄ in the case of the fired product of the gel obtained after five or six days of hydrolysis which was absent in the fired product of ten days hydrolyzed gel. The phase pure spinel was nanocrystalline in nature as revealed by the analysis of PXRD pattern. TEM images revealed porous structured nanocrystallites. The optical property of the spinel was evaluated by the diffuse reflectance spectroscopy. Raman spectrum showed five bands at 767, 698, 595, 450 and 356 cm^?1 conforming to the spinel structure.     

A novel system for the synthesis of nitriles from aldehydes using aqueous ammonia and sodium dichloroiodate

A simple and mild method for the conversion of varieties of aldehydes to the corresponding nitriles using aqueous ammonia and aqueous sodium dichloroiodate reagent at room temperature is discussed. Advantages of this system are short reaction time, easy work-up and moderate to good yields.     

A highly effective synthesis of 2-alkynyl-7-azaindoles: Pd/C-mediated alkynylation of heteroaryl halides in water

The reaction of 4-chloro-2-iodo-7-azaindole with terminal alkynes was investigated using 10% Pd/C-PPh₃-CuI as a catalyst system in water. This study afforded a new, mild and selective process for the preparation of 2-alkynyl-4-chloro-7-azaindole in good yields via C-C bond forming reaction. The resulting chloro derivative can be functionalized further via another Pd-mediated C-C bond forming reaction with arylboronic acid.