A comparison of the von Mises and Hencky equivalent strains for use in simple shear experiments

The von Mises equivalent strain increment is derived for the case of large strain simple shear (torsion testing). This is used, in conjunction with the von Mises yield surface, to define the von Mises equivalent stress as well as the incremental work per unit volume. Integration of the equivalent strain increment leads to the definition of the von Mises equivalent strain for torsion. The Hencky equivalent strain increment is derived from the Hencky strain defined as the logarithm of the semi major and minor axes of the strain ellipse. This is then used, via the incremental work, to derive the ‘Hencky equivalent stress’. In the Onaka approach, the numerical values of the principal strain increments were integrated without taking into account the continuous rotation of the strain ellipse. This invalid operation leads to an expression for the equivalent strain increment that cannot be applied to the large strains considered by Onaka. Using the correct increments of the Hencky strain, it is shown that the shear strain increments turn negative and consequently, the incremental work becomes negative when the shear is large.     

A Redox‐Confused Bismuth(I/III) Triamide with a T‐Shaped Planar Ground State

Reaction of a tethered triamine ligand with Bi(NMe₂)₃ gives a Bi triamide, for which a Bi^I electronic structure is shown to be most appropriate. The T‐shaped geometry at bismuth provides the first structural model for edge inversion in bismuthines and the only example of a planar geometry for pnictogen triamides. Analogous phosphorus compounds exhibit a distorted pyramidal geometry because of different Bi?N and P?N bond polarities. Although considerable Bi^I character is indicated for the title Bi triamide, it exhibits reactivity similar to Bi^III electrophiles, and expresses either a vacant or a filled p orbital at Bi, as evidenced by coordination of either pyridine N‐oxide or W(CO)₅. The product of the former shows evidence of coordination‐induced oxidation state change at bismuth.     

Hydrostibination

A rigid naphthalenediamine framework has been used to prepare antimony hydrides that feature LUMO shapes and energies similar to those found in secondary boranes. By exploiting this feature, we introduce the first examples of uncatalyzed hydrostibination reactions of robust C≡C, C=C, C=O, and N=N bonds as new elementary hydrometalation reactions analogous to hydroboration. These results endorse the notion of a diagonal relationship between the lightest p‐block element and the heaviest Group 15 elements and may lead to the conception of novel reaction chemistry.     

Mössbauer and magnetic studies on nanocrystalline NiFe2O4 particles prepared by ethylene glycol route

NiFe₂O₄ nanoparticles have been synthesized by co-precipitation method at 145°C in N₂ atmosphere using ethylene glycol as solvent and capping agent. This gives the promising synthesis route for nanoparticles at low temperature. The as-synthesized NiFe₂O₄ is subsequently heated at 400°C, 500°C, 700°C and 800°C. Crystallite size increases with the heat treatment temperature. The heat treatment temperature has direct effect on the electron paramagnetic resonance and intrinsic magnetic properties. The room temperature Mössbauer spectrum of the 800°C heated sample shows the two sextets pattern indicating that the sample is ferrimagnetic and Fe^3?+? ions occupy both tetrahedral and octahedral sites of spinel structure.     

Ab initio calculation of vibrational frequencies of GexSe1−x glass

We have used the density functional theory to make the models of Ge_xSe_1?x glass for which the energy is a minimum. The clusters, Ge₂Se₂, Ge₂Se₃, Ge₃Se, Ge₃Se₂, Ge₄Se, GeSe₃, GeSe₄, chain mode zig-zag Ge₄Se₃, corner sharing GeSe₄, and edge sharing Ge₂Se₆, have been made successfully and their vibrational spectra have been calculated from the first principles. We are able to optimize the bond distances as well as the bond angles. The calculated values of the frequencies of vibrations of the various clusters have been compared with those obtained from the experimental Raman spectra of actual glasses, Ge_xSe_1?x(0 < x < 0.3). The local concentration, x within 0.25 nm is nonuniform in the amorphous material. When the same cluster occurs in two stable configurations, low frequency vibrations of frequency, ν < 100 cm^?1, are found. The corner sharing GeSe₄ has low frequency modes at 54 cm^?1 and 93 cm^?1 whereas these modes disappear in the pyramidal configuration. The low frequency modes are therefore associated with the breaking of C₄ symmetry of the pyramidal configuration. The computed vibrational frequencies of clusters Ge₃, Ge₄Se₃, Ge₂Se₃, GeSe₃ and Ge₃Se₂ are actually present in the Raman spectra of the glass, Ge_xSe_1?x(0 < x < 0.3).     

Luminescence studies of diopside doped with various concentrations of Dysprosium (III)

Research on Chemical Intermediates - Diopside doped with various concentration (0.5, 1.0, 1.5, 2.0 and 2.5&nbsp;mol%) of Dysprosium were&nbsp;prepared using solid-state reaction technique....     

Conduction mechanism in amorphous Si films

dc conductivity as a function of temperature has been measured for as-evaporated and annealed films of amorphous Si, grown by the vacuum evaporation technique. The experimental data suggest that conduction in the higher temperature range (～175–300 K) is by the thermally activated holes in the localized states near the valence band edge while conduction in the lower temperature range (～77–175 K) is found to be thermally assisted tunnelling in the localized states near the Fermi level. The activation energy for both the processes is found to increase with an increase in the annealing temperature. The average hopping distance, calculated for conduction near the Fermi level, is also found to increase with an increase in the annealing temperature.     

Ab initio calculation of vibrational frequencies of GexPxS1−2x glass

The vibrational frequencies of GeS₄, GeP₄, Ge₂S₆, GeP₃, Ge₃P, Ge₂P₂, P₂S₂, P₃S, P₄S₃, α-P₄S₄, β-P₄S₄, α-P₄S₅, β-P₄S₅, P₄S₇, P₄S₉ and P₄S₁₀ are theoretically computed from the first principles. The Raman frequencies of Ge_xP_xS_1−2x glass are obtained for x varying from 0.05 to 0.019. The computed fundamental frequencies of clusters are compared with those experimentally found. In this way, we are able to identify the vibrating clusters in the real glass. The clusters identified in the real glass are found to be Ge₂P₂, P₄S₃, α-P₄S₄, β-P₄S₄, β-P₄S₅, P₄S₇, P₄S₉, β-P₄S₅, Ge₂S₆, Ge₃P.     

Solution phase synthesis of a diverse library of highly substituted isoxazoles

The iodocyclization of O-methyloximes of 2-alkyn-1-ones affords 4-iodoisoxazoles, which undergo various palladium-catalyzed reactions to yield 3,4,5-trisubstituted isoxazoles. The palladium-catalyzed processes have been adapted to parallel synthesis utilizing commercially available boronic acid, acetylene, styrene, and amine sublibraries. Accordingly, a diverse 51-member library of 3,4,5-trisubstituted isoxazoles has been generated.     

Exploring the organization and dynamics of hippocampal membranes utilizing pyrene fluorescence

The organization and dynamics of cellular membranes in the nervous system are crucial for the function of neuronal membrane receptors and signal transduction. Previous work from our laboratory has established hippocampal membranes as a convenient natural source for studying neuronal receptors. In this paper, we have monitored the organization and dynamics of hippocampal membranes and their modulation by cholesterol using pyrene fluorescence. The apparent dielectric constant experienced by pyrene in hippocampal membranes turns out to be approximately 20+/-3, depending on the experimental condition. Our results show that the polarity of the hippocampal membrane is increased upon cholesterol depletion, as monitored by changes in the ratio of pyrene vibronic peak intensities (I1/I3). This is accompanied by an increase in lateral diffusion, measured as an increase in the pyrene excimer/monomer ratio. These results are relevant in understanding the complex organization and dynamics of hippocampal membranes and could have implications in neuronal diseases characterized by defective cholesterol metabolism.