Bianchi type-II cosmological model with viscous fluid

A spatially homogeneous and locally rotationally symmetric Bianchi type-II cosmological model under the influence of both shear and bulk viscosity has been studied. Exact solutions are obtained with a barotropic equation of state (p=) and considering the linear relationships between, ², and ², which represent the fluid density, the expansion, and the shear scalars, respectively. Special cases with vanishing bulk viscosity coefficients and with the perfect fluid in the absence of viscosity have also been studied. The formal appearance of the solutions is the same for both the viscous as well as the perfect fluids. The difference is only in choosing a constant parameter which appears in the solutions. In the cases of either a fluid with bulk viscosity alone or a perfect fluid, the barotropic equation of state is no longer an additional assumption to be imposed; rather it follows directly from the field equations.     

Gibbs free energy of formation of calcium rhodite

The Gibbs free energy of formation of CaRh₂O₄(s) has been determined using two techniques viz., quadrupole mass spectrometer coupled to a Knudsen cell and solid-state cell incorporating CaF₂(s) as the solid electrolyte. In the former method, equilibrium O₂(g) pressures were measured over the phase field Rh(s)+Rh₂O₃(s), in the temperature range 793.7-909.1 K and over the three phase mixture CaRh₂O₄(s)+Rh(s)+CaO(s) was measured from 862.1 to 1022.7 K.The Gibbs free energy of formation of Rh₂O₃(s) from elements in their standard state can be given by

     

Kinetics and mechanism of acid catalysed dissociation of some octahedral complexes of cobalt(III) and chromium(III)

Summary The kinetics of dissociation of glycinepentaamminecobalt(III) and tetraaquomonoacetylacetonatochrormium(III) ions in moderately strong perchloric acid media have been investigated spectrophotometrically. From the dependence of the rate on various acidity functions and the observed isokinetic and free energy relationships, both the complexes appear to react by an associative process involving interaction of the conjugate acid form of the substrate complex and H₃O⁺.     

Crystallization kinetics of Cu3Ti2 forming from Cu60Ti40 glass

Amorphous to crystalline transformation in Cu₆₀Ti₄₀ alloy has been studied under conditions of constant heating rate experiments, using XRD and DSC. In the high temperature XRD experiment, the transformation has been monitored continuously as the integrated X-ray intensity corresponding to a chosen reflection from one of the two crystalline products forming at close by temperatures. Differentiation of the curve thus obtained gives the transformation rate curve which passes through a maximum. From the peak shift with heating rate, the activation energy for the formation of Cu₃Ti₂ crystalline phase has been obtained. The results have been compared with those obtained by DSC.     

Shell-model calculation of51V using pairing-plus-surface-tensor-interaction

Employing⁴⁸Ca as the core, the structure of⁵¹V is studied in the framework of a conventional shell-model. A pairing-plus-surface-tensor-interaction is used as the effective two-body interaction. Besides all configurations arising from 1f _7/2 and 2p _3/2 single-particle orbits, configurations of the form wheren ₁+n ₂=3 (the number of extracore protons) andn ₂ = 1, 2 are also considered. Low-lying energy levels are calculated and a satisfactory agreement with the experimental values is obtained. Our calculated density of states is higher than that reported previously. We also present theB(E2) values for transitions between low-lying levels and the spectroscopic factors for the⁵⁰Ti (³He, d)⁵¹V reaction. The dependence of the interaction parameters on the mass number of the core nucleus is also studied.     

Asymmetric Modulation of Protein Order–Disorder Transitions by Phosphorylation and Partner Binding

As for many intrinsically disordered proteins, order–disorder transitions in the N‐terminal oligomerization domain of the multifunctional nucleolar protein nucleophosmin (Npm‐N) are central to its function, with phosphorylation and partner binding acting as regulatory switches. However, the mechanism of this transition and its regulation remain poorly understood. In this study, single‐molecule and ensemble experiments revealed pathways with alternative sequences of folding and assembly steps for Npm‐N. Pathways could be switched by altering the ionic strength. Phosphorylation resulted in pathway‐specific effects, and decoupled folding and assembly steps to facilitate disorder. Conversely, binding to a physiological partner locked Npm‐N in ordered pentamers and counteracted the effects of phosphorylation. The mechanistic plasticity found in the Npm‐N order–disorder transition enabled a complex interplay of phosphorylation and partner‐binding steps to modulate its folding landscape.     

Slow Molecular Motions in Ionic Liquids Probed by Cross‐Relaxation of Nuclear Spins During Overhauser Dynamic Nuclear Polarization

Solution‐state Overhauser dynamic nuclear polarization (ODNP) at moderate fields, performed by saturating the electron spin resonance (ESR) of a free radical added to the sample of interest, is well known to lead to significant NMR signal enhancements in the steady state, owing to electron–nuclear cross‐relaxation. Here it is shown that under conditions which limit radical access to the molecules of interest, the time course of establishment of ODNP can provide a unique window into internuclear cross‐relaxation, and reflects relatively slow molecular motions. This behavior, modeled mathematically by a three‐spin version of the Solomon equations (one unpaired electron and two nuclear spins), is demonstrated experimentally on the ¹⁹F/¹H system in ionic liquids. Bulky radicals in these viscous environments turn out to be just the right setting to exploit these effects. Compared to standard nuclear Overhauser effect (NOE) work, the present experiment offers significant improvement in dynamic range and sensitivity, retains usable chemical shift information, and reports on molecular motions in the sub‐megahertz (MHz) to tens of MHz range—motions which are not accessed at high fields.     

Isolation and X-ray structural characterization of tetraisopropylpyrene cation radical

A practical synthesis of 1,3,6,8-tetraisopropylpyrene and the isolation and X-ray structural characterization of its monomeric cation radical salt are described.     

Synthesis and structural characterization of a novel dinuclear complex compound formed by the aerial oxidation of cobalt(II) having an interligand C-C sigma-bond

The aerial oxidation of cobalt(II) salt, in a methanolic solution, containing a hydrazone ligand, (E)-N'-(4-oxo-4-phenylbutan-2-ylidene)benzohydrazide (condensation product of benzoyl acetone and benzhydrazide, LH2) leads to the coupling of two such ligand units through the formation of a rather long C-C bond [1.601(6) A] giving rise to a dinuclear Co (III) hydrazone complex, [Co2(L)2(L')(].0.25H2O (L' = C-C coupled hydrazone ligand). The structure of the complex has been determined by X-ray crystallography and IR, UV-Vis spectroscopy and elemental analysis have characterized the complex.