Antipyrine and pyridine n-oxide complexes of iron(II)

Iron(II) complexes of 1-phenyl-2,3-dimethyl-5-pyrazolone (antipyrine, Apy) and pyridine N-oxide (PyO), having the formulae [Fe(Apy)6](ClO4)2, Fe(Apy)2Cl2, Fe(Apy)2Br2, Fe(Apy)4I2, [Fe(PyO)3Cl3]2 . 2H2O, [Fe(PyO)Cl2 . 2H2O]2, [Fe(PyO)3Br2]2 and [Fe(PyO)6]I2 have been prepared and characterized. [Fe(Apy)6](ClO4)2 in nitrobenzene and [Fe(PyO)6]I2 in acetonitrile behave as 1:2 electrolytes; Fe(Apy)4I2 shows considerable dissociation while Fe(Apy)2Cl2 and Fe(Apy)2Br2 are non-electrolytes and monomeric in nitrobenzene. [Fe(PyO)3Cl2]2 . 2H2O and [Fe(PyO)3Br2]2 in nitrobenzene and [Fe(PyO)Cl2 . 2H2O]2 in acetonitrile behave as non-electrolytes. All the complexes are spin-free. The i.r. spectra show that the oxygens of the CO and NO groups are the donors in the Apy and PyO complexes. A large decrease in the NO stretching frequency in [Fe(PyO)Cl2. 2H2O]2 suggests PyO acts as a bridge forming a binuclear complex. The chloro and the bromo complexes of Apy have been assigned pseudo tetrahedral structures while the rest of the complexes have octahedral or near octahedral configurations around the iron(II) on the basis of the magnetic moments and the electronic transitions.

Unsteady mixed convection flow of a thermomicropolar fluid on a long thin vertical cylinder

The unsteady laminar mixed convection boundary layer flow of a thermomicropolar fluid over a long thin vertical cylinder has been studied when the free stream velocity varies with time. The coupled nonlinear partial differential equations with three independent variables governing the flow have been solved numerically using an implicit finite difference scheme in combination with the quasilinearization technique. The results show that the buoyancy, curvature and suction parameters, in general, enhance the skin friction, heat transfer and gradient of microrotation, but the effect of injection is just opposite. The skin friction and heat transfer for the micropolar fluid are considerably less than those for the Newtonian fluids. The effect of microrotation parameter is appreciable only on the microrotation gradient. The effect of the Prandtl number is appreciable on the skin friction, heat transfer and gradient of microtation.

A mixed-split scheme for 2-D DPCM based LSF quantization

In this paper a mixed-split scheme is proposed in the context of 2-D DPCM based LSF quantization scheme employing split vector product VQ mechanism. Experimental evaluation shows that the new scheme is successfully being able to show better distortion performance than existing safety-net scheme for noisy channel even at considerably lower search complexity, by efficiently exploiting LSF trajectory behavior across the consecutive speech frames.

Rare earth exchanged (Ce3+, La3+ and RE3+) H-Y zeolites as solid acid catalysts for the synthesis of linear alkyl benzenes

Rare earth exchanged H–Y zeolites were prepared by simple ion exchange methods at 353 K and have been characterized using different physicochemical techniques. A strong peak around 58 ppm in the 27Al{1H} MAS NMR spectra of these zeolites suggests a tetrahedral coordination for the framework aluminium. Small peak at or near 0 ppm is due to hexa-coordinated extra-framework aluminium and a shoulder peak near 30 ppm is a penta-coordinated aluminium species; [Al(OH)4]−. The vapor-phase benzene alkylation with 1-decene and 1-dodecene was investigated with these catalytic systems. Under the reaction conditions of 448 K, benzene/olefin molar ratio of 20 and time on stream 3 h, the most efficient catalyst was CeH–Y which showed more than 70% of olefin conversion with 48.5% 2-phenyldecane and 46.8%, 2-phenyldodecane selectivities with 1-decene and 1-dodecene respectively.

Probing top-gated field effect transistor of reduced graphene oxide monolayer made by dielectrophoresis

We demonstrate a top-gated field effect transistor made of a reduced graphene oxide (RGO) monolayer (graphene) by dielectrophoresis. The Raman spectrum of RGO flakes of typical size of 5 mu m x 5 mu m shows a single 2D band at 2687 cm(-1), characteristic of single-layer graphene.The two-probe current-voltage measurements of RGO flakes, deposited in between the patterned electrodes with a gap of 2.5 mu m using ac dielectrophoresis, show ohmic behavior with a resistance of similar to 37 k Omega. The temperature dependence of the resistance (R) of RGO measured between 305 K and 393 K yields a temperature coefficient of resistance [dR/dT]/R similar to -9.5 x 10(-4)/K, the same as that of mechanically exfoliated single-layer graphene. The field-effect transistor action was obtained by electrochemical top-gating using a solid polymer electrolyte (PEO + LiClO4) and Pt wire. The ambipolar nature of graphene flakes is observed up to a doping level of similar to 6 x 10(12)/cm(2) and carrier mobility of similar to 50 cm(2)/V s. The source-drain current characteristics show a tendency of current saturation at high source-drain voltage which is analyzed quantitatively by a diffusive transport model. (C) 2010 Elsevier Ltd. All rights reserved.

Investigations of oxide superconductors by x-ray absorption, photoemission and cognate spectroscopies

X-ray absorption spectra, X-ray photoelectron spectra and Auger spectra of cuprate superconductors are discussed. The studies establish the absence of Cu3+ for all practical purposes, but point out the importance of oxygen holes. X-ray photoelectron spectra of BaBi0.25Pb0.75O3 and related compounds are also examined.

Synthesis of metal oxide nanorods using carbon nanotubes as templates

Nanorods of several oxides, with diameters in the range of 10-200 nm and lengths upto a few microns, have been prepared by templating against carbon nanotubes. The oxides include V2O5, WO3, MoO3 and Sb2O5 as well as metallic MoO2, RuO2 and IrO2. The nanorods tend to be single-crystalline structures. Nanotube structures have also been obtained in MoO3 and RuO2.

Solution cation-binding properties of segmented polyethylene oxide-A C-13 NMR spectroscopic study

Two segmented polyethylene oxides, SPEO-3 and SPEO-4, were prepared using a novel transetherification methodology. Their structures were confirmed by H-1 and C-13 NMR spectroscopy. The complexation of these SPEO's with alkali-metal ions in solution was investigated by C-13 NMR spectroscopy. The mole-fraction method was used to determine the complexation ratio of SPEO with LIClO4 at 25 degrees C, which showed that these formed 1:1 (polymer repeat unit/salt) complexes. The association constant, K, for the complex formation was calculated from the variation of the chemical shift values with salt concentration, using a standard nonlinear least-square fitting procedure. The maximum change in chemical shift (Delta delta) and the K values suggest that both SPEO-3 and SPEO-4 formed stronger complexes with lithium salts than with sodium salts. Unexpectedly, the K values were found to be different, when the variation of delta of different carbons was used in the fitting procedure. This suggests that several possible complexed species may be in equilibrium with the uncomplexed one. Structurally similar model compounds were also prepared and their complexation studies indicated that all of them also formed 1:1 complexes with Li salts. Interestingly, it was observed that the polymers gave higher K values suggesting the formation of more stable complexes in polymers when compared to the model analogues. (C) 2000 John Wiley & Sons, Inc.

Studies on optical absorption and photoluminescenceproperties of Pr3+ and Nd3+ doped mixed alkali chloroborate glasses

This article presents the optical absorption and emission properties of Pr3+ and Nd3+ doped two different mixed alkali chloroborate glass matrices of the type 70B(2)O(3)center dot xLiCl center dot(30 - x)NaCl and 70B(2)O(3)center dot xLiCl center dot(30 - x)KCl (x = 5, 10, 15.20 and 25). The variation of Judd-Ofelt parameters (Omega(2), Omega(4) and Omega(6)), total radiative transition probabilities (A(T)), radiative lifetimes (tau(R)) and emission cross-sections (sigma(p)) with the variation of alkali contents in the glass matrix have been discussed in detail. The changes in the peak wavelengths of the hypersensitive transition and intensity parameters with x are correlated to the structural changes in the host matrix. The estimated radiative lifetimes of certain excited states of Pr3+ and Nd3+ in these two glass matrices are reported. Peak stimulated emission cross-sections (sigma(p)) are reported for the observed emission transitions of Pr3+ and Nd3+ ions. Branching ratios (beta) of the observed emission transitions obtained from the Judd-Ofelt theory are compared with the values obtained from the emission spectra. (C) 2010 Elsevier B.V. All rights reserved.

Mixed-mode stress intensity factors for arbitrarily oriented cracks in cylindrical shells under axial pull and torsion

Results of photoelastic investigations conducted on cylindrical tubes (made of Araldite material) containing cracks oriented at 0°, 30°, 45°, 60° and 90° to the axis of the tube and subjected to axial and torsional loads are reported. The stress-intensity factors (SIFs) were determined by analysing the crack-tip stress fields. Smith and Smith's method [Engng Fracture Mech.4, 357–366 (1972)] and a new method developed by the authors by modifying Rakesh et al.'s method [Proc. 26th Congress of ISTAM, India (1981)] were employed to evaluate the mixed-mode SIFs.