Synthesis, structure, transformation studies and catalytic properties of open-framework cadmium thiosulfate compounds

Five new thiosulfate based inorganic-organic hybrid open-framework compounds have been synthesized employing mild reaction conditions. Of the five compounds, [Na-2(H2O)(8)][Cd(C10H8N2)( S2O3)(2)]center dot 2H(2)O, I and [Cd-2(C10H8N2)(2)(HS2O3)(2)(S2O3)(2)][(C10H9N2)(2)(C10H8N2)(2)]center dot 8H(2)O, II have one-dimensional (1D) structures and [Cd(C10H8N2)(H2O)(2)(S2O3)]center dot 2H(2)O, III, [Cd-2(C10H8N2)(3)(S2O3)(2)], IV and [Cd-2(C10H8N2)(2.5)(S2O3)(2)], V have three- dimensional (3D) structures. The 1D structures are somewhat related, formed by the bonding between tetrahedral Cd centers (CdN2S2) and 4,4'-bipyridine (bpy) units. The inter-chain spaces are occupied by the hanging thiosulfate units in both the cases along with Na(H2O)(6) chains in I and free bpy units in II. The three 3D structures have one-dimensional cadmium thiosulfate chains linked by bpy units. Interpenetration has been observed in all the 3D structures. The 3D structures appear to be related and can be derived from fgs net. Transformation studies on the 1D compound, [Na-2(H2O)(8)][Cd(C10H8N2)(S2O3)(2)]center dot 2H(2)O, I, indicated a facile formation of [Cd(C10H8N2)(H2O)(2)(S2O3)]center dot 2H(2)O, III. Prolonged heating of I gave rise to a 3D cadmium sulfate phase, [Cd-2(C10H8N2)(2)(H2O)(3)(SO4)(2)]center dot 2H(2)O, VI. Compound VI has one-dimensional cadmium sulfate chains formed by six-membered rings connected by bpy units to form a 3D structure, which appears to resemble the topological arrangement of III. Transformation studies of III indicates the formation of IV and V, and at a higher temperature a new 3D cadmium sulfate, [Cd(C10H8N2)(SO4)], VII. Compound VII has a 4 x 4 grid cadmium sulfate layers pillared by bpy units. All the compounds were characterized by PXRD, TGA, IR and UV-visible studies. Preliminary studies on the possible use of the 3D compounds (III-VII) in heterogeneous cyanosilylation of imines appear to be promising.

Phase relations and thermodynamic properties of compounds in the pseudobinary system BaO-Y2O3

The coexisting phases in the pseudobinary system BaO-Y2O3 have been identified by equilibrating samples containing different amounts of component oxides at 1173, 1273 and 1373 K. Only two ternary oxides, BaY2O4 and Ba3Y4O9, have been found to be stable in the temperature range of investigation. Solid state galvanic cells: Pt, O2+BaO+BaF2double vertical barBaF2+2mol%Al2O3double vertical barBaF2+BaY2O4+Y2O3+O2, Pt and Pt, O2+BaO+BaF2double vertical barBaF2+2mol% Al2O3double vertical barBaF2+BaY2O4+Ba3Y4O9+O2, Pt have been employed for determining the Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from the component oxides in the range 850 to 1250 K. A composite solid electrolyte incorporating Al2O3-dispersed BaF2 was used in the cells. To prevent interaction between the Al2O3 powder and electrode materials, the solid electrolyte was coated with pure BaF2. The Gibbs' energies of formation of BaY2O4 and Ba3Y4O9 from component oxides are given by: Δf0 (BaY2O4, s)=−128,310+5.211T (±580) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K) and ΔGfo(Ba3Y4O9, s)= −317,490 −24.704T (±1100) J mol−1, (850less-than-or-equals, slantTless-than-or-equals, slant1250 K).

Synthesis, X-ray structure and catalytic properties of a copper(II) Schiff base complex modeling the activity of the Cu-B site of dopamine beta-hydroxylase

The copper(II) complex [Cu(salgly) (bpy)] . 4H(2)O (1), where salgly is a tridentate glycinatosalicylaldimine Schiffbase Ligand, is prepared and structurally characterized. The complex is found to be catalytically active in the oxidation of ascorbic acid by dioxygen and the process is also effective in the presence of benzylamine giving benzaldehyde as a product, thus modeling the activity of the Cu-B site of dopamine beta-hydroxylase. (C) 2000 Elsevier Science S.A. All rights reserved.

Synthesis,characterization and photoluminescence properties of CaSiO3 :Dy3+ nanophosphors

CaSiO3 : Dy3+ (1-5 mol. %) nanophosphors were synthesized by a simple low-temperature solution combustion method. Powder X-ray diffraction patterns revealed that the phosphors are crystalline and can be indexed to a monoclinic phase. Scanning electron micrographs exhibited faceted plates and angular crystals of different sizes with a porous nature. Photoluminescence properties of the Dy3+-doped CaSiO3 phosphors were observed and analyzed. Emission peaks at 483, 573 and 610 nm corresponding to Dy3+ were assigned as F-4(9/2)-> H-6(15/2), F-4(9/2) -> H-6(13/2) and F-4(9/2) -> H-6(11/2) transitions, respectively, and dominated by the Dy3+ F-4(9/2) -> H-6(13/2) hyperfine transition. Experimental results revealed that the luminescence intensity was affected by both heat treatment and the concentration of Dy3+ (1-5 mol. %) in the CaSiO3 host. Optimal luminescence conditions were achieved when the concentration of Dy3+ was 2 mol. %. UV-visible absorption features an intense band at 240 nm, which corresponds to an O-Si ligand-to-metal charge transfer band in the SiO32- group. The optical energy band gap for the undoped sample was found to be 5.45 eV, whereas in Dy3+-doped phosphors it varies in the range 5.49-5.65 eV. The optical energy gap widens with increase of Dy3+ ion dopant.

Effect of Li substitution on dielectric and ferroelectric properties of ZnO thin films grown by pulsed-laser ablation

Li-doped ZnO thin films (Zn1-xLixO, x=0.05-0.15) were grown by pulsed-laser ablation technique. Highly c-axis-oriented films were obtained at a growth temperature of 500 degrees C. Ferroelectricity in Zn1-xLixO was found from the temperature-dependent dielectric constant and from the polarization hysteresis loop. The transition temperature (T-c) varied from 290 to 330 K as the Li concentration increased from 0.05 to 0.15. It was found that the maximum value of the dielectric constant at T-c is a function of Li concentration. A symmetric increase in memory window with the applied gate voltage is observed for the ferroelectric thin films on a p-type Si substrate. A ferroelectric P-E hysteresis loop was observed for all the compositions. The spontaneous polarization (P-s) and coercive field (E-c) of 0.6 mu C/cm(2) and 45 kV/cm were obtained for Zn0.85Li0.15O thin films. These observations reveal that partial replacement of host Zn by Li ions induces a ferroelectric phase in the wurtzite-ZnO semiconductor. The dc transport studies revealed an Ohmic behavior in the lower-voltage region and space-charge-limited conduction prevailed at higher voltages. The optical constants were evaluated from the transmission spectrum and it was found that Li substitution in ZnO enhances the dielectric constant.

Structural, dielectric and ferroelectric properties of four-layer Aurivillius phase Na0.5La0.5Bi4Ti4O15

Monophasic Na0.5La0.5Bi4Ti4O15 powders were synthesized via the conventional solid-state reaction route. The X-ray powder diffraction (XRD), selected area electron diffraction (SAED) and high resolution transmission electron microscopy (HRTEM) studies carried out on the as synthesized powdered samples confirmed the phase to be a four-layer Aurivillius that crystallizes in an orthorhombic A2(1)am space group. The microstructure and the chemical composition of the sintered sample were examined by scanning electron microscope (SEM) equipped with an energy dispersive X-ray analyzer (EDX). The dielectric properties of the ceramics have been studied in the 27-700 degrees C temperature range at various frequencies (100 Hz to 1 MHz). A sharp dielectric anomaly was observed at 580 degrees C for all the frequencies corresponding to the ferroelectric to paraelectric phase transition. Saturated ferroelectric hysteresis loops were observed at 200 degrees C and the associated remnant polarization (P-r) and coercive field (E-c) were found to be 7.4 mu C/cm(2) and 34.8 kV/cm, respectively. AC conductivity analysis confirmed the existence of two different conduction mechanisms in the ferroelectric region. Activation energies calculated from the Arrhenius plots were similar to 0.24 eV and similar to 0.84 eV in the 300-450 degrees C and 450-580 degrees C temperature ranges, respectively. (C) 2010 Elsevier B.V. All rights reserved.

Synthesis, characterization and photoluminescence properties of Gd2O3:Eu3+ nanophosphors prepared by solution combustion method

Gd2O3:Eu3+ (0.5-8.0 mol%) nanophosphors have been prepared by low temperature solution combustion method using metal nitrates as oxidizers and oxalyl dihydrazide (ODH) as a fuel. The phosphors are well characterized by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and photoluminescence (PL) techniques. PXRD patterns of as-formed and calcined (800 degrees C, 3 h) Gd2O3 powders exhibit monoclinic phase with mean crystallite sizes ranging from 20 to 50 nm. Eu3+ doping changes the structure from monoclinic to mixed phase of monoclinic and cubic. SEM micrographs shows the products are foamy, agglomerated and fluffy in nature due to the large amount of gases liberated during combustion reaction. Upon 254 nm excitation the photoluminescence of the Gd2O3:Eu3+ particles show red emission at 611 nm corresponding to D-5(0)-> F-7(2) transition. It is observed that PL intensity increases with calcination temperature. This might be attributed to better crystallization and eliminates the defects, which serve as centers of non-radiative relaxation for nanomaterials. It is observed that the optical energy gap (E-g) is widened with increase Eu3+ content. (C) 2010 Elsevier B.V. All rights reserved.

Sliding Modes for the Simulation of Mechanical and Electrical Systems Defined by Differential-Algebraic Equations

We offer a technique, motivated by feedback control and specifically sliding mode control, for the simulation of differential-algebraic equations (DAEs) that describe common engineering systems such as constrained multibody mechanical structures and electric networks. Our algorithm exploits the basic results from sliding mode control theory to establish a simulation environment that then requires only the most primitive of numerical solvers. We circumvent the most important requisite for the conventionalsimulation of DAEs: the calculation of a set of consistent initial conditions. Our algorithm, which relies on the enforcement and occurrence of sliding mode, will ensure that the algebraic equation is satisfied by the dynamic system even for inconsistent initial conditions and for all time thereafter. [DOI:10.1115/1.4001904]

Static and dynamic properties of incommensurate smectic-AIC liquid crystals

We study the elasticity, topological defects, and hydrodynamics of the recently discovered incommensurate smectic (AIC) phase, characterized by two collinear mass density waves of incommensurate spatial frequency. The low-energy long-wavelength excitations of the system can be described by a displacement field u(x) and a ��phason�� field w(x) associated, respectively, with collective and relative motion of the two constituent density waves. We formulate the elastic free energy in terms of these two variables and find that when w=0, its functional dependence on u is identical to that of a conventional smectic liquid crystal, while when u=0, its functional dependence on w is the same as that for the angle variable in a slightly anisotropic XY model. An arbitrariness in the definition of u and w allows a choice that eliminates all relevant couplings between them in the long-wavelength elastic energy. The topological defects of the system are dislocations with nonzero u and w components. We introduce a two-dimensional Burgers lattice for these dislocations, and compute the interaction between them. This has two parts: one arising from the u field that is short ranged and identical to the interaction between dislocations in an ordinary smectic liquid crystal, and one arising from the w field that is long ranged and identical to the logarithmic interaction between vortices in an XY model. The hydrodynamic modes of the AIC include first- and second-sound modes whose direction-dependent velocities are identical to those in ordinary smectics. The sound attenuations have a different direction dependence, however. The breakdown of hydrodynamics found in conventional smectic liquid crystals, with three of the five viscosities diverging as 1/? at small frequencies ?, occurs in these systems as well and is identical in all its details. In addition, there is a diffusive phason mode, not found in ordinary smectic liquid crystals, that leads to anomalously slow mechanical response analogous to that predicted in quasicrystals, but on a far more experimentally accessible time scale.

Effect of sintering on optical, structural and photoluminescence properties of ZnO thin films prepared by sol-gel process

Zinc oxide (ZnO) thin films have been deposited on glass substrates via sol-gel technique using zinc acetate dihydrate as precursor by spin coating of the sol at 2000 rpm. Effects of annealing temperature on optical, structural and photo luminescence properties of the deposited ZnO films have been investigated. The phase transition from amorphous to polycrystalline hexagonal wurtzite structure was observed at an annealing temperature of 400 degrees C. An average transmittance of 87% in the visible region has been obtained at room temperature. The optical transmittance has slightly increased with increase of annealing temperature. The band gap energy was estimated by Tauc's method and found to be 3.22 eV at room temperature. The optical band gap energy has decreased with increasing annealing temperature. The photoluminescence (PL) intensity increased with annealing temperature up to 200 degrees C and decreased at 300 degrees C. (c) 2010 Elsevier B.V. All rights reserved.

Formation of lead pyrophosphate glass and the role of anion disproportionation

Thermal, spectroscopic and electrical properties of lead pyrophosphate glass prepared by melt quenching have been examined. A model based on the structural disproportionation of the P2O 7 4− ions has been proposed and is shown to consistently explain all the observations. The equilibrium of various anionic species has been discussed on the basis of their electronegativities which are in turn related to their basicities.