Correlation of Oxygen Storage Capacity and Structural Distortion in Transition-Metal-, Noble-Metal-, and Rare-Earth-Ion-Substituted CeO2 from First Principles Calculation

Oxygen storage/release (OSC) capacity is an important feature common to all three-way catalysts to combat harmful exhaust emissions. To understand the mechanism of improved OSC for doped CeO2, we undertook the structural investigation by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H-2-TPR (temperature-programmed hydrogen reduction) and density functional theoretical (DFT) calculations of transition-metal-, noble-metal-, and rare-earth (RE)-ion-substituted ceria. In this report, we present the relationship between the OSC and structural changes induced by the dopant ion in CeO2. Transition metal and noble metal ion substitution in ceria greatly enhances the reducibility of Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu, Pd, Pt, Ru), whereas rare-earth-ion-substituted Ce(1-x)A(x)O(2-delta) (A = La, Y) have very little effect in improving the OSC. Our simulated optimized structure shows deviation in cation oxygen bond length from ideal bond length of 2.34 angstrom (for CeO2). For example, our theoretical calculation for Ce28Mn4O62 structure shows that Mn-O bonds are in 4 + 2 coordination with average bond lengths of 2.0 and 3.06 angstrom respectively. Although the four short Mn-O bond lengths spans the bond distance region of Mn2O3, the other two Mn-O bonds are moved to longer distances. The dopant transition and noble metal ions also affects Ce coordination shell and results in the formation of longer Ce-O bonds as well. Thus longer cation oxygen bonds for both dopant and host ions results in enhanced synergistic reduction of the solid solution. With Pd ion substitution in Ce1-xMxO2-delta (M = Mn, Fe, Co, Ni, Cu) further enhancement in OSC is observed in H-2-TPR. This effect is reflected in our model calculations by the presence of still longer bonds compared to the model without Pd ion doping. The synergistic effect is therefore due to enhanced reducibility of both dopant and host ion induced due to structural distortion of fluorite lattice in presence of dopant ion. For RE ions (RE = Y, La), our calculations show very little deviation of bonds lengths from ideal fluorite structure. The absence of longer Y-O/La-O and Ce-O bonds make the structure much less susceptible to reduction.

A role for calcium in gonadotrophin-releasing hormone (GnRH) stimulated secretion of chorionic gonadotrophin by first trimester human placental minces in vitro

In vitro studies using first-trimester human placental minces have shown that stimulation of human chorionic gonadotrophin (hCG) secretion by gonadotrophin-releasing hormone (GnRH) is dependent upon the presence of extracellular calcium. Addition of GnRH to first-trimester placental minces in vitro was found to stimulate 45Ca2+ uptake into placental minces, and the process was associated with an increase in immunoreactive hCG in the medium. Addition of GnRH to placental minces preloaded with 45Ca2+ stimulated the efflux of 45Ca2+ within one minute. The calmodulin inhibitors chlorpromazine andtrifluoperazine inhibited the basal uptake and efflux of 45Ca2+ suggesting the involvement of calmodulin in the mobilization of calcium in the placenta.

First total synthesis of a natural thapsane

A stereospecific first total synthesis of a natural thapsane 1, from the readily available cyclogeraniol 8, is described.

Effects of Zr and Ti doping on the dielectric response of CeO2: A comparative first-principles study

Zr doping in ceria (CeO2) results in enhanced static dielectric response compared to pure ceria. On the other hand, Ti doping in ceria keeps its dielectric constant unchanged. We use first-principles density functional theory calculations based on pseudopotentials and a plane wave basis to determine electronic properties and dielectric response of Zr/Ti-doped and oxygen-vacancy-introduced ceria. Softening of phonon modes is responsible for the enhancement in dielectric response of Zr-doped ceria compared to that of pure ceria. The ceria-zirconia mixed oxides should have potential use as high-k materials in the semiconductor industry. (c) 2010 Elsevier Ltd. All rights reserved.

The first structurally characterized diruthenium(II,III) complex with four bridging arylcarboxylato ligands

The diruthenium(II,III) compound [Ru2Cl(O2CC6H4-p-OMe)4](H2O)0.25 (1) has been prepared and its crystal structure determined by X-ray studies. The crystals belong to the triclinic space group, PImage , and the asymmetric unit consists of one full dimer and two half dimers. The {Ru2(O2CC6H4-p-OMe)4+} units are bridged by chloride ions into an infinite zigzag chain, with an average Ru---Cl distance and Ru---Cl---Ru angle of 2.567(2) Å and 121.0(1)°, respectively. The average Ru---Ru distance of 2.286(1) Å in 1 is comparable with that in analogous tetra-alkylcarboxylates, Ru2Cl(O2CR)4 and tetra-amidates, Ru2Cl(ArCONH)4.

A Smooth Finite Element Method Based on Reproducing Kernel DMS-Splines

The element-based piecewise smooth functional approximation in the conventional finite element method (FEM) results in discontinuous first and higher order derivatives across element boundaries Despite the significant advantages of the FEM in modelling complicated geometries, a motivation in developing mesh-free methods has been the ease with which higher order globally smooth shape functions can be derived via the reproduction of polynomials There is thus a case for combining these advantages in a so-called hybrid scheme or a `smooth FEM' that, whilst retaining the popular mesh-based discretization, obtains shape functions with uniform C-p (p >= 1) continuity One such recent attempt, a NURBS based parametric bridging method (Shaw et al 2008b), uses polynomial reproducing, tensor-product non-uniform rational B-splines (NURBS) over a typical FE mesh and relies upon a (possibly piecewise) bijective geometric map between the physical domain and a rectangular (cuboidal) parametric domain The present work aims at a significant extension and improvement of this concept by replacing NURBS with DMS-splines (say, of degree n > 0) that are defined over triangles and provide Cn-1 continuity across the triangle edges This relieves the need for a geometric map that could precipitate ill-conditioning of the discretized equations Delaunay triangulation is used to discretize the physical domain and shape functions are constructed via the polynomial reproduction condition, which quite remarkably relieves the solution of its sensitive dependence on the selected knotsets Derivatives of shape functions are also constructed based on the principle of reproduction of derivatives of polynomials (Shaw and Roy 2008a) Within the present scheme, the triangles also serve as background integration cells in weak formulations thereby overcoming non-conformability issues Numerical examples involving the evaluation of derivatives of targeted functions up to the fourth order and applications of the method to a few boundary value problems of general interest in solid mechanics over (non-simply connected) bounded domains in 2D are presented towards the end of the paper

Padé approach to potential transients: Part 1. Electron transfer without and with coupling to first-order homogeneous reactions at planar electrodes

Potential transients are obtained by using “Padé approximants” (an accurate approximation procedure valid globally — not just perturbatively) for all amplitudes of concentration polarization and current densities. This is done for several mechanistic schemes under constant current conditions. We invert the non-linear current-potential relationship in the form (using the Lagrange or the Ramanujan method) of power series appropriate to the two extremes, namely near reversible and near irreversible. Transforming both into the Pad́e expressions, we construct the potential-time profile by retaining whichever is the more accurate of the two. The effectiveness of this method is demonstrated through illustrations which include couplings of homogeneous chemical reactions to the electron-transfer step.

Enantiospecific first total synthesis and confirmation of the relative and absolute stereostructure of isocalamusenone

The enantiospecific total synthesis of two epimers of the sesquiterpene isocalamusenone has been accomplished starting from the readily available monoterpene (R)-limonene which of the natural product established the stereostructure and the absolute configuration (C) 2010 Elsevier Ltd All rights reserved

Effect of calcium depletion on the secretion of newly synthesised human chorionic gonadotropin by first trimester human placenta

Depletion of calcium in the extracellular medium used to incubate first trimester human placental minces resulted in a significant decrease in the quantity of immuno-reactive hCG in the medium and a corresponding increase in the tissue. In contrast, when secretion of newly synthesised hCG was monitored in the absence of calcium by using a radioactive amino acid precursor, a significant increase in the secretion of newly synthesised hCG in the medium was noticed. This was true of secretion of other proteins also as evidenced by the increase in the trichloroacetic acid precipitable radioactivity in the medium in the absence of calcium. These results suggest that newly synthesised hCG is preferentially released over stored hormone in the absence of calcium.

Lipid-amphotericin B complex structure in solution: A possible first step in the aggregation process in cell membranes

The interactions between the polyene antibiotic amphotericin B with dipalmitoylphosphatidylcholine were investigated in vesicles (using circular dichroism) and in chloroform solution (using circular dichroism and IH, I3C, and 31P nuclear magnetic resonance). The results show that amphotericin B readily aggregates in vesicles and that the extent of aggregation depends on the 1ipid:drug concentration ratio. Introduction of sterol molecules into the membrane hastens the process of aggregation of amphotericin B. In chloroform solutions amphotericin B strongly interacts with phospholipid molecules to form a stoichiometric complex. The results suggest that there are interactions between the conjugated heptene stretch of amphotericin B and the methylene groups of lipid acyl chains, while the sugar moiety interacts with the phosphate head group by the formation of a hydrogen bond. A model is proposed for the lipid-amphotericin B complex, in which amphotericin B interacts equally well with the two lipid acyl chains, forming a 1:l complex.

Nucleotide sequence of the first cosmid from the Mycobacterium leprae genome project: structure and function of the Rif-Str regions

The nucleotide sequence of cosmid B1790, carrying the Rif-Str regions of the Mycobacterium leprae chromosome, has been determined. Twelve open reading frames were identified in the 36716bp sequence, representing 40% of the coding capacity. Five ribosomal proteins, two elongation factors and the β and β'subunits of RNA polymerase have been characterized and two novel genes were found. One of these encodes a member of the so-called ABC family of ATP-binding proteins while the other appears to encode an enzyme involved in repairing genomic lesions caused by free radicals. This finding may well be significant as M. leprae, an intracellular pathogen, lives within macrophages.