Studies on the structural and ionic transport properties at elevated temperatures of La1-xMnO3 +/-delta synthesized by a wet chemical method

Structural transformation and ionic transport properties are investigated on wet-chemically synthesized La1-xMnO3 (X=0.0-0.18) compositions. Powders annealed in oxygen/air at 1000-1080 K exhibit cubic symmetry and transform to rhombohedral on annealing at 1173-1573 K in air/oxygen. Annealing above 1773 K in air or in argon/helium at 1473 K stabilized distorted rhombohedral or orthorhombic symmetry. Structural transformations are confirmed from XRD and TEM studies. The total conductivity of sintered disks, measured by four-probe technique, ranges from 5 S cm(-1) at 298 K to 105 S cm(-1) at 1273 K. The ionic conductivity measured by blocking electrode technique ranges from 1.0X10(-6) S cm(-1) at 700 K to 2.0X10(-3) S cm(-1) at 1273 K. The ionic transference number of these compositions ranges from 3.0X10(-5) to 5.0X10(-5) at 1273 K. The activation energy deduced from experimental data for ionic conduction and ionic migration is 1.03-1.10 and 0.80-1.00 eV, respectively. The activation energy of formation, association and migration of vacancies ranges from 1.07 to 1.44 eV. (C) 2002 Elsevier Science B.V. All rights reserved.

Effect of ester chemical structure and peptide bond conformation in fragmentation pathways of differently metal cationized cyclodepsipeptides

Fragmentation behavior of two classes of cyclodepsipeptides, isariins and isaridins, obtained from the fungus Isaria, was investigated in the presence of different metal ions using multistage tandem mass spectrometry (MS(n)) with collision induced dissociation (CID) and validated by NMR spectroscopy. During MS(n) process, both protonated and metal-cationized isariins generated product ions belonging to the identical `b-ion' series, exhibiting initial backbone cleavage explicitly at the beta-ester bond. Fragmentation behavior for the protonated and metal-cationized acyclic methyl ester derivative of isariins was very similar. On the contrary, isaridins during fragmentation produced ions belonging to the `b' or/and the `y' ion series depending on the nature of interacting metal ions, due to initial backbone cleavages at the beta-ester linkage or/and at a specific amide linkage. Interestingly, independent of the nature of the interacting metal ions, the product ions formed from the acyclic methyl ester derivative of isaridins belonged only to the `y-type'. Complementary NMR data showed that, while all metal ions were located around the beta-ester group of isariins, the metal ion interacting sites varied across the backbone for isaridins. Combined MS and NMR data suggest that the different behavior in sequence specific charge-driven fragmentation of isariins and isaridins is predetermined because of the constituent beta-hydroxy acid residue in isariins and the cis peptide bond in isaridins.

Spatial Variation of Physico-Chemical and hydrological Parameters with land-use in Venkatapura Catchment,Karnataka

Social, economic and political development of a region is dependent on the health and quantity of the natural resources. Integrated approaches in the management of natural resources would ensure sustainability, which demands inventorying, mapping and monitoring of resources considering all components of an ecosystem. The monitoring of hydrological and catchment landscape of river resources have a vital role in the conservation and management of aquatic resources. This paper presents a case study Venkatapura river basin in Uttara Kannada district of Karnataka State, India based on stream hydrology and landuse analyses. The results revealed variations in dissolved oxygen and free carbon dioxide according to the flow nature of the water, and increased amount of phosphates and coliform contamination in streams closer to anthropogenic activities.

Inverse models to analyze the spatiotemporal variations of chemical weathering fluxes in a granito-gneissic watershed: Mule Hole, South India

Water-rock reactions are driven by the influx of water, which are out of equilibrium with the mineral assemblage in the rock. Here a mass balance approach is adopted to quantify these reactions. Based on field experiments carried out in a granito-gneissic small experimental watershed (SEW), Mule Hole SEW (similar to 4.5 km(2)), quartz, oligoclase, sericite, epidote and chlorite are identified as the basic primary minerals while kaolinite, goethite and smectite are identified as the secondary minerals. Observed groundwater chemistry is used to determine the weathering rates, in terms of `Mass Transfer Coefficients' (MTCs), of both primary and secondary minerals. Weathering rates for primary and secondary minerals are quantified in two steps. In the first step, top red soil is analyzed considering precipitation chemistry as initial phase and water chemistry of seepage flow as final phase. In the second step, minerals present in the saprolite layer are analyzed considering groundwater chemistry as the output phase. Weathering rates thus obtained are converted into weathering fluxes (Q(weathering)) using the recharge quantity. Spatial variability in the mineralogy observed among the thirteen wells of Mule Hole SEW is observed to be reflected in the MTC results and thus in the weathering fluxes. Weathering rates of the minerals in this silicate system varied from few 10 mu mol/L (in case of biotite) to 1000 s of micromoles per liter (calcite). Similarly, fluxes of biotite are observed to be least (7 +/- 5 mol/ha/yr) while those of calcite are highest (1265 791 mol/ha/yr). Further, the fluxes determined annually for all the minerals are observed to be within the bandwidth of the standard deviation of these fluxes. Variations in these annual fluxes are indicating the variations in the precipitation. Hence, the standard deviation indicated the temporal variations in the fluxes, which might be due to the variations in the annual rainfall. Thus, the methodology adopted defines an inverse way of determining weathering fluxes, which mainly contribute to the groundwater concentration. (C) 2011 Elsevier B.V. All rights reserved.

Chemical potential of germanium in its solid solutions with Cu, Ag and Au

Thin foils of copper, silver and gold were equilibrated with tetragonal GeO2 under controlled View the MathML source gas streams at 1000 K. The equilibrium concentration of germanium in the foils was determined by the X-ray fluorescence technique. The standard free energy of formation of tetragonal GeO2 was measured by a solid oxide galvanic cell. The chemical potential of germanium calculated from the experimental data and the free energies of formation of carbon monoxide and carbon dioxide was found to decrease in the sequence Ag + Ge > Au + Ge > Cu + Ge. The more negative value for the chemical potential of germanium in solid copper, compared to that in solid gold, cannot be explained in terms of the strain energy factor, electro-negativity differences or the vaporization energies of the solvent, and suggests that the d band and its hybridization with s electrons are an important factor in determining the absolute values for the chemical potential in dilute solutions. However, the variation of the chemical potential with solute concentration can be correlated to the concentration of s and p electrons in the outer shell.

SOS films and interfaces: chemical aspects

The possible chemical reactions that take place during the growth of single crystal films of silicon on sapphire (SOS) are analyzed thermodynamically. The temperature for the growth of good quality epitaxial films is dependent on the extent of water vapor present in the carrier gas. The higher the water vapor content the higher the temperature needed to grow SOS films. Due to the interaction of silicon with sapphire at elevated temperatures, SOS films are doped with aluminum. The extent of doping is dependent on the conditions of film growth. The doping by aluminum from the substrate increases with increasing growth temperatures and decreasing growth rates. The equilibrium concentrations of aluminum at the silicon-sapphire interface are calculated as a function of deposition temperature, assuming that SiO2 or Al6Si2O13 are the products of reaction. It is most likely that the product could be a solid solutio n of Al2O3 in SiO2. The total amount of aluminum released due to the interaction between silicon and sapphire will account only for the formation of not more than one monolayer of reaction product unless the films are annealed long enough at elevated temperatures. This value is in good agreement with the recently reported observations employing high resolution transmission electron microscopy.

Physically consistent simulation of mesoscale chemical kinetics: The non-negative FIS-alpha method

Biochemical pathways involving chemical kinetics in medium concentrations (i.e., at mesoscale) of the reacting molecules can be approximated as chemical Langevin equations (CLE) systems. We address the physically consistent non-negative simulation of the CLE sample paths as well as the issue of non-Lipschitz diffusion coefficients when a species approaches depletion and any stiffness due to faster reactions. The non-negative Fully Implicit Stochastic alpha (FIS alpha) method in which stopped reaction channels due to depleted reactants are deleted until a reactant concentration rises again, for non-negativity preservation and in which a positive definite Jacobian is maintained to deal with possible stiffness, is proposed and analysed. The method is illustrated with the computation of active Protein Kinase C response in the Protein Kinase C pathway. (C) 2011 Elsevier Inc. All rights reserved.