Phase equilibria in the system Sm-Rh-O and thermodynamic and thermal studies on SmRhO3

Using isothermal equilibration, phase relations are established in the system Sm-Rh-O at 1273 K. SmRhO3 with GdFeO3-type perovskite structure is found to be the only ternary phase. Solid-state electrochemical cells, containing calcia-stabilized zirconia as an electrolyte, are used to measure the thermodynamic properties of SmRhO3 formed from their binary component oxides Rh2O3 (ortho) and Sm2O3 (C-type and B-type) in two different temperature ranges. Results suggest that C-type Sm2O3 with cubic structure transforms to B-type Sm2O3 with monoclinic structure at 1110 K. The standard Gibbs energy of transformation is . Standard Gibbs energy of formation of SmRhO3 from binary component oxides Rh2O3 and Sm2O3 with B-type rare earth oxide structure can be expressed as . The decomposition temperature of SmRhO3 estimated from the extrapolation of electrochemical data is 1665 (+/- 2) K in air and 1773 (+/- 3) K in pure oxygen. Temperature-composition diagrams at constant oxygen pressures are constructed for the system Sm-Rh-O. Employing the thermodynamic data for SmRhO3 from emf measurement and auxiliary data for other phases from the literature, oxygen potential-composition phase diagram and 3-D chemical potential diagram for the system Sm-Rh-O at 1273 K are developed.

Iminodiacetic acid functionalized polypyrrole modified electrode as Pb(II) sensor: Synthesis and DPASV studies

An electrochemical lead ion sensor has been developed by modification of carbon paste electrode (CPE) using polypyrrole functionalized with iminodiacetic acid (IDA-PPy) containing carboxyl group. The electrochemical response of Pb2+ ion on the IDA-PPy modified CPE has been evaluated and the controling parameters have been optimized using differential pulse anodic stripping voltammetry (DPASV). The IDA-PPy modified CPE shows a linear correlation for Pb2+ concentrations in the range of 1 x 10(-6) to 5 x 10(-9) M and the lower detection limit of Pb2+ has been found to be 9.6 x 10(-9) M concentration. Other tested metal ions, namely Cu2+, Cd2+, Co2+, Hg2+, Ni2+ and Zn2+, do not exhibit any voltammetric stripping response below 1 x 10(-7) M concentration. However, the Pb2+ response is affected in the presence of molar equivalents or higher concentrations of Cu2+, Cd2+ and Co2+ ions in binary systems with Pb2+, consequent to their ability to bind with iminodiacetic acid, while Hg2+, Ni2+ and Zn2+ do not interfere at all. A good correlation has been observed between the lead concentrations as analyzed by DPASV using IDA-PPy modified CPE and atomic absorption spectrophotometry for a lead containing industrial effluent sample. (C) 2014 Elsevier Ltd. All rights reserved.

Azide and Alkyne Terminated Polybutadiene Binders: Synthesis, Cross-linking, and Propellant Studies

In composite solid propellants, the fuel and oxidizer are held together by a polymer binder. Among the different types of polymeric binders used in solid propellants, hydroxyl terminated polybutadiene (HTPB) is considered as the most versatile. HTPB is conventionally cured using isocyanates to form polyurethanes. However, the incompatibility of isocyanates with energetic oxidizers such as ammonium dinitramide and hydrazinium nitroformate, the short pot life of the propellant slurry, and undesirable side reactions with moisture are limiting factors which adversely affect the mechanical properties of HTPB based propellant. With an aim of resolving these problems, HTPB was chemically transformed to azidoethoxy carbonyl amine terminated polybutadiene and propargyloxy carbonyl amine terminated polybutadiene by adopting appropriate synthesis strategies and characterizing them by spectroscopic and chromatographic techniques. This is the first report on 1,3-dipolar addition reaction involving azide and alkyne end groups for cross-linking HTPB. The blend of these two polymers underwent curing under mild temperature (60 degrees C) conditions through 1,3-dipolar cycloaddition reaction resulting in triazoletriazoline networks. The curing parameters were studied using differential scanning calorimetry. The kinetic parameter, viz., activation energy, was computed to be 107.6 kJ/mol, the preexponential factor was 2.79 x 10(12) s-(1), and the rate constant at 60 degrees C was computed to be 3.64 x 10-(5) s-(1). The cure profile at a given temperature was predicted using the kinetic parameters. Rheological studies revealed that the gel time for curing through the 1,3-dipolar addition is 280 min compared to 120 min for curing through the urethane route. The mechanical properties of the resultant cured polybutadiene network were superior to those of polyurethanes. The cured triazolinetriazole polymer network exhibited biphasic morphology with two glass transitions (T-g) at -56 and 42 degrees C in contrast to the polyurethane which exhibited a single transition at -60 degrees C. This was corroborated by associated morphological changes observed by scanning probe microscopy. The propellant processed using this binder has the advantages of improved pot life as indicated by the end of the mix viscosity which is 165 Pas as compared with 352 Pas for the polyurethane system along with a slow build- up rate. The mechanical properties of the propellant are superior to polyurethane with an improvement of 14% in tensile strength, 22% enhancement in elongation at break, and 12% in modulus.

Effective Degradation of Aqueous Nitrobenzene Using the SrFeO3-delta Photocatalyst under UV Illumination and Its Kinetics and Mechanistic Studies

In this article, the SrFeO3-delta photocatalyst was synthesized by a solution combustion method and applied for the photocatalytic degradation of aqueous nitrobenzene in the presence and absence of H2O2. The SrFeO3-delta photocatalyst was characterized by XRD, FT-IR, FE-SEM, TEM, TG-DTG, XPS, and UV visible spectroscopy. The band gap energy of SrFeO3-delta was found to be 3.75 eV which lies in the UV region. The XPS results indicate that the oxidation state of Sr and Fe in SrFeO3-delta was 2+ and 3+, respectively, and the surface atomic ratio of Sr and Fe is 0.995. The photocatalytic activity reveals that the degradation of nitrobenzene over the SrFeO3-delta catalyst itself (UV/SFO) is superior compared to SrFeO3-delta in the presence of H2O2 (UV/SFO/H2O2) with a degradation efficiency of 99-96%. The degradation of nitrobenzene obeys first-order kinetics in both UV/SFO and UV/SFO/H2O2 processes. The decrease in degradation efficiency with UV/SFO/H2O2 was attributed due to the formation of strontium carbonate on the photocatalyst surface.

Dynamics of ribonuclease A and ribonuclease S: Computational and experimental studies

RNase S is a complex consisting of two proteolytic fragments of RNase A: the S peptide (residues 1-20) and S protein (residues 21-124). RNase S and RNase A have very similar X-ray structures and enzymatic activities. previous experiments have shown increased rates of hydrogen exchange and greater sensitivity to tryptic cleavage for RNase S relative to RNase A. It has therefore been asserted that the RNase S complex is considerably more dynamically flexible than RNase A. In the present study we examine the differences in the dynamics of RNaseS and RNase A computationally, by MD simulations, and experimentally, using trypsin cleavage as a probe of dynamics. The fluctuations around the average solution structure during the simulation were analyzed by measuring the RMS deviation in coordinates. No significant differences between RNase S and RNase A dynamics were observed in the simulations. We were able to account for the apparent discrepancy between simulation and experiment by a simple model, According to this model, the experimentally observed differences in dynamics can be quantitatively explained by the small amounts of free S peptide and S protein that are present in equilibrium with the RNase S complex. Thus, folded RNase A and the RNase S complex have identical dynamic behavior, despite the presence of a break in polypeptide chain between residues 20 and 21 in the latter molecule. This is in contrast to what has been widely believed for over 30 years about this important fragment complementation system.

Regolith mass balance inferred from combined mineralogical, geochemical and geophysical studies: Mule Hole gneissic watershed, South India

The aim of this study is to propose a method to assess the long-term chemical weathering mass balance for a regolith developed on a heterogeneous silicate substratum at the small experimental watershed scale by adopting a combined approach of geophysics, geochemistry and mineralogy. We initiated in 2003 a study of the steep climatic gradient and associated geomorphologic features of the edge of the rifted continental passive margin of the Karnataka Plateau, Peninsular India. In the transition sub-humid zone of this climatic gradient we have studied the pristine forested small watershed of Mule Hole (4.3 km(2)) mainly developed on gneissic substratum. Mineralogical, geochemical and geophysical investigations were carried out (i) in characteristic red soil profiles and (ii) in boreholes up to 60 m deep in order to take into account the effect of the weathering mantle roots. In addition, 12 Electrical Resistivity Tomography profiles (ERT), with an investigation depth of 30 m, were generated at the watershed scale to spatially characterize the information gathered in boreholes and soil profiles. The location of the ERT profiles is based on a previous electromagnetic survey, with an investigation depth of about 6 m. The soil cover thickness was inferred from the electromagnetic survey combined with a geological/pedological survey. Taking into account the parent rock heterogeneity, the degree of weathering of each of the regolith samples has been defined using both the mineralogical composition and the geochemical indices (Loss on Ignition, Weathering Index of Parker, Chemical Index of Alteration). Comparing these indices with electrical resistivity logs, it has been found that a value of 400 Ohm m delineates clearly the parent rocks and the weathered materials, Then the 12 inverted ERT profiles were constrained with this value after verifying the uncertainty due to the inversion procedure. Synthetic models based on the field data were used for this purpose. The estimated average regolith thickness at the watershed scale is 17.2 m, including 15.2 m of saprolite and 2 m of soil cover. Finally, using these estimations of the thicknesses, the long-term mass balance is calculated for the average gneiss-derived saprolite and red soil. In the saprolite, the open-system mass-transport function T indicates that all the major elements except Ca are depleted. The chlorite and biotite crystals, the chief sources for Mg (95%), Fe (84%), Mn (86%) and K (57%, biotite only), are the first to undergo weathering and the oligoclase crystals are relatively intact within the saprolite with a loss of only 18%. The Ca accumulation can be attributed to the precipitation of CaCO3 from the percolating solution due to the current and/or the paleoclimatic conditions. Overall, the most important losses occur for Si, Mg and Na with -286 x 10(6) mol/ha (62% of the total mass loss), -67 x 10(6) mol/ha (15% of the total mass loss) and -39 x 10(6) mol/ha (9% of the total mass loss), respectively. Al, Fe and K account for 7%, 4% and 3% of the total mass loss, respectively. In the red soil profiles, the open-system mass-transport functions point out that all major elements except Mn are depleted. Most of the oligoclase crystals have broken down with a loss of 90%. The most important losses occur for Si, Na and Mg with -55 x 10(6) mol/ha (47% of the total mass loss), -22 x 10(6) mol/ha (19% of the total mass loss) and -16 x 10(6) mol/ha (14% of the total mass loss), respectively. Ca, Al, K and Fe account for 8%, 6%, 4% and 2% of the total mass loss, respectively. Overall these findings confirm the immaturity of the saprolite at the watershed scale. The soil profiles are more evolved than saprolite but still contain primary minerals that can further undergo weathering and hence consume atmospheric CO2.

Variable-Temperature EPR and Transport Studies on Poly(4,4'-methylenedianiline): Evidence for Bipolarons

The correlation between magnetic and transport properties is examined by studying poly(4,4'-methylenedianiline)(PMDA) salts and their bases using EPR and conductivity measurements. Five different PMDA salts (doped polymers)were prepared by chemical polymerization of 4,4'-methylenedianiline using different protonic acids. The PMDA bases were obtained by dedoping the salts using ammonium hydroxide. Ambient temperature electrical conductivity measurements show evidence for the doped PMDA system to be highly disordered. The EPR spectra of the samples were recorded in the range 20-200 "C, and the results were analyzed on the basis of the polaron-bipolaron model, which is typical of nondegenerate systems. Both PMDA salts and their bases consist of self-trapped, highly mobile polarons or radical cations. EPR studies on PMDA salts show evidence for the presence of thermally activated and temperature independent (or Pauli type) paramagnetism while the bases show thermally activated, Pauli and Curie-Weiss types of paramagnetism. The paramagnetism arises due to polarons.It is proposed that charge transport takes place through both polarons and bipolarons.

Structural and functional studies of Bacillus stearothermophilus serine hydroxymethyltransferase: the role of Asn(341), Tyr(60) and Phe(351) in tetrahydrofolate binding

SHMT (serine hydoxymethyltransferase), a type I pyridoxal 5'-phosphate-dependent enzyme, catalyses the conversion of L-serine and THF (tetrahydrofolate) into glycine and 5,10-methylene THE SHMT also catalyses several THF-independent side reactions such as cleavage of P-hydroxy amino acids, trans-amination, racemization and decarboxylation. In the present study, the residues Asn(341), Tyr(60) and Phe(351), which are likely to influence THF binding, were mutated to alanine, alanine and glycine respectively, to elucidate the role of these residues in THF-dependent and -independent reactions catalysed by SHMT. The N341A and Y60A bsSHMT (Bacillus stearothermophilus SHMT) mutants were inactive for the THF-dependent activity, while the mutations had no effect on THF-independent activity. However, mutation of Phe(351) to glycine did not have any effect oil either of the activities. The crystal structures of the glycine binary complexes of the mutants showed that N341A bsSHMT forms an external aldimine as in bsSHMT, whereas Y60A and F351G bsSHMTs exist as a Mixture of internal/external aldimine and gem-diamine forms. Crystal structures of all of the three Mutants obtained in the presence of L-allo-threonine were similar to the respective glycine binary complexes. The structure of the ternary complex of F351G bsSHMT with glycine and FTHF (5-formyl THF) showed that the monoglutamate side chain of FTHF is ordered in both the subunits of the asymmetric unit, unlike in the wild-type bsSHMT. The present studies demonstrate that the residues Asn(341) and Tyr(60) are pivotal for the binding of THF/FTHF, whereas Phe(351) is responsible for the asymmetric binding of FTHF in the two subunits of the dimer.

Synthesis, structure and spectroscopic studies on hydroxo-bridged heterotrinuclear complexes of cobalt(m) with ethane-l,2-diamine and ammonia as terminal ligands

Hydroxo-bridged homo- and hetero-trinuclear cobalt(III) complexes of the type [MII(H2O)2{(OH)2CoIII(N4)}2]X2·nH2O [MII= a divalent metal ion such as CoII, NiII or ZnII; N4=(en)2(en = ethane-1,2-diamine) or (NH3)4; X = SO4 or (ClO4)2; n= 3 or 5] have been prepared and spectroscopically characterized. The structure of [Cu{(OH)2Co(en)2}2][SO4]2·2H2O 1 has been determined. The geometry around copper atom is a pseudo-square-based pyramid, with the basal sites occupied by four bridging hydroxide oxygens and the apical site is occupied by a weakly co-ordinated sulfate anion [Cu–O 2.516(4)Å]. The hydroxo groups bridge pairs of cobalt(III) ions which are in near-octahedral environments. The ethylenediamine chelate rings have the twist conformation. In the crystal structure of [Cu{(OH)2Co(en)2}2][ClO4]4·2H2O 2 the perchlorate ion is not co-ordinated and the en ligands have envelope conformations. The sulfate ion in [Cu{(OH)2Co(NH3)4}2][SO4]2·4H2O 3 is not co-ordinated to the central copper ion. Electronic, infrared and variable-temperature EPR spectral data are discussed.

Synthesis and magnetic studies of flower-like nickel nanocones

Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

Synthesis and magnetic studies of flower-like nickel nanocones

Flower-like nickel nanocone structures are synthesized by a simple chemical reduction method using hydrazine hydrate as the reducing agent. The structure, morphology and magnetic properties of as synthesized products are studied by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM) and SQUID magnetometer. The morphology evolution is studied by varying the reaction temperature and concentration of nickel chloride keeping other conditions unchanged.

High-Pressure Low-Temperature Locknut Cell For Both Electron-Paramagnetic-Res And Nmr-Studies To 10 Kilobars And 77-K

A locked high-pressure cell with working pressure range up to 10 kbars suitable for low-temperature studies to 77 K has been described. It can be used for both EPR and NMR studies of single crystals (and other solid samples). The high-pressure seal and all other aspects of the cell remain the same for either application. Only a change of the bottom plug is required for a switch from a nuclear-magnetic-resonance (NMR) to an electron-paramagnetic-resonance (EPR) experiment. Details of the procedure for the calibration of pressure inside the cell at various temperatures are discussed. The performance of the cell in EPR (Cr3+ion) and NMR (27Al nucleus) studies is reported.

Conformational analysis of small disulfide loops. Spectroscopic and theoretical studies on a synthetic cyclic tetrapeptide containing cystine

The conformational analysis of the synthetic peptide Boc-Cys-Pro-Val-Cys-NHMe has been carried out, as a model for small disulfide loops, in biologically active polypeptides. 'H NMR studies (270 MHz) establish that the Val(3) and Cys(4) NH groups are solvent shielded, while 13C studies establish an all-trans peptide backbone. Circular dichroism and Raman spectroscopy provide evidence for a right-handed twist of the disulfide bond. Analysis of the vicinal (JaB)c oupling constants for the two Cys residues establishes that XI - *60° for Cys(4), while some flexibility is suggested at Cys( 1). Conformational energy calculations, imposing intramolecular hydrogen bonding constraints, favor a P-turn (type I) structure with Pro(2)-Va1(3) as the corner residues. Theoretical and spectroscopic results are consistent with the presence of a transannular 4 - 1 hydrogen bond between Cys( 1) CO and Cys(4) NH groups, with the Val NH being sterically shielded from the solvent environment.

Thermochemical and kinetic studies on the effects of cobalt salicylate on the oxidative degradation of polystyrene

The effect of cobalt salicylate on the oxidative degradation and ignition of polystyrene has been studied. It was found that cobalt salicylate sensitizes both the degradation and ignition of polystyrene by facilitating electron-transfer processes in the propagation step. From thermochemical and kinetic studies it was found that the cobalt ion, owing to its ability to exist in variable valence states, promotes electron transfer in the propagation step of polymer degradation, increasing the rate of propagation and consequently the overall rate. Using solid-phase thermal ignition theory, an attempt has been made to explain the sensitization of ignition by the cobalt ion.

Calorimetric, infrared and ESR studies of the plastically crystalline state of organic compounds

Enthalpy changes of the crystal-plastic and plastic-liquid transitions are related to the temperature range of stability of the plastic phase. Thermodynamics of the plastic state of binary mixtures have been examined. Infrared correlation times, τc, and activation energies have been measured for a few molecules in the plastic state. Molecular tumbling times, τt, have also been measured employing ESR spectra of a spin-probe. Plots of log τc(τt) 1/T are continuous through the plastic-liquid transition. Activation energies for molecular motion seem to vary in the same direction as the ΔH of the plastic-crystal transition. Infrared correlation times of solute molecules in binary solutions in the plastic and the liquid states show interesting variations with solute concentration.