Citrate-complexation synthesized Ce0.85Gd0.15O2-delta (GDC15) as solid electrolyte for intermediate temperature SOFC

A typical Ce0.85Gd0.15O2-delta (CDC15) composition of CeO2-Gd2O3 system is synthesized by modified sol - gel technique known as citrate-complexation. TG-DTA, XRD, FT-IR, Raman, FE-SEM/EDX and ac impedance analysis are carried out for structural and electrical characterization. XRD pattern confirmed the well crystalline cubic fluorite structure of CDC15 after calcining at 873 K. Raman spectral bands at 463, 550 and 600 cm(-1) are also in agreement with these structural features. FE-SEM image shows well-defined grains separated from grain boundary and good densification. Ac impedance studies reveal that GDC15 has oxide ionic conductivity similar to that reported for Ce0.9Gd0.1O2-delta (GDC10) and Ce0.8Gd0.2O2-delta (GDC20). Ionic and electronic transference numbers at 673 K are found to be 0.95 and 0.05, respectively. This indicates the possible application of GDC15 as a potential electrolyte for IT-SOFCs. (C) 2014 Elsevier B.V. All rights reserved.

Approaches toward (eta(2)-HX) (X = H, SiR (R = Me-3 or Me2Ph), CH3) sigma-complexes of ruthenium

Two new Ru(II)-complexes RuH(Tpms)(PPh3)(2)] 1 (Tpms - (C3H3N2)(3)CSO3, tris-(pyrazolyl) methane sulfonate) and Ru(OTf)(Tpms)(PPh3)(2)] 2 (OTf = CF3SO3) have been synthesized and characterized wherein Ru-H and Ru-OTf are the key reactive centers. Reaction of 1 with HOTf results in the Ru(eta(2)-H-2)(Tpms)(PPh3)(2)]OTf] complex 3, whereas reaction of 1 with Me3SiOTf affords the dihydrogen complex 3 and complex 1 through an unobserved sigma-silane intermediate. In addition, an attempt to characterize the sigma methane complex via reaction of complex 1 with CH3OTf yields complex 2 and free methane. On the other hand, reaction of Ru(OTf)(Tpms)(PPh3)(2)] 2 with H-2 and PhMe2SiH at low temperature resulted in sigma-H-2, 3 and a probable sigma-silane complexes, respectively. However, no sigma-methane complex was observed for the reaction of complex 2 with methane even at low temperature. (C) 2014 Elsevier B. V. All rights reserved.

Stability of a circular tunnel in presence of pseudostatic seismic body forces

The stability of a long circular tunnel in a cohesive frictional soil medium has been determined in the presence of horizontal pseudo-static seismic body forces. The tunnel is supported by means of lining and anchorage system which is assumed to exert uniform internal compressive normal pressure on its periphery. The upper bound finite element limit analysis has been performed to compute the magnitude of the internal compressive pressure required to support the tunnel. The results have been presented in terms of normalized compressive normal stress, defined in terms of sigma(i)/c; where sigma(i) is the magnitude of the compressive normal pressure on the periphery of the tunnel and c refers to soil cohesion. The variation of sigma(i)/c with horizontal earthquake acceleration coefficient (alpha(h)) has been established for different combinations of H/D, gamma D/c and phi where (i) H and D refers to tunnel cover and diameter, respectively, and (ii) gamma and phi correspond to unit weight and internal friction angle of soil mass, respectively. Nodal velocity patterns have also been plotted for assessing the zones of significant plastic deformation. The analysis clearly reveals that an increase in the magnitude of the earthquake acceleration leads to a significant increment in the magnitude of internal compressive pressure. (C) 2014 Elsevier Ltd. All rights reserved.

A Genetic Analysis of the Functional Interactions within Mycobacterium tuberculosis Single-Stranded DNA Binding Protein

Single-stranded DNA binding proteins (SSBs) are vital in all organisms. SSBs of Escherichia coli (EcoSSB) and Mycobacterium tuberculosis (MtuSSB) are homotetrameric. The N-terminal domains (NTD) of these SSBs (responsible for their tetramerization and DNA binding) are structurally well defined. However, their C-terminal domains (CTD) possess undefined structures. EcoSSB NTD consists of beta 1-beta 1'-beta 2-beta 3-alpha-beta 4-beta 45(1)-beta 45(2)-beta 5 secondary structure elements. MtuSSB NTD includes an additional beta-strand (beta 6) forming a novel hook-like structure. Recently, we observed that MtuSSB complemented an E. coli Delta ssb strain. However, a chimeric SSB (m beta 4-beta 5), wherein only the terminal part of NTD (beta 4-beta 5 region possessing L-45 loop) of EcoSSB was substituted with that from MtuSSB, failed to function in E. coli in spite of its normal DNA binding and oligomerization properties. Here, we designed new chimeras by transplanting selected regions of MtuSSB into EcoSSB to understand the functional significance of the various secondary structure elements within SSB. All chimeric SSBs formed homotetramers and showed normal DNA binding. The m beta 4-beta 6 construct obtained by substitution of the region downstream of beta 5 in m beta 4-beta 5 SSB with the corresponding region (beta 6) of MtuSSB complemented the E. coli strain indicating a functional interaction between the L-45 loop and the beta 6 strand of MtuSSB.

Total internal reflection Raman spectroscopy of poly(alpha-olefin) oils in a lubricated contact

The rheology of a poly(alpha-olefin) base oil (PAO) in a sliding point contact has been investigated by total internal reflection (TIR) Raman spectroscopy. TIR Raman has the sensitivity to analyse nanometer-thick lubricant films in a tribological contact. The Raman signal generated from the sliding contact was used to determine the lubricant film thickness. The experimentally obtained film thicknesses were compared with theoretical calculations and a transition from Newtonian to non-Newtonian behaviour was observed at high shear rates. The Raman spectra showed no significant changes in the conformation of the PAO chains under the applied conditions of pressure and shear, but the polarisation dependence of the spectra revealed a preferred orientation of the hydrocarbon side chains in the shear-thinned region. Monolayers formed by a boundary lubricant, arachidic acid, dissolved in the PAO could be detected on the surfaces in the elastohydrodynamic regime.

DEFINING alpha-HELIX GEOMETRY BY C-alpha ATOM TRACE vs (phi-psi) TORSION ANGLES: A COMPARATIVE ANALYSIS

A regular secondary structure is described by a well defined set of values for the backbone dihedral angles (phi,psi and omega) in a polypeptide chain. However in real protein structures small local variations give rise to distortions from the ideal structures, which can lead to considerable variation in higher order organization. Protein structure analysis and accurate assignment of various structural elements, especially their terminii, are important first step in protein structure prediction and design. Various algorithms are available for assigning secondary structure elements in proteins but some lacunae still exist. In this study, results of a recently developed in-house program ASSP have been compared with those from STRIDE, in identification of alpha-helical regions in both globular and membrane proteins. It is found that, while a combination of hydrogen bond patterns and backbone torsional angles (phi-psi) are generally used to define secondary structure elements, the geometry of the C-alpha atom trace by itself is sufficient to define the parameters of helical structures in proteins. It is also possible to differentiate the various helical structures by their C-alpha trace and identify the deviations occurring both at mid-positions as well as at the terminii of alpha-helices, which often lead to occurrence of 3(10) and pi-helical fragments in both globular and membrane proteins.

CONFORMATIONAL FEATURES OF SIGMA FACTOR/ANTI-SIGMA COMPLEXES

The association of a factors with the RNA polymerase dictates the expression profile of a bacterial cell. Major changes to the transcription profile are achieved by the use of multiple sigma factors that confer distinct promoter selectivity to the holoenzyme. The cellular concentration of a sigma factor is regulated by diverse mechanisms involving transcription, translation and post-translational events. The number of sigma factors varies substantially across bacteria. The diversity in the interactions between sigma factors also vary-ranging from collaboration, competition or partial redundancy in some cellular or environmental contexts. These interactions can be rationalized by a mechanistic model referred to as the partitioning of a space model of bacterial transcription. The structural similarity between different sigma/anti-sigma complexes despite poor sequence conservation and cellular localization reveals an elegant route to incorporate diverse regulatory mechanisms within a structurally conserved scaffold. These features are described here with a focus on sigma/anti-sigma complexes from Mycobacterium tuberculosis. In particular, we discuss recent data on the conditional regulation of sigma/anti-sigma factor interactions. Specific stages of M. tuberculosis infection, such as the latent phase, as well as the remarkable adaptability of this pathogen to diverse environmental conditions can be rationalized by the synchronized action of different a factors.

Dense network of O-H ... O and C-H ... O interactions in the solid state structure of n-pentyl-2-chloro-2-deoxy-alpha-D-manno-sept 3-uloside

Single crystal X-ray structural analysis of a septanoside, namely, n-pentyl-2-chloro-2-deoxy sept-3-uloside (1) provides many finer details of the molecular structure, in addition to its preferred twist-chair conformation, namely, (TC3,4)-T-5,6 conformation. Structural analysis reveals a dense network of O-H...O, C-H...O and van der Waals interactions that stabilize interdigitized, planar bi-layer structure of the crystal lattice. (C) 2014 Elsevier Ltd. All rights reserved.

Pressure Dependence of Glass Transition in As2Te3 Glass

Amorphous solids prepared from their melt state exhibit glass transition phenomenon upon heating. Viscosity, specific heat, and thermal expansion coefficient of the amorphous solids show rapid changes at the glass transition temperature (T-g). Generally, application of high pressure increases the T-g and this increase (a positive dT(g)/dP) has been understood adequately with free volume and entropy models which are purely thermodynamic in origin. In this study, the electrical resistivity of semiconducting As2Te3 glass at high pressures as a function of temperature has been measured in a Bridgman anvil apparatus. Electrical resistivity showed a pronounced change at T-g. The T-g estimated from the slope change in the resistivity-temperature plot shows a decreasing trend (negative dT(g)/dP). The dT(g)/dP was found to be -2.36 degrees C/kbar for a linear fit and -2.99 degrees C/kbar for a polynomial fit in the pressure range 1 bar to 9 kbar. Chalcogenide glasses like Se, As2Se3, and As30Se30Te40 show a positive dT(g)/dP which is very well understood in terms of the thermodynamic models. The negative dT(g)/dP (which is generally uncommon in liquids) observed for As2Te3 glass is against the predictions of the thermodynamic models. The Adam-Gibbs model of viscosity suggests a direct relationship between the isothermal pressure derivative of viscosity and the relaxational expansion coefficient. When the sign of the thermal expansion coefficient is negative, dT(g)/dP = Delta k/Delta alpha will be less than zero, which can result in a negative dT(g)/dP. In general, chalcogenides rich in tellurium show a negative thermal expansion coefficient (NTE) in the supercooled and stable liquid states. Hence, the negative dT(g)/dP observed in this study can be understood on the basis of the Adams-Gibbs model. An electronic model proposed by deNeufville and Rockstad finds a linear relation between T-g and the optical band gap (E-g for covalent semiconducting glasses when they are grouped according to their average coordination number. The electrical band gap (Delta E) of As2Te3 glass decreases with pressure. The optical and electrical band gaps are related as Delta E-g = 2 Delta E; thus, a negative dT(g)/dP is expected when As2Te3 glass is subjected to high pressures. In this sense, As2Te3 is a unique glass where its variation of T-g with pressure can be understood by both electronic and thermodynamic models.

Use of Composition-Graded Bi-Electrolyte Cells for Thermodynamic Studies on Lanthanum Aluminates

Innovative bi-electrolyte solid-state cells incorporating single crystal CaF2 and composition-graded solid electrolyte (LaF3) y (CaF2) 1-y (y = 0 to 0.32) were used for measurement of the standard Gibbs energy of formation of hexagonal La0.885Al11.782O19 and cubic LaAlO3 from component binary oxides La2O3 and alpha-Al2O3 in the temperature range from 875 to 1175 K. The cells were designed based on experimentally verified relevant phase relations in the systems La2O3-Al2O3LaF3 and CaF2-LaF3. The results can be summarized as: 5.891 alpha-Al2O3 + 0.4425 La2O3 (A-rare earth)-> La0.885Al11.782O19 (hex), Delta G(f(ox))(degrees)(+/- 2005)/Jmol(-1) = -80982 + 7.313(T/K); 1/2 La2O3 (A-rare earth) + 1/2 a-Al2O3 -> LaAlO3 (cubic), Delta G(f(ox))(degrees)(+/- 2100)/Jmol(-1) = -59810 + 4.51(T/K). Electron probe microanalysis was used to ascertain the non-stoichiometric range of the hexaaluminate phase. The results are critically analyzed in the light of earlier electrochemical measurements. Several imperfections in the electrochemical cells used by former investigators are identified. Data obtained in the study for LaAlO3 are consistent with calorimetric enthalpy of formation and entropy derived from heat capacity data. Estimated are the standard entropy and the standard enthalpy of formation from elements of hexagonal La0.885Al11.782O19 and rhombohedral LaAlO3 at 298.15 K. c 2014 The Electrochemical Society. All rights reserved.

High specific surface area alpha-Fe2O3 nanostructures as high performance electrode material for supercapacitors

Porous alpha-Fe2O3 nanostructures have been synthesized by a simple sol-gel route. The alpha-Fe2O3 nanostructures are poorly crystalline and porous with BET surface area of 386 m(2) g(-1). The high discharge capacitance of alpha-Fe2O3 electrodes is 300 F g(-1) when the electrodes are cycled in 0.5 M Na2SO3 at a current density of 1 A g(-1). The capacitance retention after 1000 cycles is about 73% of the initial capacitance at a current density of 2 A g(-1). The high discharge capacitance of alpha-Fe2O3 in comparison with the literature reports are attributed to high surface area and porosity of the iron oxide prepared in the present study. As the iron oxides are inexpensive, the capacity of alpha-Fe2O3 is expected to be of potential use for supercapacitor application. (C) 2014 Elsevier B.V. All rights reserved.

Profiling of Luteal Transcriptome during Prostaglandin F2-Alpha Treatment in Buffalo Cows: Analysis of Signaling Pathways Associated with Luteolysis

In several species including the buffalo cow, prostaglandin (PG) F-2 alpha is the key molecule responsible for regression of corpus luteum (CL). Experiments were carried out to characterize gene expression changes in the CL tissue at various time points after administration of luteolytic dose of PGF(2 alpha) in buffalo cows. Circulating progesterone levels decreased within 1 h of PGF(2 alpha) treatment and evidence of apoptosis was demonstrable at 18 h post treatment. Microarray analysis indicated expression changes in several of immediate early genes and transcription factors within 3 h of treatment. Also, changes in expression of genes associated with cell to cell signaling, cytokine signaling, steroidogenesis, PG synthesis and apoptosis were observed. Analysis of various components of LH/CGR signaling in CL tissues indicated decreased LH/CGR protein expression, pCREB levels and PKA activity post PGF(2 alpha) treatment. The novel finding of this study is the down regulation of CYP19A1 gene expression accompanied by decrease in expression of E-2 receptors and circulating and intra luteal E-2 post PGF(2 alpha) treatment. Mining of microarray data revealed several differentially expressed E-2 responsive genes. Since CYP19A1 gene expression is low in the bovine CL, mining of microarray data of PGF(2 alpha)-treated macaques, the species with high luteal CYP19A1 expression, showed good correlation between differentially expressed E-2 responsive genes between both the species. Taken together, the results of this study suggest that PGF(2 alpha) interferes with luteotrophic signaling, impairs intraluteal E-2 levels and regulates various signaling pathways before the effects on structural luteolysis are manifest.

Co-liposomes comprising a lipidated multivalent RGD-peptide and a cationic gemini cholesterol induce selective gene transfection in alpha v beta 3 and alpha v beta 5 integrin receptor-rich cancer cells

The alpha v beta 3 and alpha v beta 5 integrins, transmembrane glycoprotein receptors, are over-expressed in numerous tumors and in endothelial cells that constitute tumor blood vessels. As this protein selectively binds to the Arg-Gly-Asp (RGD) sequence containing peptides, it is an attractive way to target tumors. Herein we have developed novel formulations for integrin mediated selective gene delivery. These formulations are composed of a novel palmitoylated tetrameric RGD containing scaffold (named RAFT-RGD), cationic gemini cholesterol (GL5) and a natural helper lipid 1,2-dioleoyl-L-alpha-glycero-3-phosphatidylethanolamine (DOPE). We have optimized a co-liposomal formulation to introduce the multivalent RGD-containing macromolecule in GL5: DOPE (GL5D) mixture to produce GL5D-RGD. We have unambiguously shown the selectivity of these formulations towards cancer cells that over express alpha v beta 3 and alpha v beta 5 integrins. Two reporter plasmids, pEGFP-C3 and PGL-3, were employed for the transfection experiments and it was shown that GL5D-RGD Liposomes increased exclusively the transfection in alpha v beta 3 and alpha v beta 5 overexpressing HeLa cells.

Mycobacterium bovis BCG promotes tumor cell survival from tumor necrosis factor-alpha-induced apoptosis

Background: Increased incidence of lung cancer among pulmonary tuberculosis patients suggests mycobacteria-induced tumorigenic response in the host. The alveolar epithelial cells, candidate cells that form lung adenocarcinoma, constitute a niche for mycobacterial replication and infection. We thus explored the possible mechanism of M. bovis Bacillus Calmette-Guerin (BCG)-assisted tumorigenicity in type II epithelial cells, human lung adenocarcinoma A549 and other cancer cells. Methods: Cancer cell lines originating from lung, colon, bladder, liver, breast, skin and cervix were treated with tumor necrosis factor (TNF)-alpha in presence or absence of BCG infection. p53, COP1 and sonic hedgehog (SHH) signaling markers were determined by immunoblotting and luciferase assays, and quantitative real time PCR was done for p53-responsive pro-apoptotic genes and SHH signaling markers. MTT assays and Annexin V staining were utilized to study apoptosis. Gain-and loss-of-function approaches were used to investigate the role for SHH and COP1 signaling during apoptosis. A549 xenografted mice were used to validate the contribution of BCG during TNF-alpha treatment. Results: Here, we show that BCG inhibits TNF-alpha-mediated apoptosis in A549 cells via downregulation of p53 expression. Substantiating this observation, BCG rescued A549 xenografts from TNF-alpha-mediated tumor clearance in nude mice. Furthermore, activation of SHH signaling by BCG induced the expression of an E3 ubiquitin ligase, COP1. SHH-driven COP1 targeted p53, thereby facilitating downregulation of p53-responsive pro-apoptotic genes and inhibition of apoptosis. Similar effects of BCG could be shown for HCT116, T24, MNT-1, HepG2 and HELA cells but not for HCT116 p53(-/-) and MDA-MB-231 cells. Conclusion: Our results not only highlight possible explanations for the coexistence of pulmonary tuberculosis and lung cancer but also address probable reasons for failure of BCG immunotherapy of cancers.

Copper-Catalyzed Decarboxylative Sulfonylation of alpha,beta-Unsaturated Carboxylic Acids

Copper-catalyzed, ligand-promoted decarboxylative coupling of readily available a,fi-unsaturated acids with sodium aryl sulfinates is presented. This method provides a new avenue for the synthesis of vinyl sulfones via a decarboxylative radical coupling strategy by employing a catalytic amount of Cu(ClO4)(2)center dot 6H(2)O, TBHP in decane as an oxidant, and 1,10-phenanthroline as a ligand. The salient feature of this method is that it furnishes exclusively the (E)-isomer.