Uninterrupted galvanic reaction for scalable and rapid synthesis of metallic and bimetallic sponges/dendrites as efficient catalysts for 4-nitrophenol reduction

Here, we demonstrate an uninterrupted galvanic replacement reaction (GRR) for the synthesis of metallic (Ag, Cu and Sn) and bimetallic (Cu M, M=Ag, Au, Pt and Pd) sponges/dendrites by sacrificing the low reduction potential metals (Mg in our case) in acidic medium. The acidic medium prevents the oxide formation on Mg surface and facilitates the uninterrupted reaction. The morphology of dendritic/spongy structures is controlled by the volume of acid used for this reaction. The growth mechanism of the spongy/dendritic microstructures is explained by diffusion-limited aggregate model (DLA), which is also largely affected by the volume of acid. The significance of this method is that the yield can be easily predicted, which is a major challenge for the commercialization of the products. Furthermore, the synthesis is complete in 1-2 minutes at room temperature. We show that the sponges/dendrites efficiently act as catalysts to reduce 4-nitrophenol (4-NP) to 4-aminophenol (4-AP) using NaBH4-a widely studied conversion process.

A unique strategy towards high dielectric constant and low loss with multiwall carbon nanotubes anchored onto graphene oxide sheets

Multiwall carbon nanotubes (MWNTs) were anchored onto graphene oxide sheets (GOs) via diazonium and C-C coupling reactions and characterized by spectroscopic and electron microscopic techniques. The thus synthesized MWNT-GO hybrid was then melt mixed with 50/50 polyamide6-maleic anhydride-modified acrylonitrile-butadiene-styrene (PA6-mABS) blend to design materials with high dielectric constant (30) and low dielectric loss. The phase morphology was studied by SEM and it was observed that the MWNT-GO hybrid was selectively localized in the PA6 phase of the blend. The 30 scales with the concentration of MWNT-GO in the blends, which interestingly showed a very low dielectric loss (< 0.2) making them potential candidate for capacitors. In addition, the dynamic storage modulus scales with the fraction of MWNT-GO in the blends, demonstrating their reinforcing capability as well.

Porous membranes designed from bi-phasic polymeric blends containing silver decorated reduced graphene oxide synthesized via a facile one-pot approach

In this work, porous membranes were designed by selectively etching the PEO phase, by water, from a melt-mixed PE/PEO blend. The pure water flux and the resistance across the membrane were systematically evaluated by employing an indigenously developed cross flow membrane setup. Both the phase morphology and the cross sectional morphology of the membranes was assessed by scanning electron microscopy and an attempt was made to correlate the observed morphology with the membrane performance. In order to design antibacterial membranes for water purification, partially reduced graphene oxide (rGO), silver nanoparticles (Ag) and silver nanoparticles decorated with rGO (rGO-Ag) were synthesized and incorporated directly into the blends during melt mixing. The loss of viability of bacterial cells was determined by the colony counting method using E. coli as a model bacterium. SEM images display that the direct contact with the rGO-Ag nanoparticles disrupts the cell membrane. In addition, the rGO-Ag nanoparticles exhibited a synergistic effect with respect to bacterial cell viability in comparison to both rGO and Ag nanoparticles. The possible mechanism associated with the antibacterial activity in the membranes was discussed. This study opens new avenues in designing antibacterial membranes for water purification.

Detailed mechanism and kinetic study of CO oxidation on cobalt oxide surfaces

Co3O4 catalysts were prepared by combustion synthesis using different fuels glycine (G), ODH (O) and urea (U). Morphological changes of the materials were observed by using different fuels. The prepared catalysts were characterized by XRD, XPS, SEM, TEM, BET and DRIFTS analysis. All compounds showed 100% conversion of CO below 175C. The prepared catalysts exhibited very high stability and conversions did not decrease even after 50 h of continuous operation. The oxygen storage capacity (OSC) of materials was measured by H-2-TPR analysis. Co3O4-O is having high OSC among the synthesized catalysts. The activation energies of these catalysts were found to be in the range of 42.3-64.8 kJ mol(-1). With DRIFTS analysis, the surface carbonates, superoxide anions, adsorbed CO, O-2 species on the catalyst surface were found and this information was used to develop a detailed reaction pathway. A kinetic model was developed with the help of proposed mechanism and used to fit the data. (C) 2014 Elsevier B.V. All rights reserved.

Unimpeded permeation of water through biocidal graphene oxide sheets anchored on to 3D porous polyolefinic membranes

3D porous membranes were developed by etching one of the phases (here PEO, polyethylene oxide) from melt-mixed PE/PEO binary blends. Herein, we have systematically discussed the development of these membranes using X-ray micro-computed tomography. The 3D tomograms of the extruded strands and hot-pressed samples revealed a clear picture as to how the morphology develops and coarsens over a function of time during post-processing operations like compression molding. The coarsening of PE/PEO blends was traced using X-ray micro-computed tomography and scanning electron microscopy (SEM) of annealed blends at different times. It is now understood from X-ray micro-computed tomography that by the addition of a compatibilizer (here lightly maleated PE), a stable morphology can be visualized in 3D. In order to anchor biocidal graphene oxide sheets onto these 3D porous membranes, the PE membranes were chemically modified with acid/ethylene diamine treatment to anchor the GO sheets which were further confirmed by Fourier transform infrared spectroscopy (FTIR), X-ray photoelectron spectroscopy (XPS) and surface Raman mapping. The transport properties through the membrane clearly reveal unimpeded permeation of water which suggests that anchoring GO on to the membranes does not clog the pores. Antibacterial studies through the direct contact of bacteria with GO anchored PE membranes resulted in 99% of bacterial inactivation. The possible bacterial inactivation through physical disruption of the bacterial cell wall and/or reactive oxygen species (ROS) is discussed herein. Thus this study opens new avenues in designing polyolefin based antibacterial 3D porous membranes for water purification.

Giant Magnetoresistance and Related Properties of Rare Earth Manganates and Other Oxide Systems

Giant magnetoresistance (GMR), which was until recently confined to magnetic layered and granular materials, as well as doped magnetic semiconductors, occurs in manganate perovskites of the general formula Ln(1-x)A(x)MnO(3) (Ln = rare earth; A = divalent ion). These manganates are ferromagnetic at or above a certain value of x (or Mn4+ content) and become metallic at temperatures below the curie temperature, T-c. GMR is generally a maximum close to T-c or the insulator-metal (I-M) transition temperature, T-im. The T-c and %MR are markedly affected by the size of the A site cation, [r(A)], thereby affording a useful electronic phase diagram when T-c or T-im is plotted against [r(A)]. We discuss GMR and related properties of manganates in polycrystalline, thin-film, and single-crystal forms and point out certain commonalities and correlations. We also examine some unusual features in the electron-transport properties of manganates, in particular charge-ordering effects. Charge ordering is crucially dependent on [r(A)] or the e(g) band width, and the charge-ordered insulating state transforms to a metallic ferromagnetic state on the application of a magnetic field.

Studies on aluminum-isopropoxide doped poly(ethylene oxide), poly(vinyl alcohol), and poly(ethylene oxide)-poly(vinyl alcohol) blends

Poly( ethylene oxide), poly(vinyl alcohol): and their blend in a 40 : 60 mole ratio were doped with aluminum isopropoxide. Their structural, thermal, and electrical properties were studied. Aluminum isopropoxide acts as a Lewis acid and thus significantly influences the electrical properties of the polymers and the blend. It also acts as a scavanger for the trace quantities of water p-resent in them, thereby reducing the magnitude of proton transport. It also affects the structure of polymers that manifests in the thermal transformation and decomposition characteristics.

Mesostructured lamellar chromium oxide

Mesostructured lamellar chromium oxide with an interlayer separation of 29 Angstrom has been prepared by employing a cationic surfactant. The introduction of phosphate groups in the oxide increases the interlayer separation to 32 Angstrom.

Mixed convection in non-Newtonian fluids along a vertical plate in a porous medium

The problem of mixed convection from vertical surfaces in a porous medium saturated with a power-law type non-Newtonian fluid is investigated. The transformed conservation laws are solved numerically for the case of variable wall temperature conditions. Results for the details of the velocity and temperature fields as well as the Nusselt number have been presented. The viscosity index ranged from 0.5-2.0.

Mixed Convection Boundary Layer Flow Past a Horizontal Circular Cylinder Embedded in a Bidisperse Porous Medium

Adopting a two-temperature and two-velocity model, appropriate to a bidisperse porous medium (BDPM) proposed by Nield and Kuznetsov (2008), the classical steady, mixed convection boundary layer flow about a horizontal, isothermal circular cylinder embedded in a porous medium has been theoretically studied in this article. It is shown that the boundary layer analysis leads to expressions for the flow and heat transfer characteristics in terms of an inter-phase momentum parameter, a thermal diffusivity ratio, a thermal conductivity ratio, a permeability ratio, a modified thermal capacity ratio, and a buoyancy or mixed convection parameter. The transformed partial differential equations governing the flow and heat transfer in the f-phase (the macro-pores) and the p-phase (the remainder of the structure) are solved numerically using a very efficient implicit finite-difference technique known as Keller-box method. A good agreement is observed between the present results and those known from the open literature in the special case of a traditional Darcy formulation (monodisperse system).

N-acetyl cysteine enhances imatinib-induced apoptosis of Bcr-Abl(+) cells by endothelial nitric oxide synthase-mediated production of nitric oxide

Imatinib, a small-molecule inhibitor of the Bcr-Abl kinase, is a successful drug for treating chronic myeloid leukemia (CML). Bcr-Abl kinase stimulates the production of H2O2, which in turn activates Abl kinase. We therefore evaluated whether N-acetyl cysteine (NAC), a ROS scavenger improves imatinib efficacy. Effects of imatinib and NAC either alone or in combination were assessed on Bcr-Abl(+) cells to measure apoptosis. Role of nitric oxide (NO) in NAC-induced enhanced cytotoxicity was assessed using pharmacological inhibitors and siRNAs of nitric oxide synthase isoforms. We report that imatinib-induced apoptosis of imatinib-resistant and imatinib-sensitive Bcr-Abl(+) CML cell lines and primary cells from CML patients is significantly enhanced by co-treatment with NAC compared to imatinib treatment alone. In contrast, another ROS scavenger glutathione reversed imatinib-mediated killing. NAC-mediated enhanced killing correlated with cleavage of caspases, PARP and up-regulation and down regulation of pro- and anti-apoptotic family of proteins, respectively. Co-treatment with NAC leads to enhanced production of nitric oxide (NO) by endothelial nitric oxide synthase (eNOS). Involvement of eNOS dependent NO in NAC-mediated enhancement of imatinib-induced cell death was confirmed by nitric oxide synthase (NOS) specific pharmacological inhibitors and siRNAs. Indeed, NO donor sodium nitroprusside (SNP) also enhanced imatinib-mediated apoptosis of Bcr-Abl(+) cells. NAC enhances imatinib-induced apoptosis of Bcr-Abl(+) cells by endothelial nitric oxide synthase-mediated production of nitric oxide.

Macroporous metal oxide foams through self-sustained combustion reactions

A number of macroporous metal oxide foams were prepared through self-sustained combustion reactions starting from dough made of the corresponding metal nitrate, urea and starch. The nitrate ion acts as an oxidizing agent, urea as fuel and starch as an organic binder. The metal oxide foams are characterized by scanning electron microscopy and powder X-ray diffraction.

Activities in the $FeTiO_{3}-NiTiO_{3}$ Solid Solution from Alloy-Oxide Equilibria at 1273 K

Nine tie-lines between Fe-Ni alloys and FeTiO3-NiTiO3 solid solutions were determined at 1273 K. Samples were equilibrated in evacuated quartz ampoules for periods up to 10 days. Compositions of the alloy and oxide phases at equilibrium were determined by energy-dispersive x-ray spectroscopy. X-ray powder diffraction was used to confirm the results. Attainment of equilibrium was verified by the conventional tie-line rotation technique and by thermodynamic analysis of the results. The tie-lines are skewed toward the FeTiO3 corner. From the tie-line data and activities in the Fe-Ni alloy phase available in the literature, activities of FeTiO3 and NiTiO3 in the ilmenite solid solution were derived using the modified Gibbs-Duhem technique of Jacob and Jeffes [K.T. Jacob and J.H.E. Jeffes, An Improved Method for Calculating Activities from Distribution Equilibria, High Temp. High Press., 1972, 4, p 177-182]. The components of the oxide solid solution exhibit moderate positive deviations from Raoult's law. Within experimental error, excess Gibbs energy of mixing for the FeTiO3-NiTiO3 solid solution at 1273 K is a symmetric function of composition and can be represented as: Delta G(E) = 8590 (+/- 200) X-FeTiO3 X-NiTiO3 J/mol Full spectrum of tie-lines and oxygen potentials for the three-phase equilibrium involving Fe-Ni alloys, FeTiO3-NiTiO3 solid solutions, and TiO2 at 1273 K were computed using results obtained in this study and data available in the literature.

On the dielectric dispersion and absorption in nanosized manganese zinc mixed ferrites

The temperature and frequency dependence of dielectric permittivity and dielectric loss of nanosized Mn1-xZnxFe2O4 (for x = 0, 0.2, 0.4, 0.6, 0.8, 1) were investigated. The impact of zinc substitution on the dielectric properties of the mixed ferrite is elucidated. Strong dielectric dispersion and broad relaxation were exhibited by Mn1-xZnxFe2O4. The variation of dielectric relaxation time with temperature suggests the involvement of multiple relaxation processes. Cole-Cole plots were employed as an effective tool for studying the observed phenomenon. The activation energies were calculated from relaxation peaks and Cole-Cole plots and found to be consistent with each other and indicative of a polaron conduction.

Remarkable Capacity Retention of Nanostructured Manganese Oxide upon Cycling as an Electrode Material for Supercapacitor

Electrochemical capacity retention of nearly X-ray amorphous nanostructured manganese oxide (nanoMnO2) synthesized by mixing directly KMnO4 with ethylene glycol under ambient conditions for supercapacitor studies is enhanced significantly. Although X-ray diffraction (XRD) pattern of nanoMnO2 shows poor crystallinity, it is found that by Mn K-edge X-ray absorption near edge structure (XANES) measurement that the nanoMnO2 obtained is locally arranged in a δ-MnO2-type layered structure composed of edge-shared network of MnO6 octahedra. Field emission scanning electron microscopy and XANES measurements show that nanoMnO2 contains nearly spherical shaped morphology with δ-MnO2 structure, and 1D nanorods of α-MnO2 type structure (powder XRD) in the annealed (600 °C) sample. Volumetric nitrogen adsorption−desorption isotherms, inductively coupled plasma analysis, and thermal analysis are carried out to obtain physicochemical properties such as surface area (230 m2 g−1), porosity of nanoMnO2 (secondary mesopores of diameter 14.5 nm), water content, composition, etc., which lead to the promising electrochemical properties as an electrode for supercapacitor. The nanoMnO2 shows a very high stability even after 1200 cycles with capacity retention of about 250 F g−1.