Pd Supported on Titanium Nitride for Efficient Ethanol Oxidation

The excellent metal support interaction between palladium (Pd) and titanium nitride (TiN) is exploited in designing an efficient anode material. Pd-TN, that could be useful for direct ethanol fuel cell in alkaline media. The physicochemical and electrochemical characterization of the Pd-TiN/electrolyte interface reveals an efficient oxidation of ethanol coupled with excellent stability of the catalyst under electrochemical conditions. Characterization of the interface using in situ Fourier transform infrared spectroscopy (in situ FITR) shows the production CO2 at low overvoltages revealing an efficient cleaving of the C-C bond. The performance comparison of Pd supported on TiN (Pd-TiN) with that supported on carbon (Pd-C) clearly demonstrates the advantages of TiN support over carbon. A positive chemical shift of Pd (3d) binding energy confirms the existence of metal support interaction between pd and TiN, which in turn helps weaken the Pd-CO synergetic bonding interaction. The remarkable ability of TiN to accumulate -OH species on its surface coupled with the strong adhesion of Pd makes TiN an active support material for electrocatalysts.

Studies in biogas technology. Part III. Thermal analysis of biogas plants

A thermal model for a conventional biogas plant has been developed in order to understand the heat transfer from the slurry and the gas holder to the surrounding earth and air respectively. The computations have been performed for two conditions : (i) when the slurry is at an ambient temperature of 20°C, and (ii) when it is at 35°C, the optimum temperature for anaerobic fermentation. Under both these conditions, the gas holder is the major “culprit” with regard to heat losses from the biogas plant. The calculations provide an estimate for the heat which has to be supplied by external means to compensate for the net heat losses which occur if the slurry is to be maintained at 35°C. Even if this external supply of heat is realised through (the calorific value of) biogas, there is a net increase in the biogas output, and therefore a net benefit, by operating the plant at 35°C. At this elevated temperature, the cooling effect of adding the influent at ambient temperature is not insignificant. In conclusion, the results of the thermal analysis are used to define a strategy for operating biogas plants at optimum temperatures, or at higher temperatures than the ambient.

Room-temperature gas sensors based on gallium nitride nanoparticles

Room-temperature sensing characteristics for H-2, ethanol, NH3, H2S and water have been investigated with thick-film sensors based on GaN nanoparticles, prepared by a simple chemical route. In general, GaN nanoparticles exhibit satisfactory sensor properties for these gases and vapors even at room temperature. The sensitivity for ethanol is found to be highest, the sensitivity and recovery times being smallest. Gas sensor properties of GaN seem to be related to intrinsic defects, which act as sorption sites for the gas molecules. (c) 2010 Elsevier Ltd. All rights reserved.

Enhanced photodynamic effect of cobalt(III) dipyridophenazine complex on thyrotropin receptor expressing HEK293 cells

Ternary cobalt(III) complexes CoL(B)] (1-3) of a trianionic tetradentate phenolate-based ligand (L) and phenanthroline bases (B), viz. 1,10-phenanthroline (phen in 1), dipyridoquinoxaline (dpq in 2) and dipyridophenazine (dppz in 3) are synthesized, characterized from X-ray crystallographic, analytical and spectral techniques, and their utility in photodynamic therapy (PDT) of thyroid diseases caused by TSH receptor dysfunction is probed. The complexes display a visible spectral band within the PDT spectral window at similar to 690 nm. Photodynamic potential was estimated through DNA cleavage activity of the dpq and dppz complexes in UV-A light of 365 nm and red light of 676 nm. The reactions proceed via the hydroxyl radical pathway. The complexes retain their DNA photocleavage activity in red light under anaerobic conditions, a situation normally prevails in hypoxic tumor core. Investigation into the photocytotoxic potential of these complexes showed that the dppz complex 3 is approximately 4-fold more active in the HEK293 cells expressing human thyrotropin receptor (HEK293-hTSHR) than in the parental cell line and has an insignificant effect on an unrelated human cervical carcinoma cell line (HeLa). Photoexcitation of complex 3 in HEK293-hTSHR cells leads to damage hTSHR as evidenced from the decrease in cAMP formation both in absence and presence of hTSH and decrease in the TSHR immunofluorescence with a concomitant cytoplasmic translocation of the membrane protein, cadherin. The involvement of hTSHR is evidenced from the ability of complex 3 to bind to the extracellular domain of hTSHR (hTSHR-ECD) with a K-d value of 81 nM and from the photocleavage of hTSHR-ECD.

One pot synthesis of polycyclic oxygen aromatics. Part III mechanism of formation

Reaction of 6-Image -butyl-1-bromomethyl-2-(2-tetrahydropyranyloxy)-naphthalene2c with tetrachlorocatechol (TCC) in acetone in presence of K2CO3 gave diastereomers 6c and 7c. A mechanism (Scheme-1) invoking the base induced cleavage of the pyranyl ether 2 to 1,2-naphthoquinone-1-methide 8 as the first step has been postulated. The cleavage of the pyranyl ether linkage in 2 to give dimers 4 and 5 of 1,2-naphthoquinone-1-methide has been demonstrated with different bases. 1,2-Naphthoquinone-1-methide 8, thus generated, undergoes Michael addition with TCC followed by elimination of chloride ions to give a diketone, which further undergoes aldolisation with acetone to give diastereomers 6 and 7. Michael reaction of 8, generated Image from pyranyl ethers 2a-c, with tetrabromocatechol (TBC) under similar-reaction conditions gave the expected monobromo compounds 6h, 6i, 6k, 7n, 7n and 7q. The last step in the proposed mechanism, Image ., aldolisation has also been demonstrated using different ketonic solvents. Thus, reaction of 2a-c with TCC/TBC in diethyl ketone/methyl ethyl ketone under similar reaction conditions gave the expected compounds 6 and 7.

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.

Improved growth of GaN layers on ultra thin silicon nitride/Si (111) by RF-MBE

High-quality GaN epilayers were grown on Si (1 1 1) substrates by molecular beam epitaxy using a new growth process sequence which involved a substrate nitridation at low temperatures, annealing at high temperatures, followed by nitridation at high temperatures, deposition of a low-temperature buffer layer, and a high-temperature overgrowth. The material quality of the GaN films was also investigated as a function of nitridation time and temperature. Crystallinity and surface roughness of GaN was found to improve when the Si substrate was treated under the new growth process sequence. Micro-Raman and photoluminescence (PL) measurement results indicate that the GaN film grown by the new process sequence has less tensile stress and optically good. The surface and interface structures of an ultra thin silicon nitride film grown on the Si surface are investigated by core-level photoelectron spectroscopy and it clearly indicates that the quality of silicon nitride notably affects the properties of GaN growth. (C) 2010 Elsevier Ltd. All rights reserved.

Kinetic studies on the interaction of gold(III) with nucleic acids. I. Native DNA-Au(III) system-spectrophotometric studies

Kinetics of the interaction of Au(III) with native calf thymus DNA has been studied spectrophotometrically to determine the kinetic parameters and to examine their dependency on the concentrations of DNA and Au(III), temperature, ionic strength and pH. The reaction is of the first order with respect to both the nucleotide unit of DNA and Au(III) in the stoichiometry of 2∶1 respectively. The rate constants vary with the initial ratio of DNA to Au(III) and is attributed to the effect of free chloride ions and the existence of a number of reaction sites with slight difference in the rate constants. The activation energies of this interaction have been found to be 14–16 kcal/mol. From the effect of ionic strength the reaction is found to occur between a positive and a negative ion in the rate-limiting step. The logarithm of rate constants are the linear function of pH and the slopes are dependent on ther-values. A plausible mechanism has been proposed which involves a primary dissociation of the major existing species (AuCl2(OH)2)−, to give (AuCl2)+ which then reacts with a site in the nucleotide unit of DNA in the rate-liminting step followed by a rapid binding to another site on the complementary strand of the DNA double helix. There exist a number of binding sites with slight difference in reactivity.

Interaction of rhodium(III) with DNA

The nature of interaction of Rh(III) with DNA was studied using viscometry and ultraviolet, visible and infrared spectroscopy. The rate of interaction was found to be very slow at room temperature taking several days for completion. The time needed to attain equilibrium is dependent on the concentrations of metal ion, higher the concentration shorter the period required for equilibration. Visible spectra of Rh(III) were found to alter considerably in the presence of DNA. An increase in absorbance and a red shift were observed in the ultraviolet spectra of DNA in the presence of Rh(III). The specific viscosity of DNA solution was found to decrease asymptotically with time and concentrations of metal ion. The melting temperature of DNA was found to increase at lower metal ion concentrations, whereas at higher values a decrease was obtained. At still higher metal ion concentrations (Image ) a ‘nonmeltable state’ of DNA was observed. These results seem to indicate that Rh(III) binds both with the phosphate and the bases of the DNA.

Impedance parameters and the state-of-charge. III. Zinc-manganese dioxide and magnesium-manganese dioxide dry batteries

The problem of non-destructive determination of the state-of-charge of zinc- and magnesium-manganese dioxide dry batteries is examined experimentally from the viewpoint of internal impedance and open-circuit voltage at equilibrium. It is shown that the impedance is mainly charge-transfer controlled at relatively high states-of-charge and progressively changes over to diffusion control as the state-of-charge decreases in the case of zinc-manganese dioxide dry batteries. On the other hand, the impedance is mainly diffusion controlled for undischarged batteries but becomes charge-transfer controlled as soon as there is some discharge in the case of magnesium-manganese dioxide batteries. It is concluded that the determination of state-of-charge is not possible for both types of batteries by the measurement of impedance parameters due to film-induced fluctuations of these parameters. The measurement of open-circuit voltage at equilibrium can be used as a state-of-charge indicator for Zn-MnO2 batteries but not for Mg-MnO2 batteries.

Platinum particles supported on titanium nitride: an efficient electrode material for the oxidation of methanol in alkaline media

In the present study, titanium nitride which shows exceptional stability, extreme corrosion resistance, good electronic conductivity and adhesion behaviour is used to support platinum particles and then used for methanol oxidation in an alkaline medium. The catalyst shows very good CO tolerance for the electrochemical oxidation of methanol. In situ infrared spectroelectrochemical data show the remarkable ability of TiN to decompose water at low over potentials leading to -OH type functional groups on its surface which in turn help in alleviating the carbon monoxide poisoning associated with methanol oxidation. TiN supported catalysts are found to be very good in terms of long term stability, exchange current density and stable currents at low over voltages. Supporting evidence from X-ray photoelectron spectroscopic data and cyclic voltammetry clearly demonstrates the usefulness of TiN supported Pt catalysts for efficient methanol oxidation in alkaline media.

Mixed ligand cobalt(III) complexes of tetradentate N,N′-ethylenebis(acetylacetonimine) and flexidentate isonitroso-β-diketones and isonitrosomonoketones

A series of mixed ligand cobalt(III) complexes having the general formula Co(EA)X [where EA = dianion of N,N′-ethylenebis(acetylacetonimine) and X = anion of isonitroso-acetylacetone, IAA; isonitrosobenzoylacetone, IBA; isonitrosodibenzoylmethane, IDBM; isonitrosoethylacetoacetate, IEA; isonitrosoacetoacetanillide, IAN; isonitrosoethylmethylketone, IEMK; isonitrosobenzylmethylketone, IBMK and isonitrosopropiophenone, IPP] have been synthesised and characterised. A facial-cis-β structure (cis with respect to the coordinated two oxygen atoms of EA) with N,N,N,O,O,O ligational environment has been assigned for the complexes. The characterisation of the complexes has been based upon chemical analysis, electrical conductivity, magnetic moment, IR, PMR and electronic spectra.