Tungsten(0)-carbonyl complexes of naphthylazoimidazoles

The reaction of W(CO)(6) with 1-alkyl-2-(naphthyl-alpha-azo)imidazole (alpha-NaiR) has synthesized [W(CO)(5)(alpha-NaiR-N)] (alpha-NaiR-N refers to the monodentate imidazole-N donor ligand) at room temperature. The structure of[W(CO)(5)(alpha-NaiMe-N)] shows a monodentate imidazole-N coordination of 1-methyl-2-(naphthyl-alpha-azo)imidazole (alpha-NaiMe). The complexes are characterized by elemental, mass and other spectroscopic data (IR, UV-Vis, NMR). On refluxing in THF at 323 K, [W(CO)(5)(alpha-NaiR-N)] undergoes decarbonylation to give [W(CO)(4)(alpha-NaiR-N,N')] (alpha-NaiR-N,N' refers to the imidazole-N(N), azo-N(N') bidentate chelator). Cyclic voltammetry shows metal oxidation (W-0/W-1) and ligand reductions (azo/azo(-), azo(-)/azo(=)). The redox and electronic properties are explained by theoretical calculations using an optimized geometry. DFT computation of [W(CO)(5)(alpha-NaiMe-N)] suggests that the major contribution to the HOMO/HOMO - 1 come from W cl-orbitals and the orbitals of CO. The LUMOs are occupied by alpha-NaiMe functions. The back bonding interaction thus originates from the W(CO)(n) moiety to the LUMO of alpha-NaiR. A TD-DFT calculation has ascribed that HOMO/HOMO - 1 -> LUMO is a mixture of metal-to-ligand and ligand-to-ligand charge transfer underlying the CO -> azoimine contribution. The complexes show emission spectra at room temperature. [W(CO)(4)(alpha-NaiR-N,N')] shows a higher fluorescence quantum yield (phi = 0.05-0.07) than [W(CO)(5)(alpha-NaiR-N)] (phi = 0.01-0.02). (C) 2008 Elsevier Ltd. All rights reserved.

High Oxygen Storage Capacity and High Rates of CO Oxidation and NO Reduction Catalytic Properties of Ce1-xSnxO2 and Ce0.78Sn0.2Pd0.02O2-delta

Ce1-xSnxO2 (x = 0.1-0.5) solid solution and its Pd substituted analogue have been prepared by a single step solution combustion method using tin oxalate precursor. The compounds were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and H-2/temperature programmed redution (TPR) studies. The cubic fluorite structure remained intact up to 50% of Sri substitution in CeO2, and the compounds were stable up to 700 C. Oxygen storage capacity of Ce1-xSnxO2 was found to be much higher than that of Ce1-xZrxO2 due to accessible Ce4+/Ce3+ and Sn4+/Sn2+ redox couples at temperatures between 200 and 400 C. Pd 21 ions in Ce0.78Sn0.2Pd0.02O2-delta are highly ionic, and the lattice oxygen of this catalyst is highly labile, leading to low temperature CO to CO2 conversion. The rate of CO oxidation was 2 mu mol g(-1) s(-1) at 50 degrees C. NO reduction by CO with 70% N-2 selectivity was observed at similar to 200 degrees C and 100% N-2 selectivity below 260 degrees C with 1000-5000 ppm NO. Thus, Pd2+ ion substituted Ce1-xSnxO2 is a superior catalyst compared to Pd2+ ions in CeO2, Ce1-xZrxO2, and Ce1-xTixO2 for low temperature exhaust applications due to the involvement of the Sn2+/Sn4+ redox couple along with Pd2+/Pd-0 and Ce4+/Ce3+ couples.

Importance of the amino terminus in maintenance of oligomeric structure of sheep liver cytosolic serine hydroxymethyltransferase

The Role Of The Amino And Carboxyl-Terminal Regions Of Cytosolic Serine Hydroxymethyltransferase (SHMT) In Subunit Assembly And Catalysis Was Studied Using Sis Amino-Terminal (Lacking The First 6, 14, 30, 49, 58, And 75 Residues) And Two Carboxyl-Terminal (Lacking The Last 49 And 185 Residues) Deletion Mutants. These Mutants Were Constructed From A Full Length Cdna Clone Using Restriction Enzyme/PCR-Based Methods And Overexpressed In Escherichia Coli. The Overexpressed Proteins, Des-(A1-K6) SHMT And Des-(A1-W14)-SHMT Were Present In The Soluble Fraction And They Were Purified To Homogeneity. The Deletion Clones, For Des-(A1-V30)-SHMT And Des-(A1-L49)-SHMT Were Expressed At Very Low Levels, Whereas Des-(A1-R58)-SHMT, Des-/A1-G75)-SHMT, Des-(Q435-F483)-SHMT And Des-(L299-F483)-SHMT Mutant Proteins Were Not Soluble And Formed Inclusion Bodies. Des-(A1-K6)-SHMT And Des-(A1-W14)-SHMT Catalyzed Both The Tetrahydrofolate-Dependent And Tetrahydrofolate-Independent Reactions, Generating Characteristic Spectral Intermediates With Glycine And Tetrahydrofolate. The Two Mutants Had Similar Kinetic Parameters To That Of The Recombinant SHMT (Rshmt). However, At 55 Degrees C, The Des-(A1-W14)-SHMT Lost Almost All The Activity Within 5 Min, While At The Same Temperature Rshmt And Des-(A1-K6)-SHMT Retained 85% And 70% Activity, Respectively. Thermal Denaturation Studies Showed That Des-(A1-W14)-SHMT Had A Lower Apparent Melting Temperature (52 Degrees C) Compared To Rshmt (56 Degrees C) And Des-(A1-K6)-SHMT (55 Degrees C), Suggesting That N-Terminal Deletion Had Resulted In A Decrease In The Thermal Stability Of The Enzyme. Further Urea Induced Inactivation Of The Enzymes Revealed That 50% Inactivation Occurred At A Lower Urea Concentration (1.2+/-0.1 M) In The Case Of Des-(A1-W14)-SHMT Compared To Rshmt (1.8+/-0.1 M) And Des-(A1 -K6)-SHMT (1.7+/-0.1 M). The Apoenzyme Of Des-/A1-K6)-SHMT Was Present Predominantly In The Dimer Form, Whereas The Apoenzymes Of Rshmt And Des-(A1-K6)-SHMT Were A Mixture Of Tetramers (Approximate To 75% And Approximate To 65%, Respectively) And Dimers. While, Rshmt And Des-(A1-K6)-SHMT Apoenzymes Could Be Reconstituted Upon The Addition Of Pyridoxal-5'-Phosphate To 96% And 94% Enzyme Activity, Respectively Des-(A1-W14)-SHMT Apoenzyme Could Be Reconstituted Only Upto 22%. The Percentage Activity Refined Correlated With The Appearance Of Visible CD At 425 Nm And With The Amount Of Enzyme Present In The Tetrameric Form Upon Reconstitution As Monitored By Gel Filtration. These Results Demonstrate That, In Addition To The Cofactor, The N-Terminal Arm Plays An Important Role In Stabilizing The Tetrameric Structure Of SHMT.

Development of temperature-tolerant strains of Thiobacillus ferrooxidans to improve bioleaching kinetics

An isolate of Thiobacillus ferrooxidans derived from gold mine water samples was repeatedly subcultured at increasing temperatures (from 30 degrees to 42 degrees C) in 9K medium. The temperature-adapted strain was found to be more efficient in the bioleaching of pyrite mineral than the wild type. When temperature-tolerant strains were cultured repeatedly in 9K medium at 30 degrees C, the temperature tolerance was completely lost, These results indicate that the temperature tolerance was stress-dependent and not a permanent trait of the adapted strain, The potential utility of such temperature-tolerant strains of Thiobacillus ferrooxidans in sulphide mineral dissolution is demonstrated.

Assessment of luteal rescue and desensitization of macaque corpus luteum brought about by human chorionic gonadotrophin and deglycosylated human chorionic gonadotrophin treatment

The objective of the current study was to investigate the mechanism by which the corpus luteum (CL) of the monkey undergoes desensitization to luteinizing hormone following exposure to increasing concentration of human chorionic gonadotrophin (hCG) as it occurs in pregnancy. Female bonnet monkeys were injected (im) increasing doses of hCG or dghCG beginning from day 6 or 12 of the luteal phase for either 10 or 4 or 2 days. The day of oestrogen surge was considered as day '0' of luteal phase. Luteal cells obtained from CL of these animals were incubated with hCG (2 and 200 pg/ml) or dbcAMP (2.5, 25 and 100 mu M) for 3 h at 37 degrees C and progesterone secreted was estimated. Corpora lutea of normal cycling monkeys on day 10/16/22 of the luteal phase were used as controls, In addition the in vivo response to CG and deglycosylated hCG (dghCG) was assessed by determining serum steroid profiles following their administration. hCG (from 15-90 IU) but not dghCG (15-90 IU) treatment in vivo significantly (P < 0.05) elevated serum progesterone and oestradiol levels. Serum progesterone, however, could not be maintained at a elevated level by continuous treatment with hCG (from day 6-15), the progesterone level declining beyond day 13 of luteal phase. Administering low doses of hCG (15-90 IU/day) from day 6-9 or high doses (600 IU/day) on days 8 and 9 of the luteal phase resulted in significant increase (about 10-fold over corresponding control P < 0.005) in the ability of luteal cells to synthesize progesterone (incubated controls) in vitro. The luteal cells of the treated animals responded to dbcAMP (P < 0.05) but not to hCG added in vitro, The in vitro response of luteal cells to added hCG was inhibited by 0, 50 and 100% if the animals were injected with low (15-90 IU) or medium (100 IU) between day 6-9 of luteal phase and high (600 IU on day 8 and 9 of luteal phase) doses of dghCG respectively; such treatment had no effect on responsivity of the cells to dbcAMP, The luteal cell responsiveness to dbcAMP in vitro was also blocked if hCG was administered for 10 days beginning day 6 of the luteal phase. Though short term hCG treatment during late luteal phase (from days 12-15) had no effect on luteal function, 10 day treatment beginning day 12 of luteal phase resulted in regain of in vitro responsiveness to both hCG (P < 0.05) and dbcAMP (P < 0.05) suggesting that luteal rescue can occur even at this late stage. In conclusion, desensitization of the CL to hCG appears to be governed by the dose/period for which it is exposed to hCG/dghCG. That desensitization is due to receptor occupancy is brought out by the fact that (i) this can be achieved by giving a larger dose of hCG over a 2 day period instead of a lower dose of the hormone for a longer (4 to 10 days) period and (ii) the effect can largely be reproduced by using dghCG instead of hCG to block the receptor sites. It appears that to achieve desensitization to dbcAMP also it is necessary to expose the luteal cell to relatively high dose of hCG for more than 4 days.

Homogeneous precipitation from solution by urea hydrolysis: a novel chemical route to the a-hydroxides of nickel and cobalt

Homogeneous precipitation from solution by hydrolysis of urea at elevated temperatures (T=120 degrees C) yields novel ammonia-intercalated alpha-type hydroxide phases of the formula M(OH)(x)(NH3)(0.4)(H2O)(y)(NO3)(2-x) where x=2, y=0.68 for M=Ni and x=1.85, y=0 for M=Co. These triple-layered hexagonal phases (a=3.08+/-0.01 Angstrom, c=21.7+/-0.05 Angstrom) are more crystalline than similar phases obtained by chemical precipitation or electrosynthesis. This method can be adapted as a convenient chemical route to the bulk synthesis of alpha-hydroxides.

Impedance-fatigue correlated studies on SrBi2Ta2O9

Ceramic samples of SrBi2Ta2O9 (SBT) were prepared by the solid state reaction method with a view to study their electrical properties. Reasons as to why SBT shows better fatigue endurance than conventional perovskites like Pb(Zr, Ti)O-3 are looked into. Complex impedance spectroscopy (CIS) was used as a tool to do so. CIS data was acquired over the temperature range from room temperature to 500 degrees C over a wide range of frequencies. Electrical conductivity data indicates that the conductivity in SBT is essentially due to oxygen vacancies and the activation energy for conduction in the high temperature region was found to be 0.95 eV. CIS was used to separate out the bulk and the interfacial contributions to complex impedance.

The effect of ball milling on the melting behavior of Sn-Cu-Ag eutectic alloy

Sn-Ag-Cu (SAC) solder alloys are the best Pb free alternative for electronic industry. Since their introduction, efforts are made to improve their efficacies by tuning the processing and composition to achieve lower melting point and better wettability. Nanostructured alloys with large boundary content are known to depress the melting points of metals and alloys. In this article we explore this possibility by processing prealloyed SAC alloys close to SAC305 composition (Sn-3wt%Ag-0.5wt%Cu) by mechanical milling which results in the formation of nanostructured alloys. Pulverisette ball mill (P7) and Vibratory ball mills are used to carry out the milling of the powders at room temperature and at lower temperatures (-104 A degrees C), respectively. We report a relatively smaller depression of melting point ranging up to 5 A degrees C with respect to original alloys. The minimum grain sizes achieved and the depression of melting point are similar for both room temperature and low-temperature processed samples. An attempt has been made to rationalize the observations in terms of the basic processes occurring during the milling.

Fluorescence-polarization studies on binding of 4-methylumbelliferyl beta-D-galactopyranoside to Ricinus communis (castor-bean) agglutinin

The binding of Ricinus communis (castor-bean) agglutinin 1 to saccharides was studied by equilibrium dialysis and fluorescence polarization by using the fluorescently labelled sugar 4-methylumbelliferyl beta-D-galactopyranoside. No appreciable change in ligand fluorescence of 4-methylumbelliferyl beta-D-galactopyranoside was considerably polarized on its binding to the lectin. The association constants obtained by Scatchard analysis of equilibrium-dialysis and fluorescence-polarization data do not differ much from each other, and at 25 degrees C, Ka = 2.4 (+/- 0.2) X 10(4)M-1. These values agree reasonably well with that reported in the literature for Ricinus agglutinin 1. The number of binding sites obtained by the different experimental procedures is 1.94 +/- 0.1 per molecule of 120 000 daltons and is equal to the reported value of 2. The consistency in the values of Ka and number of binding sites indicate the absence of additional subsites on Ricinus agglutinin 1 for its specific sugars. In addition, the excellent agreement between the binding parameters obtained by equilibrium dialysis and fluorescence polarization indicate the potential of ligand-fluorescence-polarization measurements in the investigation of lectin-sugar interactions.

Co-assembly of a Nafion-Mesoporous Zirconium Phosphate Composite Membrane for PEM Fuel Cells

Synthesis of mesoporous zirconium phosphate (MZP) by co-assembly of a tri-block copolymer, namely pluronic-F127, as a structure-directing agent, and a mixture of zirconium butoxide and phosphorous trichloride as inorganic precursors is reported. MZP with a specific surface area of 84 m(2) g(-1) average pore diameter of about 17 nm and pore volume of 0.35 cm(3) g(-1) has been prepared, and characterised by X-ray diffraction (XRD) and transmission electron microscopy. Nafion-MZP composite membrane is obtained by employing MZP as a surface-functionalised solid-super-acid-proton-conducting medium as well as all inorganic filler with high affinity to absorb water and fast proton-transport across the electrolyte membrane even under low relative humidity (RH) conditions. The composite membranes have been evaluated in H-2/O-2 polymer electrolyte fuel cells (PEFCs) at varying RH values between 18 and 100%; a peak power density of 355 mW cm(-2) at a load current density of 1,100 mA cm(-2) is achieved with the PEFC employing Nafion-MZP composite membrane while operating at optimum temperature (70 degrees C) under 18% RH and ambient pressure. On operating the PEFC employing Nafion-MZP membrane electrolyte with hydrogen and air feeds at ambient pressure and a RH value of 18%, a peak power density of 285 mW cm(-2) at the optimum temperature (60 degrees C) is achieved. In contrast, operating under identical conditions, a peak power density of only similar to 170 mW cm(-2) is achieved with the PEFC employing Nafion-1135 membrane electrolyte.

Novel Self-Supported Natural and Synthetic Polymer Membranes for Air Humidification

Novel self-supported natural and synthetic polymer membranes of chitosan-hydroxy ethyl Cellulose-montmorillonite (CS-HEC-MMT) and polyvinyl alcohol (PVA)-polystyrene sulfonic acid (PSSA) are prepared by solution casting method followed by crosslinking. These membranes are employed for air humidification at varying temperatures between 30 degrees C and 70 degrees C and their performances are compared with commercial Nafion membranes. High hater fluxes with desired humidified-air output have been achieved for CS-HEC-MMT and PVA-PSSA hybrid membranes at air-flow rates of 1-10 slpm. Variation in the air/water mixing ratio, dew point, and relative humidity that ultimately results in desired water flux With respect to air-flow rates are also quantified for all the membranes. Water flux values for CS-HEC-MMT are less than those for Nafion (R) and PVA-PSSA membranes, but the operational Stability of CS-HEC-MMT membrane is higher than PVA-PSSA and comparable with Nafion (R) both of which can operate up to 70 degrees C at repetitive cycles of humidification.

Magnesium/Copper Nanocomposite through Digestive Ripening

Composing nanocomposites: Co-digestive ripening of as-prepared Mg and Cu colloids prepared by the solvated metal atom dispersion method results in a highly monodisperse colloid of Mg/Cu nanocomposite with an average particle size of 3.0 +/- 0.5 nm. Annealing of these samples at 300 degrees C gives the Cu/MgO nanocomposite.

Evidence for H2O2 as the product of reduction of oxygen by alternative oxidase in mitochondria from potato tubers

Oxygen Consumption by alternative oxidase (AOX), present in mitochondria of many angiosperms, is known to be cyanide-resistant in contrast to cytochrome oxidase. Its activity in potato tuber (Solarium tuberosum L.) was induced following chilling treatment at 4 degrees C.About half of the total O-2 consumption of succinate oxidation in such mitochondria was found to be sensitive to SHAM, a known inhibitor of AOX activity. Addition of catalase to the reaction mixture of AOX during the reaction decreased the rate of SHAM-sensitive oxygen consumption by nearly half, and addition at the end of the reaction released nearly half of the consumed oxygen by AOX, both typical of catalase action on H2O2. These findings with catalase suggest that the product of reduction of AOX is H2O2 and not H2O, as previously Surmised. In potatoes Subjected to chill stress (4 degrees C) for periods of 3, 5 and >= 8 days the activity of AOX in mitochondria increased progressively with a corresponding increase in the AOX protein detected by immunoblot of the protein.

Synthesis, characterization and photocatalytic activity of MxCe1-xVO4 (M = Li, Ca and Fe)

Non-stoichiometric substituted cerium vanadates, MxCe1-xVO4 (M = Li, Ca and Fe), were synthesized by solid-state reactions. The crystal structure was analyzed by powder X-ray diffraction and it exhibits a tetragonal zircon Structure, crystallizing in the space group I4(1)/amd with a = 7.3733(4) and c = 6.4909(4) angstrom and Z = 4. Particle sizes were in the range of 600-800 nm, as observed by scanning electron microscopy. The thermal analysis of the compounds showed phase stability up to 1100 degrees C. The UV diffuse reflectance spectra indicated that the compounds have band gaps in the range of 2.6-2.9 eV. The photocatalytic activity of these Compounds was investigated for the first time for the degradation of different dyes, and organics, the oxidation of cyclohexane and the hydroxylation of benzene. The degradation of dyes was modeled using the Langmuir-Hinshelwood kinetics, while the oxidation of cyclohexane and hydroxylation of benzene were modeled using a free radical mechanism and a series reaction mechanism, respectively.

Film cooling at hypersonic Mach numbers using forward facing array of micro-jets

Experimental investigations are carried out in the IISc hypersonic shock tunnel on film cooling effectiveness of a single jet (diameter 2 mm and 0.9 mm), and an array forward facing of micro-jets (diameter 300 mu m each) of same effective area (corresponding to the respective single jet). The single jet and the corresponding micro-jets are injected from the stagnation zone of a blunt cone model (58, apex angle and nose radius of 35 mm). Nitrogen and Helium are injected as coolant gases. Experiments are performed at freestream Mach number 5.9, at 0 degrees angle of attack, with a stagnation enthalpy of 1.84 MJ/kg, with and without injections. The ratios of the jet stagnation pressure to the freestream pitot pressure used in the present study are 1.2 and 1.45. Up to 50% reduction in surface heat transfer rate was observed with the array of micro-jets, compared to that of the respective single jet with nitrogen as the coolant, while the corresponding eduction was up to 37% for helium injection, with the schlieren flow visualizations showing no major change in the shock standoff distance, and thus no major changes in other aerodynamic aspects such as drag.