Iron(II, III) complexes with N, N'-DI(2-)Pyridyl Thiourea. Moumlssbauer and other spectroscopic studies

Several iron(II, III) complexes of N, N'-di(2-)pyridyl thiourea have been synthesized. The preparation of the complexes from iron(III) salts proceeds through a reduction of iron(III) to iron(II) followed by a subsequent reoxidation. The Moumlssbauer, electronic and infrared spectra of these complexes have been measured. The results are concordant with the coordination of pyridine nitrogens and thiocarbonyl sulfur yielding polymeric complexes. A variable temperature NMR study of the free ligand shows that two conformation are accessible for it in solution at subambient temperatures.

Vanadate stimulates oxidation of NADH to generate hydrogen peroxide

Vanadate in the polymeric form of decavanadate, but not other forms, stimulated oxidation of NADH to NAD+ NADPH was also oxidized with comparable rates. This oxidation of NADH was accompanied by uptake of oxygen and generated hydrogen peroxide with the following stoichiometry: NADH + H+ + O2 → NAD+ + H2O2. The reaction followed second-order kinetics. The rate was dependent on the concentration of both NADH and vanadate and increased with decreasing pH. The reaction had an obligatory requirement for phosphate ions. Esr studies in the presence of the spin trap dimethyl pyrroline N oxide indicated the involvement of Superoxide anion as an intermediate. The reaction was sensitive to Superoxide dismutase and other scavengers of superoxide anions.

Thermal degradation of polystyrene

The importance of the study of thermal degradation of polymeric fuels arises from their role in the combustion of solid propellants. Estimation of the condensed-phase heat release during combustion can be facilitated by the knowledge of the enthalpy change associated with the polymer degradation process. Differential scanning calorimetry has been used to obtain enthalpy data. Kinetic studies on the polymeric degradation process have been carried out with the following objectives. The literature values of activation energies are quite diverse and differ from author to author. The present study has tried to locate possible reasons for the divergence in the reported activation energy values. A value of 30 kcal has been obtained and found to be independent of the technique employed. The present data on the kinetics support to chain-end initiation and unzipping process. The activation energies are further found to be independent of the atmosphere in which the degradation of polymer fuel is carried out. The degradation in air, N2, and O2 all yield a value of 30 kcal/mole for the activation energies.

Synthesis of a one-dimensional coordination polymer containing pendant hydrosulfide groups

In view of the recent interest in compounds containing M-SH units, an organotin hydrosulfide compound, Me2Sn(SH)(O2CMe) (1) was prepared by controlled hydrolysis of the diorganotin thioacetate. Under similar mild hydrolytic conditions the corresponding benzoate could not be isolated. Instead, the thiobenzoate complex, Me2Sn(SOCPh)(2) (3) was obtained in excellent yields indicating that there was no hydrolysis. Both 1 and 3 were characterized by X-ray crystallography. Some properties of the polymeric compound 1, such as spectral, electrical conductivity and NLO response were also studied. The reactivity and properties were explained using density functional calculations.

Komplexe von 2,6-Dimethylpyridin-1-oxid mit Lanthanidjodiden

Complexes of 2,6-dimethylpyridine 1-oxide with lanthanide iodides of the formulaeLn(2,6-LTNO)5I3 whereLn=La, Tb and Yb,Ln(2,6-LTNO)4I3 whereLn=Pr and Nd and Er(2,6-LTNO)4.5I3 have been prepared and characterised by chemical analysis, infrared and conductance studies. Infrared and conductance data have been interpreted in terms of dimeric (or polymeric) structures involving bridging amine oxide groups.

Hybrid Sol-Gel Combustion Synthesis of Nanoporous Anatase

Nanoporous anatase with a thin interconnected filmlike morphology has been synthesized in a single step by coupling a nonhydrolytic condensation reaction of a Ti precursor with a hybrid sol-gel combustion reaction. The method combines the advantages of a conventional sol-gel method for the formation of porous structures with the high crystallinity of the products obtained by combustion methods to yield highly crystalline, phase-pure nanoporous anatase. The generation of pores is initiated by the formation of reverse micelles in a polymeric polycondensation product, which expand during heating, leading to larger pores. A reaction scheme involving a complex formation and nonhydrolytic polycondensation reaction with ester elimination leads to the formation of ail extended Ti-O-Ti network. The effect of process parameters, such as temperature and relative ratio of cosurfactants, on phase formation has been studied. The possibility of band gap engineering by controlled doping during synthesis and the possibility of attachment of molecular/nanoparticle sensitizers provide opportunities for easy preparation of photoanodes for solar cell applications.

Novel organic-inorganic composite polymer-electrolyte membranes for DMFCs

Organic-inorganic composite membranes comprising Nation with inorganic materials such as silica, mesoporous zirconium phosphate (MZP) and mesoporous titanium phosphate (MTP) are fabricated and evaluated as proton-exchange-membrane electrolytes for direct methanol fuel cells (DMFCs). For Nation-silica composite membrane, silica is impregnated into Nation matrix as a sol by a novel water hydrolysis process precluding the external use of an acid. Instead, the acidic nature of Nation facilitates in situ polymerization reaction with Nation leading to a uniform composite membrane. The rapid hydrolysis and polymerization reaction while preparing zirconia and titania sols leads to uncontrolled thickness and volume reduction in the composite membranes, and hence is not conducive for casting membranes. Nafion-MZP and Nafion-MTP composite membranes are prepared by mixing pre-formed porous MZP and MTP with Nation matrix. MZP and MTP are synthesised by co-assembly of a tri-block co-polymer, namely pluronic-F127, as a structure-directing agent, and a mixture of zirconium butoxide/titanium isopropoxide and phosphorous trichloride as inorganic precursors. Methanol release kinetics is studied by volume-localized NMR spectroscopy (employing ``point resolved spectroscopy'', PRESS), the results clearly demonstrating that the incorporation of inorganic fillers in Nation retards the methanol release kinetics under osmotic drag. Appreciable proton conductivity with reduced methanol permeability across the composite membranes leads to improved performance of DMFCs in relation to commercially available Nafion-117 membrane.

Poly (vinyl alcohol) hydrogel membrane as electrolyte for direct borohydride fuel cells

A direct borohydride fuel cell (DBFC) employing a poly (vinyl alcohol)hydrogel membrane electrolyte (PHME) is reported. The DBFC employs an AB(5) Misch metal alloy as anode and a goldplated stainless steel mesh as cathode in conjunction with aqueous alkaline solution of sodium borohydride as fuel and aqueous acidified solution of hydrogen peroxide as oxidant. Room temperature performances of the PHME-based DBFC in respect of peak power outputs; ex-situ cross-over of oxidant, fuel,anolyte and catholyte across the membrane electrolytes; utilization efficiencies of fuel and oxidant, as also cell performance durability are compared with a similar DBFC employing a NafionA (R)-117 membrane electrolyte (NME). Peak power densities of similar to 30 and similar to 40 mW cm(-2) are observed for the DBFCs with PHME and NME, respectively. The crossover of NaBH4 across both the membranes has been found to be very low. The utilization efficiencies of NaBH4 and H2O2 are found to be similar to 24 and similar to 59%, respectively for the PHME-based DBFC; similar to 18 and similar to 62%, respectively for the NME-based DBFC. The PHME and NME-based DBFCs exhibit operational cell potentials of similar to 1 center dot 2 and similar to 1 center dot 4 V, respectively at a load current density of 10 mA cm(-2) for similar to 100 h.

Hydrogel membrane electrolyte for electrochemical capacitors

Polymer electrolytes are known to possess excellent physicochemical properties that are very useful for electrochemical energy systems. The mobility in polymer electrolytes is understood to be mainly due to the segmental motion of polymer chains and the ion transport is generally restricted to the amorphous phase of the polymer. Gel polymer electrolytes (GPE) that are formed using plastizicers and polymers along with ionic salts are known to exhibit liquid-like ionic conductivity while maintaining the dimensional stability of a solid matrix. In the present study, the preparation and characterization of poly(vinyl alcohol)-based hydrogel membranes (PHMEs) as electrolyte for electrochemical capacitors have been reported. VaryingHClO4 dopant concentration leads to different characteristics of the capacitors. The EC comprising PHME doped with 2 M HClO4 and black pearl carbon (BPC) electrodes has been found to exhibit a maximum specific capacitance value of 97 F g(-1), a phase angle value of 78A degrees, and a maximum charge-discharge coulombic efficiency of 88%.

NUPARM and NUCGEN: software for analysis and generation of sequence dependent nucleic acid structures

Software packages NUPARM and NUCGEN, are described, which can be used to understand sequence directed structural variations in nucleic acids, by analysis and generation of non-uniform structures. A set of local inter basepair parameters (viz. tilt, roll, twist, shift, slide and rise) have been defined, which use geometry and coordinates of two successive basepairs only and can be used to generate polymeric structures with varying geometries for each of the 16 possible dinucleotide steps. Intra basepair parameters, propeller, buckle, opening and the C6...C8 distance can also be varied, if required, while the sugar phosphate backbone atoms are fixed in some standard conformation ill each of the nucleotides. NUPARM can be used to analyse both DNA and RNA structures, with single as well as double stranded helices. The NUCGEN software generates double helical models with the backbone fixed in B-form DNA, but with appropriate modifications in the input data, it can also generate A-form DNA ar rd RNA duplex structures.

Surfactant-Mediated Synthesis of Functional Metal Oxide Nanostructures Via Microwave Irradiation-Assisted Chemical Synthesis

In the present work we report a rapid microwave irradiation-assisted chemical synthesis technique for the growth of nanoparticles, nanorods, and nanotubes of a variety of metal oxides in the presence of an appropriate surfactant (cationic, anionic, non ionic and polymeric), without the use of any templates. The method is simple, inexpensive, and helps one to prepare nanostructures in quick time, measured in seconds and minutes. This method has been applied successfully to synthesize nanostructures of a variety of binary and ternary metal oxides such as ZnO, CdO, Fe2O3, CuO, Ga2O3, Gd2O3, ZnFe2O4, etc. There is an observed variation in the morphology of the nanostructures with changes in different process parameters, such as microwave power, irradiation time, identity of solvent, type of surfactant, and its concentration.

Nafion and modified-Nafion membranes for polymer electrolyte fuel cells: An overview

Polymer electrolyte fuel cells (PEFCs) employ membrane electrolytes for proton transport during the cell reaction. The membrane forms a key component of the PEFC and its performance is controlled by several physical parameters, viz. water up-take, ion-exchange capacity, proton conductivity and humidity. The article presents an overview on Nafion membranes highlighting their merits and demerits with efforts on modified-Nafion membranes.

Dispersibility of Barium Titanate Suspension in the Presence of Polyelectrolytes: A Review

Dispersibility of colloidal barium titanate suspensions is reviewed with an emphasis on the use of various polyelectrolytes as dispersants. The fundamentals of colloidal stability are discussed followed by the colloidal properties of barium titanate powder. Dispersion behavior of BaTiO3 in both nonaqueous and aqueous media has been reviewed. Several studies on the stabilization of micron and nano-sized barium titanate using various polymeric dispersants and a rhamnolipid biosurfactant are presented and discussed. The article attempts to provide a comprehensive review of the current state-of-the-art in the area of colloidal processing of barium titanate.

Crystal structure of 3-acetylcoumarin-o-aminobenzoylhydrazone and synthesis, spectral and thermal studies of its transition metal complexes

Transition metal [Mn(II), Co(II), Ni(II), Cu(II), Zn(II) and Cd(II)] complexes of a new Schiff base, 3-acetylcoumarin-o-aminobenzoylhydrazone were synthesized and characterized by elemental analyses, magnetic moments, conductivity measurements, spectral [Electronic, IR, H-1 and C-13 NMR, EPR] and thermal studies. The ligand crystallizes in the monoclinic system, space group P2(1)/n with a = 9.201(5), b = 16.596( 9), c = 11.517(6) angstrom, beta= 101.388(9)degrees, V = 1724.2 (17) angstrom(3) and Z = 4. Conductivity measurements indicated Mn(II) and Co(II) complexes to be 1 : 1 electrolytes whereas Ni(II), Cu(II), Zn(II) and Cd(II) complexes are non-electrolytes. Electronic spectra reveal that all the complexes possess four-coordinate geometry around the metal.

Synthesis, spectral characterization, in-vitro microbiological evaluation and cytotoxic activities of novel macrocyclic bis hydrazone

A macrocyclic hydrazone Schiff base was synthesized by reacting 1,4-dicarbonyl phenyl dihydrazide with 2,6-diformyl-4-methyl phenol and a series of metal complexes with this new Schiff base were synthesized by reaction with Co(II), Ni(II) and Cu(II) metal salts. The Schiff base and its complexes have been characterized by elemental analyses, IR, H-1 NMR, UV-vis, FAB mass, ESR spectra, fluorescence, thermal, magnetic and molar conductance data. The analytical data reveal that the Co(II), Ni(II) and Cu(II) complexes possess 2:1 metal-ligand ratios. All the complexes are non-electrolytes in DMF and DMSO due to their low molar conductance values. Infrared spectral data suggest that the hydrazone Schiff base behaves as a hexadentate ligand with NON NON donor sequence towards the metal ions. The ESR spectral data shows that the metal-ligand bond has considerable covalent character. The electrochemical behavior of the copper(II) complex was investigated by cyclic voltammetry. The Schiff base and its complexes have also been screened for their antibacterial (Escherichia coli, Staphylococcus aureus, Shigella dysentery, Micrococcus, Bacillus subtilis, Bacillus cereus and Pseudomonas aeruginosa) and antifungal activities (Aspergillus niger, Penicillium and Candida albicans) by MIC method. The brine shrimp bioassay was also carried out to study their in-vitro cytotoxic properties. (C) 2009 Elsevier Masson SAS. All rights reserved.