Pseudopotential in the study of superconducting state parameters of metallic glasses

A well recognized model potential is used to study the superconducting state parameters (SSP) viz. electron–phonon coupling strength λ, Coulomb pseudopotential μ¹, transition temperature T_C, isotope effect exponent α and effective interaction strength N₀V of some binary metallic glasses of simple, non-simple and transition metals. Five local field correction functions proposed by Hartree (H), Taylor (T), Ichimaru–Utsumi (IU), Farid et al. (F) and Sarkar et al. (S) are used in the present investigation to study the screening influence on the aforesaid properties. Instead of using Vegard’s law, pseudo-alloy-atom model (PAA) in the present investigation is proposed and found successful. The present results of the SSP are found in qualitative agreement with other such earlier reported data wherever exist, which confirms the superconducting phase in the metallic glasses.     

Iridodials: enantiospecific synthesis and stereochemical assignment of the pheromone for the golden-eyed lacewing, Chrysopa oculata

1R,2S,5R,8R; 1R,2S,5R,8S; 1S,2S,5R,8R; and 1S,2S,5R,8S-Iridodials have been prepared in five steps from 4aS,7S,7aR and 4aS,7S,7aS-nepetalactones, major components of catnip oil. 1R,2S,5R,8R-Iridodial has been identified as a male-produced male-aggregation pheromone for Chrysopa oculata, the first pheromone of any kind identified for lacewings.     

Synthesis of O,O Ethane Bridged Bis-copper(II) Macrocycles. Selective Enzyme Model for Catecholase Activity

New mononuclear and dinuclear complexes [3-hydroxyethyl-1,3,5,8,11pentaazacyclotridecane]copper(II) (1)/nickel(II) (2) perchlorate and O,O ethane bridged bis-copper(II) (3)/nickel(II) (4) macrocycles have been synthesized and characterized by various spectroscopic techniques, viz. i.r., n.m.r., e.p.r., u.v.–vis. and conductance measurements. Spectral data and conductance measurements reveal that all the complexes are consistent with square-planar geometry and are ionic in nature. The catalytic activity of the dinuclear Cu(II) complex (3) in the presence of pyrocatechol was determined spectrometrically by monitoring the increase of the o-benzoquinone characteristic absorption band at 25,000 cm⁻¹ with respect to time in DMF saturated with molecular oxygen. The kinetic parameters V_max (2.8×10⁻³ M s⁻¹) and K_M (1.4×10⁻³ mm) have been determined by Michaelis–Menten method. Electrochemistry of the dinuclear Cu(II) complex has been studied in the presence of molecular oxygen with pyrocatechol and without pyrocatechol at a scan rate of 0.1 V s⁻¹ by cyclic voltammetry. On addition of pyrocatechol, complex shows a shift in E_pc, E_pa and E_1/2 values indicating the oxidation of substrate (pyrocatechol).     

Studies on ion association. Calorimetric study of the formation of monoazido complexes of Ni(II), Zn(II) and Cd(II)

From rehydration experiments the hydrates Ba(OH)₂ · 8 H₂O, Ba(OH)₂ · 3 H₂O β-Ba(OH)₂, · 1 H₂O, and γ-Ba(OH)₂ · 1 H₂O have been found in the system Ba(OH)₂-H₂O. Thermoanalytical measurements (DTA, TG, DTG, high temperature X-ray diffraction, high temperature Raman scattering) on these hydrates are reported. Thermal decomposition of Ba(OH)₂ · 8 H₂O and Ba(OH)₂ · 3 H₂O always results in the formation of β-Ba(OH)₂ · 1 H₂O, the stable form of the monohydrates at ambient temperature. Dehydration of β- and γ-Ba(OH)₂ · 1 H₂O, both of which form anhydrous β-Ba(OH)₂ as the first product of decomposition, starts at 105 and 115°C, respectively. Single crystals of Ba(OH)₂ · 3 H₂O and γ-Ba(OH)₂ · 1 H₂O were prepared from Ba(OH)₂ · 8 H₂O meltings and from ethanolic solutions of Ba(OH)₂ , respectively. The crystal data are: Ba(OH)₂ · 3 H₂O (orthorhombic, Pnma): a = 764.0(2), b = 1140,3(5), c = 596.5(1) pm, Z = 4; γ-Ba(OH)₂ · 1 H₂O (monoclinic, P2₁/m or P2₁): a = 704.9(2), b = 418.4(1), c = 633.3(1) pm, β = 111.45(2)°, Z = 2.     

Crystallographic evidence of hexacoordination at phosphorus via intramolecular coordination of donor groups on phosphane and phosphane sulphide

The X-ray structure analysis of bis(8-dimethylamino-l-naphthyl)phenylphosphane (3) and of the corresponding sulphide 4 has revealed hexacoordination at phosphorus in both cases, the N … P separations being less than the sum of the van der Waal radii. Furthermore, in both cases the overall geometry corresponds to a distorted bicapped tetrahedron. The optimum geometry calculated for 4 via the program developed by Autodesk (MM + method) suggests that the structure of the molecule is a function not only of steric requirements but also of electronic effects.     

Thermodynamics of 2,2′-dipyridinium ion and its iron(II) complex in methanol—water mixture at 25°C

The enthalpies of formation of the 2,2′-dipyridinium ion and the 2,2′-dipyridyl-iron(II) complex in methanol—water media at 25°C have been determined by caloriumetry. The entropy-changes have been calculated combining the enthalpy values with the corresponding free-energy changes previously reported. The role of solvents on the thermodynamic parameters has been discussed.     

Synthesis, spectra and biomimetic properties of copper(II)-copper(II) and copper(II)-zinc(II) binuclear complexes with CuN5 chromophores

X-band electron spin resonance (ESR) and UV-vis spectra of a homobinuclear [(Bipy)2Cu-E-Im-Cu(Bipy)2](BF4)3 and a heterobinuclear [(Bipy)2Cu-E-Im-Zn(Bipy)2](BF4)3 complexes, E-Im=2-ethylimidazolate ion have been described as possible models for superoxide dismutase (SOD). Magnetic moment and ESR spectral measurements of the homobinuclear complex have shown an antiferromagnetic exchange interaction. From pH-dependent ESR and UV-vis spectral measurements studies, these complexes have been found to be stable over 8.5-10.5 pH range. These complexes catalyze the dismutation of superoxide (O2-) at biological pH. All the observations indicate that these complexes act as good possible models for superoxide dismutase.     

Biomimetic reduction of nimesulide with NaBH4 catalyzed by metalloporphyrins

The biomimetic reduction of anti-inflammatory drug, nimesulide (1) with sodium borohydride catalyzed by 5,10,15,20-tetraarylporphyrinatoiron(III) chlorides [TAPFe(III)Cl] has been studied in organic solvents under anaerobic and aerobic conditions.