Activation-controlled outer-sphere electron transfer reactions: reduction of heteropoly 11-tungstovanadophosphate and heteropoly 10-tungstodivanado phosphate by thiourea in aqueous acid medium

The kinetics of reduction of heteropoly 11-tungstovanadophosphate, [PV^VW₁₁O₄₀]⁴⁻, (HPA1) and heteropoly 10-tungstodivanadophosphate, [PV^VV^VW₁₀O₄₀]⁵⁻, (HPA2) by thiourea has been investigated in HClO₄/phthalate/acetate buffer solutions spectrophotometrically at 25 °C in aqueous medium. The stoichiometry of the reaction is 1:1 in both cases. The HPAs are converted into the corresponding one-electron reduced heteropoly blues, namely, [PV^IVW₁₁O₄₀]⁵⁻ and [PV^IVV^VW₁₀O₄₀]⁶⁻, and thiourea is oxidised to formamidine disulphide. The reaction shows first-order dependence in both [HPA] and [thiourea] at constant pH. The rate–pH profile shows the participation of both the neutral and deprotonated forms of thiourea in the reaction. The reaction proceeds through an outer sphere electron transfer mechanism in which activation-controlled electron transfer is the rate-determining step. Self-exchange rate constants for the couples [PV^VW₁₁O₄₀]⁴⁻/[PV^IVW₁₁O₄₀]⁵⁻, [PV^VV^VW₁₀O₄₀]⁵⁻/[PV^IVV^VW₁₀O₄₀]⁶⁻ and H₂NCSNH₂/H₂NCS^·+NH₂ have been evaluated by Marcus theory.     

Regio- and stereoselective syntheses of piperidine derivatives via ruthenium-catalyzed coupling of propargylic amides and allylic alcohols

Intermolecular selective coupling of linear allylic alcohols and propargylic amides occurs in the presence of a catalytic amount of the cationic ruthenium complex [Cp*Ru(NCCH(3))(3)]PF(6) followed by condensation to generate six-membered cyclic enamides or hemiaminal ethers with water as the only side product.     

Isomorphous substitution of Mn(II), Ni(II) and Zn(II) in AlPO-31 molecular sieves and study of their catalytic performance

Isomorphously substituted molecular sieves, MAPO-31, NAPO-31 and ZAPO-31, were prepared under mild hydrothermal conditions from gels containing sources of aluminium, phosphorus, appropriate metal and dipropylamine (DPA), presumably acting as a structure-directing template. They were characterized by XRD, FTIR, TGA, inductively coupled plasma (ICP), ESR, Brunauer, Emmett, Teller (BET) and diffusion reflectance spectroscopy (DRS) techniques. In the XRD, the peak at 2θ = 16.7° of the metal substituted AlPO-31 is more intense than that of pure AlPO-31 suggesting preferential occupation of the plane corresponding to it as compared to other planes. The O-H stretch in the IR spectra of the metal-substituted molecular sieves is blue-shifted with respect to the parent AlPO-31 molecular sieves possibly due to metal substitution. Theg values obtained from the ESR spectra of MAPO-31 and NAPO-31 also substantiate framework substitution. Ethylation of toluene was carried out between 300 and 450°C over the above catalysts as a model test reaction. The high toluene conversion over metal-substituted molecular sieves proves the isomorphic substitution of metal ions in the AlPO-31 framework.     

Synthesis, complexation studies and biological applications of some novel stilbenophanes, indolophanes and bisindolostilbenophanes via McMurry coupling

Various types of stilbenophanes, indolophanes and bisindolostilbenophanes were synthesized by intra-, inter- and tandem intra-, intermolecular McMurry coupling. Some of the indolophanes and bisindolostilbenophanes exhibited significant activity against the growth of various bacteria. Complexation of some of the cyclophanes with TCNQ has also been studied.     

Chiral α-alkylation/arylation in 1-phenyl-2-(1-pyrrolidinyl)-1-propanol through Grignard reactions

Complete asymmetric induction has been achieved during Grignard alkylations/arylations resulting in (1S,2R)- and (1R,2R)-1-phenyl-1-alkyl/aryl-2-(1-pyrrolidinyl)-1-propanols which are isolated as hydrochlorides.     

Numerical solution of three‐dimensional velocity–vorticity Navier–Stokes equations by finite difference method

This paper describes the finite difference numerical procedure for solving velocity–vorticity form of the Navier–Stokes equations in three dimensions. The velocity Poisson equations are made parabolic using the false‐transient technique and are solved along with the vorticity transport equations. The parabolic velocity Poisson equations are advanced in time using the alternating direction implicit (ADI) procedure and are solved along with the continuity equation for velocities, thus ensuring a divergence‐free velocity field. The vorticity transport equations in conservative form are solved using the second‐order accurate Adams–Bashforth central difference scheme in order to assure divergence‐free vorticity field in three dimensions. The velocity and vorticity Cartesian components are discretized using a central difference scheme on a staggered grid for accuracy reasons. The application of the ADI procedure for the parabolic velocity Poisson equations along with the continuity equation results in diagonally dominant tri‐diagonal matrix equations. Thus the explicit method for the vorticity equations and the tri‐diagonal matrix algorithm for the Poisson equations combine to give a simplified numerical scheme for solving three‐dimensional problems, which otherwise requires enormous computational effort. For three‐dimensional‐driven cavity flow predictions, the present method is found to be efficient and accurate for the Reynolds number range 100?Re?2000. Copyright © 2004 John Wiley & Sons, Ltd.     

Investigation of two‐dimensional channel flow with a partially compliant wall using finite volume–finite difference approach

This paper presents a numerical simulation of steady two‐dimensional channel flow with a partially compliant wall. Navier–Stokes equation is solved using an unstructured finite volume method (FVM). The deformation of the compliant wall is determined by solving a membrane equation using finite difference method (FDM). The membrane equation and Navier–Stokes equation are coupled iteratively to determine the shape of the membrane and the flow field. A spring analogy smoothing technique is applied to the deformed mesh to ensure good mesh quality throughout the computing procedure. Numerical results obtained in the present simulation match well with that in the literature. Copyright © 2005 John Wiley & Sons, Ltd.     

Metallation of ethylenediamine based Schiff base with biologically active Cu(II), Ni(II) and Zn(II) ions: synthesis, spectroscopic characterization, electrochemical behaviour, DNA binding, photonuclease activity and in vitro antimicrobial efficacy

A new ligand [C28H20N6O8] (L2) has been synthesized by the condensation reaction of 3-hydroxy-4-nitrobenzaldehydenephenylhydrazine (L1) with diethyloxalate. This ligand L2 is allowed to react with bis(ethylenediamine)Cu(II)/Ni(II)/Zn(II) complexes. It affords [(L2)Cu(en)2]Cl2(1)/[(L2)Ni(en)2]Cl2(2)/[(L2)Zn(en)2]Cl2(3) complexes, respectively. These complexes (1-3) have been characterized by the spectral and analytical techniques. The interaction of these complexes with calf thymus (CT) DNA is characterized by the absorption spectra which exhibit a slight red shift with hypochromic effect. Electrochemical analyses and viscosity measurements have also been carried out to determine the mode of binding. The shift in ΔEp, E1/2 and Ipc values explores the interaction of CT DNA with the above metal complexes. The slight increase in the viscosity of CT DNA indicates that these complexes bind to CT DNA through a partial non-classical intercalative mode. Cleavage experiments using pBR322 DNA in presence of H2O2 indicate that these complexes behave as efficient artificial chemical nucleases in the order of 1>2>3. Moreover, the antibacterial and antifungal studies reveal that complex 1 is highly active against the bacterial and fungal growth.