• Volume 113, Issue 1

      February 2001,   pages  1-76

    • Peroxidase-like catalytic activities of ionic metalloporphyrins supported on functionalised polystyrene surface

      Mikkiv Vinodu M Padmanabhan

      More Details Abstract Fulltext PDF

      Metalloderivatives of anionic tetrasulphonated tetraphenylporphyrin (MTPPS, M = Mn(III), Fe(III) and Co(III)) were synthesized and immobilized on cationically functionalised divinylbenzene(DVB)-crosslinked polystyrene(PS). These supported catalysts (PS-MTPPS) were found to exhibit peroxidase-like activity. The co-oxidation of 4-aminoantipyrine and phenol by H2O2 was attempted with these catalysts to mimic this enzyme function. The catalytic efficiency of all these immobilized MTPPS was found to be superior to the corresponding unsupported MTPPS in solution. The effect of the central metal ion of the porphyrin, pH of the reaction medium and also the temperature effect are investigated. The ideal pH was seen to be in the 8.0–8.5 range, with maximum effect at 8.2. The efficiency order for the various PS-MTPPS was seen to be Co>Mn>Fe, with CoTPPS showing efficiency comparable to that of horseradish peroxidase. The catalytic efficiency was found to be increasing with temperature for all the catalysts. The re-usability of these PS-MTPPS systems for peroxidase-like activity was also studied and it was found that they exhibited a very high degree of recyclability without much poisoning.

    • Synthesis and spectral characterization of homo-and hetero-dinuclear complexes with a new septadentate Schiff base ligand

      J K Nag D Das S Pal C Sinha

      More Details Abstract Fulltext PDF

      Reaction between 3-formylsalicylic acid and bis-(2-aminophenyl)-disulphide yields a septadentate Schiff base with N2SO4 donor frame of which the inner compartment is N2SO2 and the outer is O2O2 type. It forms several complexes with inner copper centre and outer nontransition/transition metal ions. The complexes have been characterised by elemental analyses, spectral (IR, absorption, diffused reflectance), thermal and magnetic data. Dinuclear copper complexes exhibit subnormal magnetic moments (≈ 0.80 BM), showing magnetic exchange, and six-line solid-state ESR spectra at 77 K.

    • Synthetic, spectral and solution studies on imidazolate-bridged copper(II)-copper(II) and copper(II)-zinc(II) complexes

      Subodh Kumar R N Patel P V Khadikar K B PAndeya

      More Details Abstract Fulltext PDF

      Synthesis, spectral and solution studies on 2-ethyl imidazolate-bridged (2-EtIm) homo-binuclear copper(II)-copper(II) and hetero-binuclear copper(II)-zinc(II) homologue are described. Magnetic moment values of homo-binuclear complexes indicate that the imidazolate group can mediate antiferromagnetic interactions. Optical spectra of hetero-binuclear complex at varying pH values suggest that the imidazolate-bridged complex is stable over the pH-range 7.15–10.0.

    • Synthesis of cyano-bridged bimetallic complexes of η5-indenyl ruthenium(II): Characterization and spectroscopic studies

      K Mohan Rao E K Rymmai

      More Details Abstract Fulltext PDF

      Reactions of the cyanide complexes of the type [(Ind)Ru(PPh3)2CN] (1), [(Ind)Ru(dppe)CN] (2), [(Cp)Ru(PPh3)2CN] (3), with the corresponding chloro complexes [(Ind)Ru(PPh3)2Cl] (4), [(Ind)Ru(dppe)Cl] (5), [(Cp)Ru(PPh3)2Cl] (6), in the presence of NH4PF6 salt give homometallic cyano-bridged compounds of the type [(Ind)(PPh3)2Ru-CN-Ru(PPh3)2(Cp)]PF6 (7), [(Ind)(PPh3)2Ru-CN-Ru(PPh3)2(Ind)] PF6 where Ind = indenyl, η5-C9H7, (8), [(Cp)(PPh3)2Ru-CN-Ru(dppe)(Ind)]PF6, dppe = (Ph2PCH2CH2PPh2) (9), [(Ind(dppe)Ru-CN-Ru(PPh3)2(Ind)PF6 (10) and [(Ind)(dppe)Ru-CN-Ru(PPh3)2(Cp)]PF6 (11) respectively. Reaction of complex3 with [(p-cymene)RuCl2]2 dimer gave a mixed dimeric complex [(Cp)Ru(PPh3)2-CN-RuCl2(p-cymene)] (12). All these complexes have been characterized by IR,1H,13C and31P NMR spectroscopy and C, H, N analyses.

    • Can Co(II) or Cd(II) substitute for Zn(II) in zinc fingers?

      P Rabindra Reddy M Radhika

      More Details Abstract Fulltext PDF

      Zinc finger domains consist of sequences of amino acids containing cysteine and histidine residues tetrahedrally coordinated to a zinc ion. The role of zinc in a DNA binding finger was considered purely structural due to the absence of redox chemistry in zinc. However, whether other metals e.g. Co(II) or Cd(II) can substitute Zn(II) is not settled. For an answer the detailed interaction of Co(II) and Cd(II) with cysteine methylester and histidine methylester has been investigated as a model for the zinc core in zinc fingers. The study was extended to different temperatures to evaluate the thermodynamic parameters associated with these interactions. The results suggest that zinc has a unique role.

    • Kinetics and mechanism of the oxidation of some diols by benzyltrimethylammoniumtribromide

      Garima Goswami Seema Kothari Kalyan K Banerji

      More Details Abstract Fulltext PDF

      The kinetics of oxidation of five vicinal and four non-vicinal diols, and two of their monoethers by benzyltrimethylammonium tribromide (BTMAB) have been studied in 3:7 (v/v) acetic acid-water mixture. The vicinal diols yield the carbonyl compounds arising out of the glycol bond fission while the other diols give the hydroxycarbonyl compounds. The reaction is first-order with respect to BTMAB. Michaelis-Menten type kinetics is observed with respect to diol. Addition of benzyltrimethylammonium chloride does not affect the rate. Tribromide ion is postulated to be the reactive oxidizing species. Oxidation of [1,1,2,2-2H4] ethanediol shows the absence of a kinetic isotope effect. The reaction exhibits substantial solvent isotope effect. A mechanism involving a glycol-bond fission has been proposed for the oxidation of the vicinal diols. The other diols are oxidized by a hydride ion transfer to the oxidant, as are the monohydric alcohols.

    • Small-angle neutron scattering study of sodium cholate and sodium deoxycholate interacting micelles in aqueous medium

      J Santhanalakshmi G Shantha Lakshmi V K Aswal P S Goyal

      More Details Abstract Fulltext PDF

      Small angle neutron scattering (SANS) measurements of D2O solutions (0.1 M) of sodium cholate (NaC) and sodium deoxycholate (NaDC) were carried out atT= 298 K. Under compositions very much above the critical micelle concentration (CMC), the bile salt micelle size growths were monitored by adopting Hayter-Penfold type analysis of the scattering data. NaC and NaDC solutions show presence of correlation peaks atQ = 0.12 and 0.1 å-1 respectively. Monodisperse ellipsoids of the micelles produce best fits. For NaC and NaDC systems, aggregation number (9.0, 16.0), fraction of the free counterions per micelle (0.79, 0.62), semi-minor (8.0 å) and semi-major axes (18.4, 31.7 å) values for the micelles were deduced. Extent of micellar growth was studied using ESR correlation time measurements on a suitable probe incorporating NaC and NaDC micelles. The growth parameter (axial ratio) values were found to be 2.3 and 4.0 for NaC and NaDC systems respectively. The values agree with those of SANS.

    • An insight into the passivation of cupronickel alloys in chloride environment

      J Mathiyarasu N Palaniswamy V S Muralidharan

      More Details Abstract Fulltext PDF

      Cupronickels offer enhanced corrosion protection in marine environments by the formation of passive films on the surface. Cyclic voltammetric studies were carried on cupronickels in chloride solutions at pH 6.3 to understand the role of chloride ions in passive film formation. Increase in nickel content of the alloy and of chloride ions in solution decreases film resistance. Chloride ions take part in reduction of the passive film to copper. A solid-state model for passive film formation involving chloride ions has been attempted.

  • Journal of Chemical Sciences | News

    • Editorial Note on Continuous Article Publication

      Posted on July 25, 2019

      Click here for Editorial Note on CAP Mode

© 2017-2019 Indian Academy of Sciences, Bengaluru.