Indian Journal of Chemistry

Sect. A: Inorganic, Bio-inorganic, Physical, Theoretical & Analytical

CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (online)

http://www.niscair.res.in; http://nopr.niscair.res.in

Total visitors: 5171 since 08-07-2011

 

VOLUME 50A

NUMBER 7

JULY 2011

CONTENTS

 

959

 

Study of the glycine amide and water dimer using density functional theory

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yongfeng Guo

 

 

 

The hydrogen bonding in complexes formed between glycine amide and water molecule have been investigated by DFT at
6-311++g(d,p) basis set.  There are four reasonable geometries of the confomer I-water system, with the global minimum being a cyclic double-hydrogen bonded structure.

 

 

 

 

970

 

Performance of phosphoric acid doped polyaniline as electrode material for aqueous redox supercapacitor

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Radhakrishnan, R Muthukannan, U Kamatchi, Chepuri R K Rao* & M Vijayan

 

 

 

Chemical and electrochemical syntheses of phosphoric acid doped polyaniline have been carried out in the  presence and absence of surfactant for aqueous redox supercapacitor application of energy storage devices. The electrochemically grown samples exhibit higher capacitance values (244-305 F/g) than the chemically grown samples.

 

 

979

 

Mechanistic investigations on manganese(II) catalyzed oxidation of substituted
4-oxo-4-arylbutanoic acids by bromate in acid medium

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Cherkupally Sanjeeva Reddy* &
Padma Sunitha Manjari

 

 

 

Participation of the neighboring group of 4–oxo acid and intramolecular catalysis of Mn(II) is proposed in
Mn(II)
-catalyzed acid bromate oxidation of  4–oxo acids, wherein both the C–C bond-breaking and C–O bond-making are involved. However, these two processes are influenced in different ways by the electron withdrawing and electron releasing substituents, leading to a non-linear Hammett’s plot.

 

 

 

 

991

 

Environmental remediation of wastewater containing azo dyes with a heterostructured nanophotocatalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Priti Bansal, Amit Dhir, N Tejo Parksh &
Dhiraj Sud*

 

 

 

The heterostructured ZnO/TiO2 nanophotocatalyst with a molar ratio of 1:9 (ZnO:TiO2) shows promising photocatalytic activity with a higher rate of decolourisation of the azo dye than
TiO2-P25 Degussa. The efficiency of the photocatalyst is maximum at pH 7, an important aspect in its commercial application in wastewater treatment.

 

 

 

Notes

 

996

 

DNA binding and cleavage activities of cationic dinuclear copper(II) and nickel(II) complexes with novel oxime-thiosemicarbazones

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

P Haribabu & K Hussain Reddy*

 

 

 

Dinuclear copper(II) and nickel(II) complexes with novel oxime-thiosemicarbazones are synthesized and characterized based on spectral data. The complexes show significant oxidative cleavage of double strand pBR 322 plasmid DNA. The complexes bind CT-DNA very strongly (105 – 106 M-1) due to supramolecular (non-covalent) interaction  between cationic complexes and negatively charged phosphate diester backbone of DNA.

 

 

 

 

1002

 

Oxidation of alcohols with hydrogen peroxide catalyzed by supported Fe(III) porphyrins

 

 

 

 

 

 

 

 

 

 

 

 

Shahla Masoudian* & Hooriye Yahyaei

 

 

 

Mild and efficient oxidation of alcohols into carbonyl compounds with hydrogen peroxide catalyzed by iron(III) tetrakis(p-sulfonato-phenylporphyrinato) acetate, supported on polyvinylpyridine and Amberlite IRA-400, at room temperature is reported. The catalysts show high activity, not only in the oxidation of benzyl and linear alcohols, but also in the oxidation of secondary alcohols at room temperature.

 

 

1006

 

L-cysteine-nano-gold modified glassy carbon electrode and its application for determination of dopamine hydrochloride

 

 

 

 

 

 

 

 

Yang Song, Yuan-Zhi Song*, An-Feng Zhu &
Hui Zhong

 

 

 

Electrochemical behaviour of dopamine hydrochloride at
l-cysteine-gold-nanoparticle modified glassy carbon electrode is investigated. The
CGN-modified electrode promotes the electrochemical oxidation/reduction of dopamine hydrochloride by considerably accelerating the rate of electron transfer. The modified electrode shows a detection limit of
0. 3 mg L-1.

 

Authors for correspondence are indicated by (*)

 

 

 

 

Indian Journal of Chemistry

Vol. 50A, July 2011, pp.  959-969

 

Study of the glycine amide and water dimer using
density functional theory

Yongfeng Guo

College of Life Science, Qufu Normal University, Shandong, Qfnu, 273165, People’s Republic of China

Email: dongmei1969@163.com

Received 20 December 2010; revised and accepted 18 June 2011

The hydrogen bonding of complexes formed between glycine amide and water molecule has been investigated using density functional theory at 6-311++g(d,p) basis set.  Seven stable stationary points, corresponding to three pairs of mirror-image conformers and one symmetry conformer are observed. Thirteen reasonable geometries on the potential energy hypersurface of glycine amide with water system have been considered with the global minimum being a cyclic double-hydrogen bonded structure. Due to the formation of the hydrogen bond, the force constants of the bond involved in the hydrogen-bonding are reduced and the frequencies are red shifted. At the same time, the increase in the change of the vibrational dipole moments leads to the enhancement of the IR intensities.  The solution phase studies have also been carried out using the Polarized Continuum model at B3LYP/6-311++g(d,p) level for the isolated glycine amide molecule and the hydrogen bonded complexes of glycine amide with water. The results indicate that the more polar the solvent, the more stable is the conformation.

Keywords:  Theoretical chemistry, Density functional calculations, Hydrogen bonds, Glycine amide, Water

 

Indian Journal of Chemistry

Vol. 50A, July 2011, pp. 970-978

 

Performance of phosphoric acid doped polyaniline as electrode material for aqueous redox supercapacitor

S Radhakrishnan, R Muthukannan, U Kamatchi, Chepuri R K Rao*,† & M Vijayan

Functional Materials Division, CSIR-Central Electrochemical Research Institute, Karaikudi 630 006, India

Email: ramchepuri@gmail.com

Received 3 May 2011; revised and accepted 10 June 2011

Phosphoric acid doped polyaniline has been synthesized chemically and electrochemically and tested for its specific capacitance properties by constructing a supercapacitor using stainless steel electrodes. Both the samples are characterized by UV-vis, FTIR, XRD and electrochemical methods. The electrochemically grown samples exhibit higher capacitance values in the range of 244-305 F/g. This is due to the higher purity of the electrochemically prepared polymer due to repeated cycling of the potential. Chemically prepared samples show lower capacitance values due to over-oxidation of the polymer and presence of impurities.

Keywords: Electrochemistry, Conducting polymers, Polymers, Electrode materials, Polyaniline,
Specific capacitance, Charge-discharge, Cyclic voltammetry

 

Indian Journal of Chemistry

Vol. 50A, July 2011, pp. 979-990

 

Mechanistic investigations on manganese(II) catalyzed oxidation of substituted 4-oxo-4-arylbutanoic acids by bromate in acid medium

Cherkupally Sanjeeva Reddy* & Padma Sunitha Manjari

Department of Chemistry, Kakatiya University, Warangal 506 009, India

Email: chsrkuc@yahoo.co.in

Received 8 March 2011; revised and accepted 23 June 2011

The manganese(II)-catalyzed oxidation of substituted 4-oxo-4-arylbutanoic acids (4-oxo acids) by bromate, in aqueous acetic acid medium containing sulphuric acid, has been studied. The reaction is first order each in [bromate] and [acid], less than unity order in both [substrate] and [catalyst], and also shows solvent isotope effect of 0.60 (kc′ (H2O)/kc′ (D2O)). Oxidation rate is not much affected by electron withdrawing substituents, although it is susceptible to electron demand at the seat of the reaction. The linear free-energy relationship is characterized by smooth curves in Hammett plots of log k versus σ. However, the plots are linear with excellent correlation coefficient at all the studied temperatures when Brown’s σ+ values are used. The reaction constant is negative and increases with decrease in temperature. The mechanism involving decomposition of the complex, formed by participation of the neighboring group of 4-oxo acid and intramolecular catalysis of Mn(II) is proposed, wherein, both the C–C bond-breaking and C–O bond-making in the oxidation are involved. However, these two processes are influenced in different ways by the electron withdrawing and electron releasing substituents. A π-complex formation between Mn(II) and -ene of the enol form of oxo acid is proposed.

Keywords: Kinetics, Reaction mechanisms, Oxidation, Bromate oxidation, Arylbutanoic acids, Isokinetic relationships, Manganese

 

Indian Journal of Chemistry

Vol. 50A, July 2011, pp. 991-995

 

Environmental remediation of wastewater containing azo dyes with a heterostructured nanophotocatalyst

Priti Bansala, Amit Dhirb, N Tejo Prakashb & Dhiraj Suda, *

aDepartment of Chemistry, Sant Longowal Institute of Engineering and Technology
(Deemed University), Longowal 148 106, Punjab, India

bDepartment of Biotechnology & Environmental Sciences, Thapar University, Patiala 147 004, India

Email: suddhiraj@yahoo.com

Received 4 January 2011; revised and accepted 24 June 2011

The synthesis, characterization and photocatalytic activity of heterostructured ZnO/TiO2 nanophotocatalyst is reported. The photocatalyst ZnO/TiO2 prepared in molar ratio of 1:9 (ZnO: TiO2) and characterized with X-ray diffraction, SEM-EDX and UV–vis data. The photocatalytic activity has been evaluated using acid orange 7 as a model organic compound. The rate of decolorization has been estimated from residual concentration spectrophotometrically and mineralization rate studied by measuring COD. The results have been compared with TiO2-P25 Degussa. ZnO/TiO2 shows promising photocatalytic activity and 12% higher rate of decolourisation of the dye than that of TiO2 -P25 Degussa. The effect of operational parameters such as pH of reaction medium and concentration of dye on the decolorization rate of AO7 in water has also been investigated. The efficiency of the photocatalyst is maximum at pH 7, an important aspect from the view of its commercial application in waste water treatment technology.

Keywords: Photochemistry, Photocatalyst, Dye degradation, Decolorization, Azo compounds, Wastewater

 

Indian Journal of Chemistry

Vol 50A, July 2011, pp. 996-1001

 

DNA binding and cleavage activities of cationic dinuclear copper(II) and nickel(II) complexes with novel oxime-thiosemicarbazones

P Haribabu & K Hussain Reddy*

Department of Chemistry, Sri Krishnadevaraya University,
Anantapur 515 003, India

Email: khussainreddy@yahoo.co.in

Received 11 February 2011; revised and accepted 28 June 2011

Complexes of Cu(II) and Ni(II) with novel type of ligands, viz., diacetylmonoximethiosemicarbazone, diacetylmonoxime-N(4)-methylthiosemicarbazone, diacetylmonoxime-N(4)-ethylthiosemicarbazone and diacetylmonoxime-N(4)-phenyl- thiosemicarbazone have been synthesized and characterized based on molar conductance, magnetic moment, electronic, IR and ESR spectral data. Electrochemical behaviour of these complexes is investigated by cyclic voltammetric studies. The binding properties of these complexes with calf-thymus DNA have been investigated using absorption spectrophotometry. Cleavage activity of these complexes has been investigated on double stranded pBR 322 plasmid DNA by gel electrophoresis experiments in the absence and in the presence of oxidant.

Keywords: Bioinorganic chemistry, DNA cleavage, Copper, Nickel, Thiosemicarbazones, Oximes

 

Indian Journal of Chemistry

Vol. 50A, July 2011, pp. 1002-1005

 

Oxidation of alcohols with hydrogen peroxide catalyzed by
supported Fe(III) porphyrins

Shahla Masoudian* & Hooriye Yahyaei

Department of Chemistry, Islamic Azad University Zanjan-Branch, Zanjan, Iran

Email: sh_m_chem@yahoo.com

Received 11 November 2010; revised and accepted 17 June 2011

Mild and efficient oxidation of alcohols with hydrogen peroxide catalyzed by iron(III)
tetrakis(p-sulfonatophenylporphyrinato)acetate, supported on polyvinylpyridine and Amberlite IRA-400 at room temperature is reported. The cata
lysts used in this study show high activity, not only in the oxidation of benzyl and linear alcohols but also in the oxidation of secondary alcohols at room temperature. The catalysts can be reused several times without significant loss of their activity.

Keywords: Catalysts, Supported calaysts, Oxidation, Alcohols, Metalloporphyrins, Hydrogen Peroxide, Iron

 

Indian Journal of Chemistry

Vol. 50A, July 2011, pp. 1006-1009

 

L-cysteine-nano-gold modified glassy carbon electrode and its application for determination of dopamine hydrochloride

Yang Songa, Yuan-Zhi Songb, *, An-Feng Zhub & Hui Zhongb

aCollege of Materials Science and Engineering, Beijing University of Chemical Technology, Peking 100029,
People’s Republic of China

Email: songyuanzhi@126.com

bJiangsu Province Key Laboratory for Chemistry of Low-Dimensional Materials, School of Chemistry & Chemical Engineering, Huaiyin Normal University, Huai An 223300, People’s Republic of China

Received 8 March 2011; revised and accepted 20 June 2011

A sensor based on l-cysteine-gold-nanoparticle modified glassy carbon electrode has been prepared. Electrochemical behaviour of dopamine hydrochloride at l-cysteine-gold-nanoparticle modified glassy carbon electrode is investigated. A simple, sensitive, and inexpensive method for determination of dopamine hydrochloride is proposed.

Keywords:   Electrochemistry, Sensors, Modified electrode, Gold, Dopamine hydrochloride