Indian Journal of Chemistry

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

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

Total visitors: 4070 since 05-06-2013

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

 

 

 

 

 

VOLUME 52A

NUMBER 6

JUNE 2013

 

CONTENTS

 

 

709

 

Epoxidation of mixed bi-olefins with air over nanosized Co3O4 assisted by ultrasonic waves

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

J Lei, X-H Lu*, J-L Zhang, X-L Wei, D Zhou &
Q-H Xia
*

 

 

 

Nanosized Co3O4 prepared by a simple method is active in the epoxidation of mixed bi-olefins with dry air aided by ultrasonic waves. When α-methylstyrene and α-pinene are mixed in the molar ratio of 1:1, both conversion and selectivity are distinctly promoted and are much superior to those of α-methylstyrene or
α-pinene alone. Varying effects are seen with other alkenes mixed with cyclooctene at the molar ratio of 1:5.

 

 

 

 

717

 

Copper(II) promoted hydrolysis of 2,4,6-tris(2-pyridyl)-1,3,5-triazine: Synthesis, characterization and biological activities of the hydrolytic products

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ram N Patel*, Vishnu P Sondhiya,

Dheerendra K Patel, Krishna K Shukla,
Dinesh K Patel & Yogendra Singh

 

 

 

Two new copper(II) complexes, viz., [Cu(IDA)C6H5N2O].2H2O and [Cu{(NC5H4CO)2N}(H2O)2]NO3.2H2O, have been synthesized and structurally characterized by single crystal X-ray diffraction studies. Both the complexes show significant hydrogen bonding and non-covalent ππ stacking interactions.

 

 

 

 

724

 

Cu(II)-catalysed oxidation of bioactive substrates by methylene blue in acidic medium assisted by Zn(II): Possible role of nanoparticles

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

K K Mishra*, Ritu Gupta, Maya Shukla,
Ranu Chaturvedi, Mahender Pal & Ranjana Sharma

 

 

 

Cysteine hydrochloride and 2-mercaptoethylamine hydrochloride are catalyzed by Cu(II) in acidic medium involving the participation of Cu nanoparticles. On addition of Zn(II) (an inactive metal ion) to the reaction, the rate increases appreciably. TEM and SAED studies reveal a change in morphology of the nanoparticles on adding Zn(II) which probably causes its synergetic effect.

 

 

 

 

 

732

 

Influence of cetyltrimethylammonium bromide/ sodium dodecyl sulfate micelles on the oxidation
of L-arginine by N-bromophthalimide in presence
of HClO4

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yokraj Katre*, Namita Goyal, Radhika Sharma & Ajaya Kumar Singh

 

 

 

Oxidation reaction of L-arginine by N-bromophthalimide has been studied in micellar systems of CTAB and SDS. CTAB strongly enhances the rate of reaction while SDS has an inhibitory action.

 

 

 

 

Notes

 

739

 

Mechanochemical synthesis of sodium doped hydroxyapatite powder

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sharifah Adzila, Iis Sopyan*, Ramesh Singh,
Erlani Pusparini & Mohd. Hamdi

 

 

 

Sodium ion is doped into HA by sodium hydroxide precursor in a dry mixture of Ca(OH)2 and (NH3)2HPO4. A mixture of rods and spheres is found in the Na+ doped HA.

 

 

IC3616-GA.tif

 

 

 

744

 

Synthesis and properties of polypyrrole obtained from a new Fe(III) complex as oxidizing agent

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Chepuri R K Rao*, R Muthukannan, J Adriel Jebin,
T Antony Raj & M Vijayan

 

 

 

Highly conducting polypyrrole (50 S/cm) is obtained with a new complex synthesized from FeCl3 and lauryl sulphate as oxidizing agent.

 

 

 

 

 

749

 

Hydrothermal synthesis and characterization of bis(4,4′-bipyridinium) dodecatungstosilicate dihydrate

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rajarshi Chatterjee, Dipak K Hazra,
Monika Mukherjee, M Nethaji & Mahammad Ali
*

 

 

 

 

 

 

753

 

Guide to Authors

 

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

Indian Journal of Chemistry

Vol. 52A, June 2013, pp. 709-716

 

 

Epoxidation of mixed bi-olefins with air over nanosized Co3O4
assisted by ultrasonic waves

J Lei, X-H Lu*, J-L Zhang, X-L Wei, D Zhou & Q-H Xia*

Ministry-of-Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules
&
Hubei Collaborative Innovation Center for Advanced Organochemical Materials, Hubei University,
Wuhan 430062, PR China

Email: xinhuan003@yahoo.com.cn (XHL)/ xiaqh518@aliyun.com (QHX)

Received 9 July 2012; revised and accepted 16 May 2013

Nanosized Co3O4 prepared by a simple method is considerably active in the ultrasonic waves assisted epoxidation of mixed bi-olefins with dry air. Both conversions and selectivities are distinctly promoted with
α-methylstyrene and α-pinene mixed in the molar ratio of 1:1, as compared to α-methylstyrene or to α-pinene alone. When other alkenes are mixed with cyclooctene at 1:5 (molar ratio), different effects are observed. The mixture of styrene and cyclooctene shows almost the same increase in activity as the mixture of α-methylstyrene and α-pinene. While isophorone could assist the epoxidation of cyclooctene, by itself it could not be oxidized by molecular oxygen under the present conditions. When indene is mixed with cyclooctene, its conversion increases; however, the reactivity of cyclooctene decreases notably. UV-vis spectral analysis shows that these observations may be due to the intermolecular electron transfer which is very important for the enhancement of reactivities of bi-olefinic molecules.

Keywords: Epoxidation, Hydrocarbons, Olefins, Biolefins, Epoxides, Mixed alkenes, Nanomaterials, Cobalt oxide

Indian Journal of Chemistry

Vol. 52A, June 2013, pp. 717-723

 

 

Copper(II) promoted hydrolysis of 2,4,6-tris(2-pyridyl)-1,3,5-triazine:
Synthesis, characterization and biological activities of the hydrolytic products

Ram N Patel*, Vishnu P Sondhiya, Dheerendra K Patel, Krishna K Shukla,
Dinesh K Patel & Yogendra Singh

Department of Chemistry, APS University, Rewa 486 003, MP, India

Email: rnp64@ymail.com

Received 8 January 2013; revised and accepted 23 May 2013

The hydrolysis of 2,4,6-tris(2-pyridyl)-1,3,5-triazine (tptz) yield the compounds bis(2-pyridylcarbonyl)amide and 2-picolinamide. From these hydrolytic products, two copper(II) complexes viz,. [Cu(IDA)(2-pa)].2H2O (1) and [Cu(bpca)(H2O)2]NO3.2H2O (2) [where IDA = iminodiacetic acid, 2-pa = 2-picolinamide and bpca = bis(2-pyridyl-carbonyl)amido] have been isolated and structurally characterized by single crystal X-ray diffraction studies. Both complexes belong to the triclinic crystal system having space group P-1. Complex (2) shows significant hydrogen bonding and non-covalent ππ stacking interactions. In complex (2), Bifurcated (three centered) hydrogen bonds have been detected. The electron paramagnetic mononuclear copper(II) complexes display X-band epr spectra in 100% DMSO at 77 K giving g> g^> 2.0023, indicating dx2-y2ground state in a square pyramidal geometry. In-vitro antibacterial study has been assayed against some selected microorganisms using agar disc diffusion method. The DNA cleavage activities of both complexes are also investigated by gel electrophoresis using pBR 322 DNA.

Keywords: Coordination chemistry, X-ray crystal structure, Bifurcated hydrogen bonding, Hydrogen bonding,

EPR spectroscopy, DNA cleavage, Copper, Triazines

Indian Journal of Chemistry

Vol. 52A, June 2013, pp. 724-731

 

 

Cu(II)-catalysed oxidation of bioactive substrates by methylene blue in
acidic medium assisted by Zn(II): Possible role of nanoparticles

K K Mishra*, Ritu Gupta, Maya Shukla, Ranu Chaturvedi, Mahender Pal & Ranjana Sharma

Department of Chemistry, Rani Durgavati University, Jabalpur 482 001, India
Email:kkmishra.chem@gmail.com

Received 1 November 2012; revised and accepted 21 May 2013

The bioactive sulphydryl substrates, cysteine hydrochloride (cys) and 2-mercaptoethylamine hydrochloride
(2-ME) react with methylene blue in acidic medium in presence of Cu(II) as a catalyst. While Zn(II) has no catalytic role on its own, when it is added along with Cu(II) to the reaction system, the corresponding rate constants increase by about 25%. TEM images of the representative cys-Cu-MB system reveal the formation of the nanorods, while on adding Zn(II) to the reaction system, the morphology of the nanoparticles changes from nanorods to nanogranules. These findings are also substantiated by electron diffraction studies. It thus appears that the morphology of nanoparticles and the possible synergetic effect of Zn(II) are correlated. The synergetic effect of Zn(II) is also favoured by the presence of amino group in the substrate molecule while carboxylic group hinders it.

Keywords: Kinetics, Reaction mechanism, Nanoparticles, Synergism, Catalysis, Copper, Zinc, Metal ion catalysis, Methylene blue

 

Indian Journal of Chemistry

Vol 52A, June 2013, pp. 732-738

 

 

Influence of cetyltrimethylammonium bromide/ sodium dodecyl sulfate micelles on the oxidation of L-arginine by N- bromophthalimide in presence of HClO4

Yokraj Katrea,*, Namita Goyala, Radhika Sharmaa & Ajaya Kumar Singhb

aDepartment of Chemistry, Kalyan Post Graduate College, Bhilai Nagar, Durg, Chhattisgarh 490 006, India

bDepartment of Chemistry, Government Vishwanath Yadav Tamaskar Post Graduate Autonomous College,
Durg, Chhattisgarh 491 001 India

Email: yrkatre.chem@gmail.com

Received 11 February 2012; revised and accepted 23 May 2013

The kinetics of oxidation of L-arginine by N-bromophthalimide in the presence of HClO4 has been investigated in different media, viz., aqueous and micellar media of cetyltrimethylammonium bromide (CTAB) and
sodium dodecyl sulfate (SDS). The reaction is found to be dependent on substrate, [H+], CH3COOH and surfactant. The order of oxidation is found to be positive fractional order with respect to L-arginine and negative fractional order with respect to [H+]. Polarity of the medium also has an effect on the rate of reaction. Based on experimental findings, a mechanism has been proposed and discussed for the oxidation reaction. The micelles influence the rate of reaction significantly. Rate enhancement is observed in the presence of CTAB while an inhibiting effect is observed in the presence of SDS. These effects have been further analysed by means of the pseudo-phase models based on which the rate constant and binding constants have been evaluated.

Keywords: Kinetics, Micellar kinetics, Oxidation, N-Bromophthalimide, L-Arginine, Cetyltrimethylammonium bromide, Sodium dodecyl sulfate

Indian Journal of Chemistry

Vol. 52A, June 2013, pp. 739-743

 

 

Mechanochemical synthesis of sodium doped hydroxyapatite powder

 

Sharifah Adzilaa, c, Iis Sopyanb, *, Ramesh Singha, Erlani Pusparinid & Mohd. Hamdia

aDepartment of Engineering Design and Manufacture, Faculty of Engineering, University of Malaya,
50603 Kuala Lumpur, Malaysia

bDepartment of Manufacturing and Materials Engineering, Faculty of Engineering,
International Islamic University Malaysia, 50728 Kuala Lumpur, Malaysia

Email: sopyan@iium.edu.my

cDepartment of Materials Engineering and Design, Faculty of Mechanical and
Manufacturing Engineering, Universiti Tun Hussein Onn Malaysia, 86400 Johor, Malaysia

dState Ministry for Research and Technology Republic of Indonesia,
Jalan MH. Thamrin 8, Jakarta 10340, Indonesia

Received 30 November 2012; revised and accepted 10 May 2013

Bioactive hydroxyapatite (HA) with nanosized spherical shape has been synthesized through mechanochemical synthesis of calcium hydroxide and diammonium hydrogen phosphate. Sodium ion has been doped into HA by using sodium hydroxide precursor in a dry mixture of Ca(OH)2 and (NH3)2HPO4. Both Na-free HA and Na-doped HA (1%-9%) are characterized by X-ray diffraction and Fourier transform infrared analyses. Reduction of the peak intensity and adsorption bands is observed with increasing Na+ concentration in the Na-doped HA structure. Increasing Na+ content expands the lattice parameters and unit cell volume of HA, while the crystallite size and degree of crystallinity decrease with increasing Na+ level. A mixture of rods and spheres are found in the Na+ doped HA. Characterization of the obtained powder suggests that Na doped HA has a potential to be used in clinical applications.

Keywords: Bioceramics, Hydroxyapatites, Doping, Sodium doping, Calcium phosphate

 

Indian Journal of Chemistry

Vol. 52A, June 2013, pp. 744-748

 

 

Synthesis and properties of polypyrrole obtained from a new Fe (III) complex as oxidizing agent

 

Chepuri R K Rao*, , R Muthukannan, J Adriel Jebin, T Antony Raj & M Vijayan

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

Email: ramchepuri@gmail.com

Received 31 August 2012; revised and accepted 20 May 2013

A new complex is synthesized from FeCl3 and lauryl sulphate and used as oxidizing agent for the synthesis of polypyrrole. This process yields highly conducting polypyrrole (50 S/cm). The polymer is characterized by FT-IR, UV-vis, conductivity measurements and electrochemical and thermal analyses. Cyclic voltammetry of the polymer suggests moderate specific capacitance values.

Keywords: Polymers, Conducting Polymers, Polypyrrole, Conductivity, Oxidizing agents, Iron

 

 

 

Indian Journal of Chemistry

Vol. 52A, June 2013, pp. 749-752

 

 

Hydrothermal synthesis and characterization of bis(4,4′-bipyridinium) dodecatungstosilicate dihydrate

Rajarshi Chatterjeea, Dipak K Hazrab, Monika Mukherjeeb M Nethajic & Mahammad Ali a, *

aDepartment of Chemistry, Jadavpur University, Kolkata 700 032, India

Email: mali@chemistry.jdvu.ac.in

bDepartment of Solid State Physics, Indian Association for the Cultivation of Science,
Jadavpur, Kolkata 700 032, India

cDepartment of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India

Received 11 July 2012; re-revised and accepted 8 May 2013

Hydrothermal synthesis and structural characterization of a new organic polyoxometalate, namely,
bis(4,4′-bipyridinium) dodecatungstosilicate dihydrate, [4,4′-bipyH2]2[SiW12O40].2H2O (1) is reported. The crystal structure of (1) consists of a [SiW12O40]4- Keggin anion situated on a two-fold axis, two unique
4,4′-bipyridinium cations, one of which is situated on a two-fold axis, and two independent lattice water molecules. The cations and anions are linked by H-bonding.

Keywords: Hydrothermal synthesis, Organic polyoxometalates, Polyoxometalates, Dodecatungstosilicate, Tungsten