Indian Journal of Chemistry

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

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

 

 

VOLUME 52A

NUMBER 12

DECEMBER 2013

 

CONTENTS

 

 

1557

 

Facile synthesis of highly dispersed PtSn nanoparticles on carbon nanotubes with excellent ethanol electrooxidation performance

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Bohua Wu*, Ming Gong, Jia Chu, Xiaoqin Wang & Shanxin Xiong

 

 

 

Highly dispersed PtSn nanoparticles on carbon nanotubes surface obtained by the ionic liquid polymer method show improved electrochemical performance for ethanol oxidation.

 

 

 

 

 

1564

 

Solvent-free synthesis of jasminaldehyde using double metal cyanide based solid acid catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Mallikarjun V Patil, Sumeet K Sharma &
Raksh V Jasra
*

 

 

 

Solvent-free synthesis of jasminaldehyde using Fe-Zn double metal cyanide catalysts is reported. In presence of the catalyst prepared with tert-butanol as complexing agent, 93% conversion of 1-heptanal with 77% selectivity to jasminaldehyde is achieved.

 

 

 

 

1570

 

Mechanochemical synthesis of nanohydroxyapatite bioceramics

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sharifah Adzila, Iis Sopyan, Tan Chou Yong,
Ramesh Singh*, Wong Yew Hoong, J Purbolaksono
& Mohd. Hamdi

 

 

 

Nanosized hydroxyapatite powder is synthesized by mechanochemical method using a dry mixture of calcium hydroxide and diammonium hydrogen phosphate. Increase in rotation speed (370 rpm) increases the crystallite size (9-21 nm). At 370 rpm, the sample sintered at 1250 °C shows the maximum relative density of 95.3% as well as hardness of 5.3 GPa.

 

 

 

 

 

1576

 

DNA binding and cleavage activity of a structurally characterized oxobridged diiron(III) complex

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Bhaskar Biswas, Merry Mitra, Abhijit Pal,
Anirban Basu,
Subramaniyam Rajalakshmi, Partha Mitra, Nuria Aliaga-Alcalde, Gopinatha Suresh Kumar, Balachandran Unni Nair* & Rajarshi Ghosh*

 

 

 

Synthesis, crystal structure and variable temperature magnetic measurement of an oxobridged dinuclear Fe(III) complex [Fe2O(phen)4Cl2](NO3)2 is reported. Spectroscopic and viscosity investigations reveal a mixed mode involving groove binding along with partial intercalative interaction of the Fe(III) complex with CT-DNA. The complex is found to induce oxidative cleavage of the DNA from its supercoiled form to both nicked circular and linear forms in a concentration-dependent manner.

 

 

 

 

1584

 

Kinetics and mechanism of (salen)MnIII catalyzed oxidation of methyl phenyl sulfides with sodium metaperiodate

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Arunachalam Chellamani* & Ramasamy Subramanian

 

 

 

Mechanistic studies of (salen)MnIII complexes catalyzed oxidation of aryl methyl sulfides with NaIO4 have been carried out. The reaction follows an SN2 mechanism.

 

 

 

 

 

Notes

 

1591

 

Solvothermal synthesis and characterization of zinc sulphide nanoparticles

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Deepti Mishra, Priyanka Prabhakar, Swati Lahiri,
S S Amritphale * & Navin Chandra

 

 

Phase pure zinc sulphide nanoparticles have been synthesized by solvothermal approach and characterized by XRD, FESEM, EDX, TEM, IR, TGA and DSC techniques.

 

 

 

 

1595

 

Annual Index

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

Indian Journal of Chemistry

Vol. 52A, December 2013, pp. 1557-1563

 

Facile synthesis of highly dispersed PtSn nanoparticles on carbon nanotubes
with excellent e
thanol electrooxidation performance

Bohua Wua, *, Ming Gonga, Jia Chua, Xiaoqin Wanga & Shanxin Xionga, b

aCollege of Chemistry and Chemical Engineering, Xi’an University of Science & Technology, Xi'an, 710054, PR China

Email:wubohua2005@126.com

bState Key Laboratory of Polymer Materials Engineering, Sichuan University, Chengdu, 610065, PR China

Received 4 April 2013; revised and accepted 18 November 2013

Stable and uniform PtSn nanoparticles on the surface of carbon nanotubes with ultrafine particle sizes have been prepared via the ionic liquid polymer method. Morphology and electrochemical properties of the PtSn nanoparticles supported on the ionic liquid (IL) polymer-functionalized carbon nanotubes (PtSn/CNTs-f nanohybrids) have been investigated by transmission electron microscopy and cyclic voltammetry. The average diameter of PtSn nanoparticles in the PtSn/CNTs-f nanohybrids is 1.6±0.5 nm, which is much smaller than that deposited on pristine carbon nanotubes (PtSn/CNTs-p nanohybrids, 6±2 nm). The electrochemical active surface area (ESA) of the PtSn/CNTs-f nanohybrids
is about twice as high as that of the PtSn/CNTs-p nanohybrids. In comparison to the PtSn/CNTs-p nanohybrids, PtSn/CNTs-f nanohybrids exhibit unexpectedly high activity and stability towards ethanol electrooxidation which may be attributed to the higher dispersion, smaller particle size and higher ESA of the PtSn nanoparticles on the IL polymer functionalized CNTs material. The results indicate that PtSn/CNTs-f nanohybrids are promising anodic electrocatalyst for direct ethanol fuel cells.

Keywords: Nanoparticles, Electrocatalysts, Carbon nanotubes, Electrooxidation, Ionic liquid polymer method, Fuel cells, Platinum, Ethanol, Tin

 

Indian Journal of Chemistry

Vol. 52A, December 2013, pp. 1564-1569

 

Solvent-free synthesis of jasminaldehyde using double metal cyanide based
solid acid catalysts

Mallikarjun V Patil, Sumeet K Sharma, Raksh V Jasra, *

Discipline of Inorganic Materials and Catalysis, CSIR-Central Salt and Marine Chemicals Research Institute (CSMCRI),
GB Marg, Bhavnagar, 364 021, Gujarat, India

Email: rakshvir.jasra@ril.com (RVJ)/ sumeetsharma036@gmail.com (SKS)

Received 12 July 2013; revised and accepted 14 November 2013

The catalytic activity of Fe-Zn double metal cyanide catalysts is studied for the solvent-free synthesis of jasminaldehyde by liquid phase condensation of benzaldehyde and 1-heptanal at 433 K. The highest conversion of
1-heptanal (93%) with 77% selectivity to jasminaldehyde is achieved under the optimum reaction conditions. The presence of co-ordinatively unsaturated Zn2+ in the structural framework of Fe-Zn double metal cyanide assists the condensation reaction. The effects of complexing and co-complexing agent, amount of catalyst, benzaldehyde to
1-heptanal molar ratio and temperature on the selectivity of jasminaldehyde is reported.

Keywords: Catalysts, Double metal cyanide, Jasminaldehyde, Heptanal, Benzaldehyde, Solid acid catalyst, Aldol condensation

 

Indian Journal of Chemistry

Vol. 52A, December 2013, pp. 1570-1575

 

Mechanochemical synthesis of nanohydroxyapatite bioceramics

Sharifah Adzilaa, b, Iis Sopyanc, Tan Chou Yonga, Ramesh Singha, *, Wong Yew Hoonga, J Purbolaksonoa & Mohd. Hamdia

aCentre of Advanced Manufacturing and Material Processing, Department of Mechanical Engineering, Faculty of Engineering,
University of Malaya, 50603 Kuala Lumpur, Malaysia

Email: ramesh79@um.edu.my

bDepartment of Materials Engineering and Design, Faculty of Mechanical and Manufacturing Engineering,
University of Tun Hussein Onn Malaysia, 86400 Johor, Malaysia

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

Received 12 April 2013; revised and accepted 19 November 2013

Nanosized hydroxyapatite powder has been synthesized by the mechanochemical method using a dry mixture of calcium hydroxide and diammonium hydrogen phosphate. The effect of mechanochemical process on powder properties has been investigated. Three rotation speeds of 170 rpm, 270 rpm and 370 rpm have been employed with
15 hours milling time. Characterization of the nanopowders has been accomplished by Fourier transform infra red, X-ray diffraction and transmission electron microscopy analyses. The samples have been prepared and sintered in air at varying temperatures ranging from 1050–1350
°C. Results show that increase in rotation speed (370 rpm) increases the crystallite size (9–21 nm). Agglomerate formation with irregular shapes is found in the samples prepared at 270 and 370 rpm. The sintering process influences the stability of powder by yielding TCP phase at all the sintering temperatures. At 370 rpm, the sample sintered at 1250 °C shows the maximum relative density of 95.3% as well as hardness of 5.3 GPa.

Keywords: Mechanochemical synthesis, Nanomaterials, Hydroxyapatite, Bioceramics

 

Indian Journal of Chemistry

Vol. 52A, December 2013, pp. 1576-1583

 

DNA binding and cleavage activity of a structurally characterized
oxobridged diiron(III) complex

Bhaskar Biswasa, †, Merry Mitraa, Abhijit Pala, Anirban Basub, Subramaniyam Rajalakshmic, Partha Mitrad,
Nuria Aliaga-Alcaldee, Gopinatha Suresh Kumarb,
Balachandran Unni Nairc, * & Rajarshi Ghosha, *

aDepartment of Chemistry, The University of Burdwan, Burdwan 713 104, India

bBiophysical Chemistry Laboratory, Chemistry Division, CSIR-Indian Institute of Chemical Biology, Kolkata 700 032

cChemical Laboratory, Central Leather Research Institute, Council of Scientific and Industrial Research, Adyar, Chennai 600 020, India

dDepartment of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India

eICREA & Departament de Química Inorgànica, Universitat de Barcelona, Diagonal, 647, 08028 Barcelona, Spain

Email: bunair@clri.res.in (BUN)/ rajarshi_chem@yahoo.co.in (RG)

Received 1 January 2013; revised and accepted 12 November 2013

The synthesis, crystal structure and variable temperature magnetic measurement of an oxobridged dinuclear Fe(III) complex [Fe2O(phen)4Cl2](NO3)2 (1) [phen =1,10-phenanthroline] is reported. From X-ray diffractometry, it is shown that each Fe(III) in the compound is in distorted octahedral environment. Variable temperature magnetic study reveals strong antiferromagnetic behaviour of (1) with = –104±2 cm-1, p = 0.8% and TIP = 280×10-6 cm-1, fixing g = 2.00. The binding property of the complex with calf thymus DNA has been investigated using absorption and emission studies, circular dichroism spectral investigations, thermal melting and viscosity experiments. The binding constant and the linear Stern-Volmer quenching constant of the complex have been determined to be 1.49×103 M-1 (R = 0.99922 for five points) and 2.02×103 (R = 0.99917 for five points), respectively. Spectroscopic and hydrodynamic investigations reveal a mixed mode involving groove binding along with partial intercalative interaction of (1) with CT-DNA. (1) is found to induce oxidative cleavage of the DNA from its supercoiled to both nicked circular and linear forms in a concentration-dependent manner.

Keywords: Coordination chemistry, Iron, Dinuclear compounds, Oxobridged diiron(III) complex, Crystal structure,
DNA binding, DNA cleavage

 

Indian Journal of Chemistry

Vol. 52A, December 2013, pp. 1584-1590

 

Kinetics and mechanism of (salen)MnIII catalyzed oxidation of
methyl phenyl sulfides with sodium metaperiodate

Arunachalam Chellamani* & Ramasamy Subramanian

Department of Chemistry, Manonmaniam Sundaranar University, Tirunelveli 627 012, India

Email: achellamani@yahoo.co.in

Received 16 November 2012; revised and accepted 8 October 2013

The kinetics of (salen)MnIII complexes-catalyzed oxidation of phenyl methyl sulfides with periodate in 90%
acetonitrile-10% water (v/v) mixture at 20 °C has been studied spectrophotometrically. The oxidation follows an overall second order kinetics, first order each in sulfide and oxo(salen)manganese(V) complex. Electron-releasing substituents
in the phenyl ring accelerate the rate, whereas electron-withdrawing substituents produce the opposite effect. The log k2 values show better correlation with
sp (r = –1.84 ± 0.06, r = 0.998) than with s+/s(r = –0.976 ± 0.08, r = 0.979).
Electron-releasing substituents at the 5,5
¢-positions of the salen ligand decrease the rate while the electron-withdrawing substituents enhance the rate of oxidation. Substituent, acid and solvent effect studies reveal an SN2 mechanism for the oxidation of aryl methyl sulfides with periodate catalyzed by (salen)MnIII complexes.

Keywords: Kinetics, Reaction mechanisms, Organic sulfides, Sodium metaperiodate, Manganese, Salen

 

Indian Journal of Chemistry

Vol. 52A, December, 2013, pp. 1591-1594

 

Solvothermal synthesis and characterization of zinc sulphide nanoparticles

Deepti Mishra, Priyanka Prabhakar, Swati Lahiri, S S Amritphale* & Navin Chandra

Materials From Wastes, Nanomaterials & Interdisciplinary Studies Division, CSIR-Advanced Materials and Processes
Research Institute, Hoshangabad Road, Bhopal 462 064, India

Email: ssamritphalerrl@yahoo.co.in

Received 12 February 2013; revised and accepted 18 November 2013

Zinc sulphide nanoparticles have been synthesized by solvothermal approach involving refluxing of an aqueous solution of zinc acetate and sodium sulphide in presence of ethylene glycol and cetyl trimethyl ammonium bromide as surfactant. The nanoparticles have been characterized by X-ray diffraction, Fourier transform infrared spectroscopy, field emission scanning electron microscopy, energy-dispersive X-ray spectroscopy, differential scanning calorimetry, thermogravimetric analysis, ultraviolet-visible spectroscopy and transmission electron microscopy. The FESEM results indicate that the particles are almost spherical in shape with size varying in the range of 27.7–49.5 nm, whereas TEM micrograph indicates formation of particles of size in the range of 5–8 nm. EDX spectrum reveals the predominance of carbon, zinc, oxygen and sulphur.

Keywords: Zinc sulphide, Nanoparticles, Solvothermal method