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 54A

NUMBER 2

FEBRUARY 2015

 

CONTENTS

 

 

155

 

Hydrothermal synthesis and LPG sensing ability of SnS nanomaterial

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

A Muthuvinayagam & B Viswanathan*

 

 

SnS nanoparticles with high crystallinity have been prepared
by hydrothermal method
with good control over particle size.
The prepared nanomaterial shows good gas sensing response for liquefied petroleum gas at low operating temperatures.

 

 

 

 

161

 

New tertiary phosphine derivatives of Os3(CO)12:
X-ray structures of 1,2-[Os3(CO)10-{PhP(o-Tol)2}2],
1,2,3-[Os3(CO)9{(4-FC6H4)3P}3], 1,2,3-[Os3(CO)9{PhP(Cy)2}3] and [Os3(µ-OH)2(CO)8{(4-FC6H4)3P}2]

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Abdur R Miah, Subas Rajbangshi, Ahibur Rahaman, Kamal Hossain, Tasneem A Siddiquee &
Shariff E Kabir
*

 

 

 

Di- and tri-substituted compounds, 1,2-[Os3(CO)10(PR3)2] and 1,2,3-[Os3(CO)9(PR3)3], along with the dihydroxyl-bridged complexes, 1,2-[Os3(CO)8(PR3)2(µ-OH)2] {PR3 = (4-FC6H4)3P, PhP(o-Tol)2 and PhP(Cy)2}, are obtained from the reactions of 1,2-[Os3(CO)10(NCMe)2] with PR3.

 

 

 

 

170

 

Synthesis, crystal structure, catecholase activity,
DNA cleavage and anticancer activity of a dinuclear manganese(III)-bipyridine complex

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Dhananjay Dey, Abhranil De, Sukanta Pal,
Partha Mitra,
Anandan Ranjani,
Loganathan Gayathri,
Saravanan Chandraleka, Dharumadurai Dhanasekaran, Mohammad Abdulkadhar Akbarsha, Niranjan Kole & Bhaskar Biswas
*

 

 

 

X-ray crystallographically characterized dinuclear acetate-oxo-bridged Mn(III) complex has been evaluated as model system for the catechol oxidase enzyme by using 3,5-di-tert-butylcatechol as the substrate in methanol medium. The complex cleaves the
pBR 322 supercoiled DNA without addition of an activating agent. Anticancer activity on human hepatocarcinoma cell line shows the efficacy of the complex to induce 55% of apoptotic for 24 h.

 

 

 

179

 

Polarizable continuum model solvation analysis of some isatin derivatives

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

P Vidhya, V Kannappan* & V Sathyanarayanamoorthi

 

 

 

Polarizable continuum model analysis has been carried out for
5-chloroisatin, 5-methylisatin and 5-methoxyisatin in ten solvents at 298 K. The electrostatic, dispersion and repulsion interaction components of Gibb’s free energy of solution along with cavitation energies and induced dipole moments are computed.

 

 

 

 

 

Notes

 

187

 

Electrochemical behavior of ascorbic acid and rutin on poly(L-arginine)-graphene oxide modified electrode

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yan Luo, Qingqing Hu, Gen Liu* & Dengming Sun*

 

 

 

Compared with graphene oxide modified electrode (GO/GCE) and bare GCE, poly(L-arginine)-graphene oxide modified electrode (PLA-GO/GCE) has high electrocatalytic ability for ascorbic acid (AA) and rutin.

 

 

 

 

193

 

Model-free thermal degradation kinetics of bio-based phenolic resin derived from vanillin oxime

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Narendra Pal Singh Chauhan*,
Nirmala Kumari Jangid, Jyoti Chaudhary,
Ritu Tomar & Paridhi Kataria

 

 

 

A new terpolymer resin is synthesized with the monomer vanillin oxime and p–bromoacetophenone and formaldehyde as a condensing agent and characterized by FTIR, 1H NMR, GPC, DSC and TG-DTG data. The apparent activation energy values for different conversions (0.1≤α≤0.7) are close to each other. The solid state decomposition mechanism is three dimensional deceleration type.

 

 

image description

 

 

199

 

Hydroisomerization of long chain saturated hydrocarbon over Pt/SiO2-Al2O3 catalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

J K Satyarthi, T Chiranjeevi*, Sudha Tyagi &
D T Gokak

 

 

 

Hydroisomerization of hexadecane and the linear saturated hydrocarbon product obtained from the hydroprocessing of jatropha oil have been carried out over different silica-alumina supported platinum catalysts for the reduction of pour point. The 0.3% Pt and amorphous silica-alumina support with SiO2/Al2O3 ratio as 0.67 is found to be optimum.  Under the optimized conditions for hexadecane, pour point as low as –15 °C and
–10 °C has been obtained for the batch as well as continuous fixed bed reactor respectively, along with good conversion and selectivity.

 

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203

 

 

Corrigendum

 

 

 

 

204

 

 

Author Guidelines for Online Submission

 

 

 

 

 

Authors for correspondence are indicated by (*)

Indian Journal of Chemistry

Vol. 54A, February 2015, pp. 155-160

 

 

Hydrothermal synthesis and LPG sensing ability of SnS nanomaterial

A Muthuvinayagama & B Viswanathanb, *

aDepartment of Physics, National Institute of Technology, Calicut 673 601, India

bNCCR, Indian Institute of Technology Madras, Chennai 600 036, India

Email: bvnathan@iitm.ac.in

Received 19 December 2014; accepted 29 January 2015

The preparation of nanoparticles of tin sulfide is reported employing the hydrothermal method. The X-ray diffraction results of tin sulfide nanopowder confirm its orthorhombic crystalline structure. Transmission electron micrographs show that the as-prepared SnS nanoparticles are spherical in shape with the average size of 3-5 nm. Control over the particle size and size distribution have been achieved by optimizing the experimental parameters such as precursor concentration, water concentration, reaction time and temperature. The scanning electron micrographs suggest the presence of spherical aggregates of smaller as well as larger sizes. Thermal stability of these nanoparticles is investigated by thermogravimetric analysis and differential scanning calorimetry. The prepared nanomaterial shows good gas sensing response for liquefied petroleum gas at low operating temperatures. The high crystallinity and control over the particle size make the as-synthesized SnS an ideal candidate for LPG sensing.

Keywords: Nanoparticles, Semiconductors, Gas sensors; Hydrothermal method, Tin sulphide

 

Indian Journal of Chemistry

Vol. 54A, February 2015, pp. 161-169

 

 

New tertiary phosphine derivatives of Os3(CO)12: X-ray structures of
1,2-[Os3(CO)10{PhP(o-Tol)2}2], 1,2,3-[Os3(CO)9{(4-FC6H4)3P}3],
1,2,3-[Os3(CO)9{PhP(Cy)2}3] and [Os3(µ-OH)2(CO)8{(4-FC6H4)3P}2]

Abdur R Miaha, Subas Rajbangshia, Ahibur Rahamana, Kamal Hossaina,
Tasneem A Siddiqueeb & Shariff E Kabira, *

aDepartment of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh

Email: skabir_ju@yahoo.com

bDepartment of Chemistry, Tennessee State University, 3500 John A Merritt Blvd, Nashville, TN 37209, USA

Received 3 November 2014; revised and accepted 12 January 2015

Reactions of 1,2-[Os3(CO)10(NCMe)2] (1) with tertiary phosphines such as tris(4-fluorophenyl)phosphine
(4-FC6H4)3P, bis(o-tolyl)(phenyl)phosphine PhP(o-Tol)2 and dicyclohexyl(phenyl)phosphine PhP(Cy)2 have been examined at room temperature and found to yield the di- and tri-substituted products 1,2-[Os3(CO)10(PR3)2] {(2), PR3 = (4-FC6H4)3P; (3), PR3 = PhP(o-Tol)2; (4), PR3 = PhP(Cy)2} and 1,2,3-[Os3(CO)9(PR3)3] {(5), PR3 =
(4-FC6H4)3P; (6), PR3 = PhP(o-Tol)2; 7, PR3 = PhP(Cy)2} as the major products, in addition to the dihydroxyl-bridged complexes 1,2-[Os3(CO)8(PR3)2(µ-OH)2] {(8), PR3 = (4-FC6H4)3P; (9), PR3 = PhP(o-Tol)2; (10), PR3 = PhP(Cy)2} in trace amounts. Compounds (2)-(10) have been characterized by a combination of elemental analyses, infrared, NMR and mass spectral data together with single crystal X-ray diffraction studies for (3), (5), (7) and (8).

Keywords: Coordination chemistry, Osmium, Cluster compounds, Tertiary phosphines, X-ray structures

Indian Journal of Chemistry

Vol. 54A, February 2015, pp. 170-178

 

 

Synthesis, crystal structure, catecholase activity, DNA cleavage and anticancer activity of a dinuclear manganese(III)-bipyridine complex

Dhananjay Deya, Abhranil Dea, Sukanta Pala, Partha Mitrab, Anandan Ranjanic, Loganathan Gayathric,
Saravanan Chandralekad, Dharumadurai Dhanasekaranc, Mohammad Abdulkadhar Akbarshae,
Niranjan Kolea & Bhaskar Biswasa, *

aDepartment of Chemistry, Raghunathpur College, Purulia 723 133, India

Email: mr.bbiswas@rediffmail.com/ icbbiswas@gmail.com

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

cDepartment of Microbiology, Bharathidasan University, Tiruchirappalli 620 024, India

dDepartment of Chemistry, Urumu Dhanalakshmi College, Tiruchirappalli 620 019, India

eMahatma Gandhi-Doerenkamp Center, Bharathidasan University, Tiruchirappalli 620 024, India

Received 23 April 2014, revised and accepted 19 January 2015

Design and synthesis of a dinuclear manganese(III) complex [Mn2(µ-O)(μ-O2CMe)2(H2O)2(2,2'-bipy)2](NO3)2.5H2O (1) [2,2'-bipy = 2,2'-bipyridine] with mono-m-oxo and di-m-acetato bridge has been reported. Single crystal X-ray diffraction study reveals that (1) crystallizes in monoclinic system with P21/n space group. Evaluation of (1) as a model system for the catechol oxidase enzyme by using 3,5-di-tert-butylcatechol (DTBC) as the substrate in methanol medium, reveals that the complex exhibits efficient catalytic activity with kcat value of 8.89×102. (1) cleaves the pBR 322 DNA without addition of an activating agent. Further, the anticancer activity of (1) on human hepatocarcinoma cell line (HepG2) has been examined. The apoptosis in the cell line has been assessed by the changes in cell morphology, which shows the efficacy of (1) to induce 55% of apoptotic for 24 h. Interestingly, the observed IC50 values reveal that (1) effects conformational change on DNA strongly and exhibits remarkable cytotoxicity.

Keywords: Coordination chemistry, Manganese, X-ray structure, Catecholase activity, DNA cleavage,
Anticancer activity

 

Indian Journal of Chemistry

Vol. 54A, February 2015, pp. 179-186

 

 

Polarizable continuum model solvation analysis of some
isatin derivatives

P Vidhyaa, V Kannappanb, * & V Sathyanarayanamoorthic

aResearch and Development Centre, Bharathiar University, Coimbatore 641 046, India

bPG and Research Department of Chemistry, Presidency College, Chennai 600 005, India
Email: vkannappan48@gmail.com

cPG and Research Department of Physics, PSG College of Arts and Science, Coimbatore 641 014, India

Received 7 October 2014; revised and accepted 27 January 2015

Polarizable continuum model analysis has been carried out for 5-chloroisatin, 5-methylisatin and
5-methoxyisatin in ten solvents with a wide range of dielectric constants and at 298 K. The electrostatic, dispersion and repulsive interaction components of Gibb’s free energy of solution along with cavitation energies for these systems are computed by the B3LYP method with 6-311++G(d,p) basis set. The induced dipole moments of these compounds are also calculated for the three isatin derivatives in the studied solvents. The thermodynamic properties of the systems are discussed in terms of physical properties such as dielectric constant, index of refraction and surface tension of the solvents. The influence of substituent at 5-position on the solubility of biologically and industrially important isatin molecule is investigated.

Keywords:   Polarizable continuum model analysis, Isatin, Substituent effect, Substituted isatin,
Electrostatic interaction, Dispersive interaction, Repulsive interaction, Cavitation energy, Free energy

 

Indian Journal of Chemistry

Vol. 53A, February 2015, pp. 187-192

 

 

Electrochemical behavior of ascorbic acid and rutin on poly(L-arginine)-
graphene oxide modified electrode

Yan Luo, Qingqing Hu, Gen Liu* & Dengming Sun*

School of Chemistry and Materials Science, Huaibei Normal University, Huaibei 235000, PR China

Email: liugen7084@126.com; sundengming@126.com

Received 8 December 2014; revised and accepted 24 January 2015

The electrochemical behavior of ascorbic acid and rutin using a poly(L-arginine)-graphene oxide modified glassy carbon electrode (PLA-GO/GCE) has been studied by cyclic voltammetry and chronoamperometry. The modified electrode succeeds in distinguishing the electrochemical responses of ascorbic acid and rutin in a mixture solution due to its high electron transfer rate and good catalytic ability. The number of electrons involved in the reaction of ascorbic acid and rutin are calculated to be 1.994 and 1.968, respectively. The redox reaction of rutin is mainly an adsorption controlled process and the oxidation of ascorbic acid is a diffusion controlled process in pH 2.0 phosphate buffer. The diffusion coefficient of ascorbic acid is found to be 3.003×10-6 cm2 s-1. In the case of rutin, the surface coverage concentration is 6.17×10-9 mol cm-2, and the electron transfer coefficient is 0.51, while the rate constant of electrode reaction is 0.967 s-1. The PLA-GO/GCE electrode is of high sensitivity and selectivity, and has been successfully applied for simultaneous determination of ascorbic acid and rutin.

Keywords: Electrochemistry, Electrodes, Modified electrodes, Graphene, Graphene oxide, L-Arginine,
Ascorbic acid, Rutin

 

Indian Journal of Chemistry

Vol. 54A, February 2015, pp. 193-198

 

 

Model-free thermal degradation kinetics of bio-based phenolic resin
derived from vanillin oxime

Narendra Pal Singh Chauhana, *, Nirmala Kumari Jangidb, Jyoti Chaudharyc, Ritu Tomara & Paridhi Katariac

aDepartment of Chemistry, Bhupal  Nobles Post Graduate College, Udaipur 313 001, Rajasthan, India

Email: narendrapalsingh14@gmail.com/ rajveerchauhan14@gmail.com

bDepartment of Chemistry, University College of Science, Mohan Lal Sukhadia University,
Udaipur 313 001, Rajasthan, India

cDepartment of Polymer Science, University College of Science, Mohan Lal Sukhadia University,
Udaipur 313 001, Rajasthan, India

Received 4 June 2014; re-revised and accepted 28 January 2015

A new terpolymer resin is synthesized from vanillin oxime and p-bromoacetophenone with formaldehyde by solution condensation technique in the presence of an acid. The structure of the terpolymer resin is confirmed by IR and NMR spectroscopy. The average molecular weight and the polydispersity index for the terpolymer are found to be 12,852 g/mol and 2.65 as calculated by gel permeation chromatography. The phase transition temperature (102-214 °C) has been determined by differential scanning calorimetry (DSC).  Thermal degradation characterstics and kinetic parameters such as activation energy are investigated by TG-DTG. The apparent activation energy of terpolymer resin using Kissinger-Akahira-Sunose, and Friedman methods are 10.2 and 10.8 kJ mol1, respectively. The most likely solid state decomposition process is D3 deceleration type as shown by Craido method and master plots.

Keywords: Resins, Terpolymer resins, Phenolic resins, Vanillin, Oximes, Decomposition, Degradation,
Model-free kinetics, Solid state mechanism

 

Indian Journal of Chemistry

Vol. 54A, February 2015, pp. 199-202

 

 

Hydroisomerization of long chain saturated hydrocarbon
over Pt/SiO2-Al2O3 catalysts

J K Satyarthi, T Chiranjeevi*, Sudha Tyagi & DT Gokak

Corporate R&D Centre, Bharat Petroleum Corporation Ltd., Greater Noida 201 301, UP, India

Email: chiranjeevit@bharatpetroleum.in

Received 11 August 2014; revised and accepted 2 February 2015

Hydroisomerization of hexadecane and the products obtained from hydroprocessing of jatropha oil has been carried out over different silica-alumina supported Platinum catalysts for the reduction of pour point. Amorphous silica-alumina support is found to be suitable for the required conversion and selectivity. Optimum reaction conditions such as platinum loading, silica-alumina ratio and various reaction conditions have been determined.

Keywords: Isomerization, Hexadecane, Pour point, Platinum, Silica-alumina support