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 10

OCTOBER 2013

 

CONTENTS

 

 

Rapid Communication

 

 

 

1247

 

On trialkyl sulfonium salts of triiodomercury(II) and structure of the trimethyl salt

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Pradip Ghosh & Animesh Chakravorty*

 

 

 

In the array of trigonal planar [HgI3]- ions in the lattice of the salt [Me3S][HgI3] (formulation of P C Ry, 1930), the interionic (dotted lines) contacts have significant influence on bond parameters within the anion.

 

 

 

IC3804-GA2

 

 

 

Papers

 

 

 

1251

 

Spectroscopic and electrochemical monitoring on the binding of idarubicin as a chemotherapy drug with ds-DNA

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Reza Hajian* & Farkhondeh Panahi

 

 

 

The dominant interaction between idarubicin and DNA is electrostatic at low ionic strength and intercalative at high ionic strength.

 

 

 

 

GA

 

 

 

 

1257

 

Preparation and characterization of visible light-driven praseodymium-doped mesoporous titania coated magnetite photocatalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Xiaobo Liu, Jun Xing, Jingping Qiu* & Xiaogang Sun

 

 

 

Higher degradation of methyl orange has been achieved with praseodymium-doped mesoporous titania coated magnetite photocatalyst. The 0.30mol% Pr-doped catalyst shows the highest photocatalytic activity.

 

 

 

 

 

1263

 

Peroxidative oxidation of cycloalkane by di-, tetra- and polynuclear copper(II) complexes

 

 

 

 

 

 

 

 

Mahasweta Nandi & Partha Roy*

 

 

 

Di-, tetra- and polynuclear copper(II) complexes with N2O donor ligands are used as catalysts for the oxidation of cycloalkanes in the presence of hydrogen peroxide as the oxidant. The oxidized products are cycloalkanol and cycloalkanone.

 

 

 

 

 

 

1269

 

Controlled-release performance of chitosan-polyuronic acid adducts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Mahesh U Chhatbar, Ramavatar Meena,
Chirag B Godiya & A K Siddhanta
*

 

 

 

Controlled release performance of chitosan-polyuronic acid adducts is evaluated using five structurally different drugs. Paracetamol, indomethacine and isoniazid, all containing
-NH-CO- moieties, show the highest release rate at pH 1.2 and lowest at pH 7.4, while atenolol and pravastatin, having no
-NH-Co- moiety, show a reverse trend.

 

 

 

 

 

 

 

 

 

1275

 

Phase behavior and rheological properties of sodium
deoxycholate/sodium oleate mixed systems

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M Wang, Z N Wang*, X Liu, F M Guo, X B Ma,
X L Wei & W Zhou

 

 

 

Liquid crystals formed in NaDC/NaOL systems have a lamellar structure. With change in NaDC:NaOL ratio from 1:1 to 1:2 and 1:3, the bi-continuous cubic phase transforms into the plate lamellar phase.

 

 

 

 

 

 

1284

 

Cloud point and thermodynamic parameters of a
non-ionic surfactant heptaoxyethylene dodecyl ether (C12E7) in presence of various organic and inorganic additives

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

P Parekh*, Usha R Yerramilli & P Bahadur

 

 

 

Non-ionic surfactants show phase separation with increase in heat or in the presence of additives.

 

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

Indian Journal of Chemistry

Vol. 52A, October 2013, pp. 1247-1250

 

On trialkyl sulfonium salts of triiodomercury(II) and structure of
the trimethyl salt

Pradip Ghosh & Animesh Chakravorty*

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

Email: icac@iacs.res.in

Received 2 September 2013; accepted 16 September 2013

The salt, [Me3S][HgI3], is a text book example of the relatively rare phenomenon of tricoordination among transition metal complexes of simple ligands. It was structurally characterized decades after P C Rys formulation of the [R3S] [HgI3] family of salts in 1930. We now report its structure at low temperature (150 K). The [Me3S]+ and [HgI3]- ions are respectively pyramidal and trigonal planar. The span of the three Hg-I distances and the three I-Hg-I angles are 2.69-2.74 and 110-125o respectively. The Hg atom is 0.12 displaced from the plane of the iodine atoms. Weak supramolecular Hg---I interactions among adjacent molecules are present in the lattice and these influence the trend of bond lengths and angles in the [HgI3]- ion. The S-C distances and C-S-C angles in the cation span the ranges 1.75-1.81 and 100-103o respectively.

Keywords: Triiodomercuric ion, Mercury, Trimethyl sulfonium salt, Crystal structure, Tricoordination, Supramolecular interactions

 

Indian Journal of Chemistry

Vol. 52A, October 2013, pp. 1251-1256

 

Spectroscopic and electrochemical monitoring on the binding of idarubicin
as a chemotherapy drug with ds-DNA

Reza Hajiana, b, * & Farkhondeh Panahic

aInstitute of Advanced Technology, University Putra Malaysia, 43400 Serdang, Selangor, Malaysia

bYoung Researchers Club, Gachsaran Branch, Islamic Azad University, 75818-63876, Gachsaran, Iran

cDepartment of Chemistry, Gachsaran Branch, Islamic Azad University, 75818-63876, Gachsaran, Iran

Email: hajian@iaug.ac.ir

Received 01 April 2013; revised and accepted 18 September 2013

The interaction between idarubicin, a heterocyclic anticancer drug, and fish sperm DNA has been investigated in physiological buffer (pH 7.4) using methylene blue dye as a spectral probe by UVvis absorption, cyclic voltammetry, fluorescence spectroscopy, as well as viscosity measurements. The hypochromicity effect on the spectra of idarubicin in the presence of DNA with a partial red shift is observed. The results indicate that idarubicin molecule can bind to DNA and the major binding mode is intercalative binding in high ionic strength while the electrostatic binding is dominant in low ionic strength. The binding constants and the number of binding sites of idarubicin molecule with DNA are obtained by UV-vis spectrophotometry and fluorescence quenching methods. The thermodynamic parameters, ΔH, ΔS and ΔG are calculated as 1.95104 J mol-1, 1.52102 J mol-1 K-1 and
-2.51
104 J mol-1 respectively, showing that the binding of idarubicin to DNA is driven mainly by hydrophobic interaction. The diffusion coefficient for the free drug is found to be 2.610-3 cm2 s-1, whereas in the presence of DNA, it is 1.210-3 cm2 s-1.

Keywords: Idarubicin, Fish sperm DNA, Spectroscopy, Cyclic voltammetry, Fluorescence, Viscosity, Hypochromicity, DNA binding, Intercalative binding, Hydrophobic interaction

 

Indian Journal of Chemistry

Vol. 52A, October 2013, pp. 1257-1262

 

Preparation and characterization of visible light-driven praseodymium-doped mesoporous titania coated magnetite photocatalyst

Xiaobo Liu, Jun Xing, Jingping Qiu* & Xiaogang Sun

School of Resources & Civil Engineering, Northeastern University, Shenyang 110 819, China

Email: jpqiu1916@163.com

Received 27 December 2012; revised and accepted 29 August 2013

A visible light-driven magnetic composite photocatalyst, viz., (Pr/MTiO2/Fe3O4), has been prepared by coating photoactive praseodymium-doped mesoporous titania (Pr/MTiO2) onto magnetic Fe3O4 via hydrolysis of tetrabutyl titanate (Ti(OBu)4) with Pr(NO3)36H2O and Ti(OBu)4 as precursors in the presence of Fe3O4 particles. The photocatalytic activities of the obtained photocatalysts under visible light are estimated by measuring the degradation rate of methylene orange in aqueous solution. Results show that the prepared photocatalyst is activated by visible light and may be used as effective catalyst in photooxidation reactions. In addition, the possibility of cyclic usage of the prepared photocatalyst is also confirmed; ca. 88% of the photocatalytic activity of as-prepared Pr/MTiO2/Fe3O4 is retained after being used four times. Moreover, the photocatalyst can be easily recovered by application of external magnetic field and reused without any mass loss up to four cyclicity. The photocatalyst therefore may be potentially applied for the treatment of water contaminated by organic pollutants.

Keywords: Mesoporous titania, Titania, Magnetite, Praseodymium doping, Doped catalyst, Photocatalyst, Photocatalytic activity, Degradation, Dye degradation

 

Indian Journal of Chemistry

Vol. 52A, October 2013, pp. 1263-1268

 

Peroxidative oxidation of cycloalkane by di-, tetra- and polynuclear
copper(II) complexes

Mahasweta Nandia & Partha Royb, *

aIntegrated Science Education and Research Centre, Siksha Bhavana, Visva-Bharati University, Santiniketan 731 235, India

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

Email: proy@chemistry.jdvu.ac.in

Received 1 March 2013; revised and accepted 5 September 2013

Di-, tetra- and polynuclear copper(II) complexes with N2O donor system, [Cu2(L1)(μ2-pz)(CH3COO)2] (1), [Cu4(L1)24-O)(μ2-CH3COO)21,1-N3)(N3)] (2) and [Cu2(L2)(μ1,1-N3)(μ1,3-N3)2] (3) respectively (where pz = pyrazolato, HL1 = 2,6-bis(morpholinomethyl)-4-tert-butylphenol and HL2 = 2,6-bis(morpholinomethyl)-4-methylphenol) have been employed as catalysts for the peroxidative oxidation of cyclohexane and cycloheptane in the presence of hydrogen peroxide as the oxidant at room temperature and under atmospheric pressure. The oxidized products of cyclohexane are cyclohexanol and cyclohexanone, whereas cycloheptane is oxidized to cycloheptanol and cycloheptanone.

Keywords: Oxidation, Peroxidative oxidation, Reaction mechanism, Polynuclear complexes, Copper

 

Indian Journal of Chemistry

Vol. 52A, October 2013, pp. 1269-1274

 

Controlled-release performance of chitosan-polyuronic acid adducts

Mahesh U Chhatbara, Ramavatar Meenaa, b, Chirag B Godiyaa & A K Siddhantaa, b, *

 

aMarine Biotechnology and Ecology Discipline, CSIR-Central Salt & Marine Chemicals Research Institute,
GB Marg, Bhavnagar 364 002, Gujarat, India

bAcademy of Scientific & Innovative Research, Anusandhan Bhavan, 2 Rafi Marg, New Delhi 110 001, India

Email: aks@csmcri.org

Received 20 June 2013; revised and accepted 17 September 2013

Controlled release performance of chitosan-polyuronic acid (polymannuronic and polyguluronic acid) adducts, has been evaluated using five structurally different drugs, i.e., paracetamol (PCT), indomethacine (IND), isoniazid (INH), atenolol (ATN) and pravastatin (PST). The release rates of PCT, INH and ATN, all containing -NH-CO-moieties, show an inverse correlation with the change in pH, i.e., highest at pH 1.2 and lowest at pH 7.4. A reversed trend is noted with IND and PST, having no -NH-CO-moieties; the release rates are highest at pH 7.4 and lowest at pH 1.2. This appears to have a correlation with the structural features of the adducts and the drugs alike, containing -NH-CO-groups, manifesting pH-dependent preferential interactions of -NH-CO-groups through intermolecular hydrogen bonding facilitated at a higher pH. This study presents an array of biopolymer-based materials, which can be harnessed for delivering specific dosage schedules and would be of potential utility in pharmaceutical formulations.

Keywords: Polyuronic acid, Chitosan, Drug release studies, Polymannuronic acid, Polyguluronic acid, X-ray diffraction

 

Indian Journal of Chemistry

Vol. 52A, October 2013, pp. 1275-1283

 

Phase behavior and rheological properties of sodium deoxycholate/sodium oleate mixed systems

M Wanga, Z N Wanga, *, X Liua, F M Guoa, X B Maa, X L Weib & W Zhoua

 

aCollege of Chemistry, Chemical Engineering and Materials Science, Key Laboratory of Molecular and Nano Probes, Ministry of Education, Shandong Normal University, Jinan 250014, PR China

Email: zhongniw@hotmail.com

bCollege of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, PR China

Received 1 October 2012; revised and accepted 19 September 2013

The phase diagram and rheological measurements have been made for a series of sodium deoxycholate (NaDC)/sodium oleate (NaOL) mixed systems. At the NaDC/NaOL mass ratio of 1/2, a lamellar liquid crystal phase is found in NaDC/NaOL/Isopropyl myristate (IPM)/H2O system. At the surfactant/oil mass ratio of 9/1, with increasing water content, elastic G' and viscous G" modulus decrease. At the surfactant/water mass ratio of 6/4, with increase of IPM content, elastic G' and viscous G" modulus decrease. When the IPM is replaced by oleic acid, the lamellar liquid crystal region is smaller. The viscosity decreases with increase in the shear rate, but the samples exhibit a platform when the shear rate is between 1 and 50 s-1. Moreover, at a relatively high water or oil component content, the elastic G' and viscous G" modulus of the IPM system are higher than that of the oleic acid system. Further, it is found that for the IPM system at the NaDC/NaOL mass ratio of 1/3, the lamellar liquid crystal phase still exists, but the elastic G' and viscous G" modulus are smaller in comparation with that for NaDC/NaOL mass ratio of 1/2. In the NaDC/NaOL system with mass ratio of 1/1, there is a bi-continuous cubic phase, while the lamellar liquid crystal phase disappears. Interestingly, the values of elastic G' and viscous G" modulus of the cubic phase are in between those of the NaDC/NaOL (1/2) and NaDC/NaOL (1/3) systems.

Keywords: Phase behavior, Rheological properties, Lamellar liquid crystals, Liquid crystals, Sodium deoxycholate

 

Indian Journal of Chemistry

Vol. 52A, October 2013, pp. 1284-1290

 

Cloud point and thermodynamic parameters of a non-ionic surfactant
heptaoxyethylene dodecyl ether (C12E7) in presence of various organic
and inorganic additives

P Parekh*, Usha R Yerramilli & P Bahadur

 

Department of Chemistry, Veer Narmad South Gujarat University, Surat 395 007, India

Email: paresh7884@gmail.com

Received 28 March 2013; revised and accepted 10 September 2013

Cloud points (CPs) of heptaoxyethylene dodecyl ether (C12E7) in the presence of varying concentrations of additives such as inorganic salts, alkanols, diols, glycols and their ethers, hydroptopes and short chain tetraalkylammonium salts are measured and the increase/decrease in CP is discussed. While inorganic anions decrease the CP due to the salting out (dehydration) effect and follow the Hofmeister series, an increase in CP by CNS- and I- ions is governed by the salting in effect. Short chain alcohols (< C4), diols (< C6) and ethylene glycol ethers, diethylene glycol, propylene glycol, dipropylene glycol (< C4) increase the CP whereas a decrease is seen in the case of higher homologues. This increasing/decreasing effect of alcohols and diols and their monoalkyl ethers is ascribed to their function as a cosolvent/cosurfactant for C12E7 micellar systems. Both hydrotropes and short chain tetraalkylammonium salts increased CP of C12E7 to 100 C at very low concentration. The thermodynamic parameters of these mixtures are also calculated at varying additive concentrations. As the solubility of non-ionic surfactant containing heptapolyoxyethylene hydrophilic chain is highest at the cloud point, the thermodynamic parameters are calculated at this temperature. The results show that the standard Gibbs free energy change (), the enthalpy () and the entropy () at the cloud point are positive or negative depending on the nature of the additives.

Keywords: Surfactants, Non-ionic surfactants, Thermodynamic parameters, Cloud point, Additives, Heptaoxyethylene dodecyl ether