Indian Journal of Chemistry

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

 

VOLUME 46A

NUMBER 2

February 2007

 

CONTENTS

 

 

227

 

Ternary iron(II) complexes of phenanthroline bases showing DNA binding and cleavage activity

 

 

 

 

  

 

 

 

Mithun Roy, Ashis K Patra, Arindam Mukherjee, Munirathinam Nethaji & Akhil R Chakravarty*

 

 

 

The synthesis, structure, DNA binding and cleavage activity of three new ternary complexes [FeII(L1)B](PF6)2 containing a tetradentate ligand (L1) and planar phenanthroline bases (B) are described. The dipyridoquinoxaline and dipyridophenazine complexes show photonuclease activity at 365 nm by
1O2 pathway.

 

 

238

 

QSAR modeling of thalidomide analogs as antiangiogenic and prostate cancer inhibitor using AM1 calculations

 

 

 

 

 

Monica Dua, S Revathi, Love Kumar Soni,
Arun Kumar Gupta & S G Kaskhedikar*

 

 

 

 

 

QSAR studies have been carried out on thalidomide analogues acting as dual inhibitors of angiogenesis and prostrate cancer using a combination of various electronic, thermodynamic and spatial descriptors. QSAR studies show that the presence of fluorine atom is essential for both activities. LUMO and partition coefficient play a significant role in antiangiogenic activity while repulsive energy and molar refractivity contribute to anticancer activity. The correlation of inhibitory activity with charge density at 6th, 8th and 16th position of template implies electronic interaction of the molecule with receptor site.

 

 

247

 

Synthesis, spectral studies, thermal decomposition kinetics, reactivity and antibacterial activity of some lanthanide(III) nitrate complexes of 2-(N-indole-2-one)amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo-[b]thiophene

 

 

 

 

 

 

 

 

 

 

 

M Thankamony & K Mohanan*

 

 

 

 

252

 

Investigation of molecular interactions in ternary liquid mixtures using ultrasonic velocity

 

 

 

 

 

R Palani* & K Meenakshi

 

 

 

Ultrasonic velocity, density and viscosity measurements have been carried out in three ternary liquid mixtures of benzene, toluene and CCl4 with ethane 1,2 diol in a polar component of acetone at 303 K. The study shows that weak molecular interactions exist in the mixtures which may be due to the dominance of dispersion forces and dipolar interaction between the unlike molecules. Molecular interaction in the mixture is of the order: CCl4 > toluene > benzene.

 

 

258

 

Acrylic acid grafted PVC membrane based ion selective electrode for calcium and hardness measurement of water

 

 

 

  D Nanda, M S Oak* & M Pravin Kumar

 

 

 

A poly(vinyl chloride) based membrane ion selective electrode has been developed in which acrylic acid has been grafted on poly(vinyl chloride) powder. The ion selective electrode system, prepared without an internal solution, contains DBP (plasticizer) and NaTPB (anion excluder), and shows near Nernstian response to Mg2+, Cu2+ and super-Nernstian response to Ca2+ in the concentration range 10-1 – 10-5 mol L-1.

 

Notes

 

263

 

Photochemical substitution reactions involving nitrosylpentacyanoferrate(II) iodide system using cadmium sulphide as semiconductor

 

 

 

 

 

 

 

 

 

  

 

Mahaveer Singh Chouhan, Sadhana Singh* &
R C Khandelwal

 

 

 

The photochemical reaction of pentacyanonitrosyl ferrate(II), [Fe(CN)5(NO)]2ˉ, in the presence of iodide as a ligand is reported.

 

Na2[Fe(CN)5(NO)]      Na2[Fe(CN)5(NO)]*

Na2[Fe(CN)5(NO)]*  +  H2O   

Na[Fe(CN)4(NO)(H2O)]*+CN

Na[Fe(CN)4(NO)(H2O)]*  +  I-  

Na2[Fe(CN)4(NO)(I)]+H2O

Na2[Fe(CN)4(NO)(I)]+I-

Na2[Fe(CN)3(NO)(I)2]+CN-

 

266

 

Electrochemical reactions at sacrificial electrodes: Synthesis of zinc(II) alkoxides. Part XVII

 

 

 

  

 

 

J S Banait*, Baljit Singh & Harpreet Kaur

 

 

 

Electrochemical reactions of various alcohols like methanol, ethanol, propan-1-ol, butan-1-ol, pentan-1-ol and hexan-1-ol have been carried out at sacrificial zinc anode and inert platinum cathode using tetrabutylammonium chloride as supporting electrolyte and acetonitrile as solvent. Solid products obtained from the anode compartment have been identified as
zinc(II) alkoxides by elemental analysis and infrared spectral data. The current efficiencies of these systems have been found to be very high.

 

 

269

 

Studies on hydrolysis of methyl parathion with Zr(IV), Hf(IV) and Cu(II) catalysts in acidic aqueous solutions

 

 

 

 

 

 

 

  

 

 

 

 

Tushar Amar Algiwale, C P Shinde* & Purnanand

 

 

 

Hydrolysis of O,O-dimethyl O-p-nitrophenyl phosphorothionate (methyl parathion) has been studied in acidic medium with catalysts such as Zr4+, Hf4+ and Cu2+ cations.

 

 

 

 

273

 

Catalysis by onium salts on the monochromate oxidation of benzhydrols in non-polar media —
A kinetic study

 

 

 

 

 

K Muhammad Basheer, Joy Joseph &
T D Radhakrishnan Nair*

 

 

 

Kinetics of the oxidation of benzhydrols with phase transferred monochromate in non-polar media using tricapryl-methylammonium chloride, tetrabutylammonium bromide and tetrabutylphosphonium bromide as phase transfer catalysts is reported. The oxidation is found to be selective with quantitative formation of benzophenone. The reaction is first order in the [oxidant] as well as the [substrate]. The rate limiting decomposition of the ester involves ruptures of the a C–H bond and O–Cr bond through a cyclic transition state leading to the formation of the product.

 

276

 

Ferrocene encapsulated lipid and surfactant film on electrode surface: A voltammetric sensor for the determination of trace amounts of thiourea

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rimki Bhattacharjya & Diganta Kumar Das*

 

 

 

Ferrocene gives well-defined reversible cyclic voltammograms due to the ferrocene/ferrocenium couple on glassy carbon electrode surface. Both the cathodic and anodic peak currents decrease when thiourea is added to the electrolytic solution.

 

 

280

 

Electrochemical determination of proteins using arsenazo I as voltammetric probe

 

 

 

 

 

 

 

 

 

 

 

  

 

 

 

 

Wei Sun*, Na Zhao & Kui Jiao

 

 

 

A new electrochemical method is proposed for the determination of trace amounts of proteins using arsenazo I as a voltammetric probe.

 

 

 

284

 

Biosorption of hexavalent chromium from aqueous solution by using prawn pond algae (Sphaeroplea)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Srinivasa R Popuri, Kalyani S, Suresh R Kachireddy & Krishnaiah A*

 

 

 

Biosorption of chromium(VI) on prawn pond biomass Sphaeroplea algae in natural and acid treated forms is reported.. The equilibrium biosorption level is a function of solution pH, agitation time, initial metal ion concentration and adsorbent dose at room temperature. At the optimum conditions, the maximum adsorption capacity is found to be 29.8 mg/g and 158.7 mg/g in natural and acid treated forms respectively.

 

 

290

 

Use of 2,4-undecanedione as a liquid chelating ion exchanger for the recovery of various metal ions

 

 

 

 

 

 

Niki Vithlani & Anjali Patel*

 

 

 

A liquid chelating ion exchanger, 2,4-undecanedione,  containing β-diketo group has been synthesized using octanoic acid and characterized by FTIR and UV visible spectroscopy. The synthesized ion exchanger has been used for the extraction of various metal ions such as Ni(II), Zn(II), Cd(II), Co(II), Hg(II) and Ce(II). The use of 2,4 undecanedione for the removal of these metal ions from industrial effluents, and water from river and domestic water has been proposed.

 

 

Authors for correspondence are indicated by (*)


Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 227-237

 

Ternary iron(II) complexes of phenanthroline bases showing DNA binding and cleavage activity

 

Mithun Roy, Ashis K Patra, Arindam Mukherjee, Munirathinam Nethaji & Akhil R Chakravarty*

Received 5 December 2006; accepted 19 January 2007

Ternary iron(II) complexes [Fe(L1)B](PF6)2 (1-3), where L1 is formed from FeCl3 mediated cyclization of N,N'-(2-hydroxypropane-1,3-diyl)bis(pyridine-2-aldimine) (L2) and B is a phenanthroline base, viz. 1,10-phenanthroline (phen, 1), dipyrido[3,2-d:2¢,3¢-f]quinoxaline (dpq, 2) and dipyrido[3,2-a:2¢,3¢-c]phenazine (dppz, 3), are synthesized and complex 1 is structurally characterized by X-ray crystallography. The diamagnetic iron(II) complexes with L1 and B showing respective tetradentate and bidentate chelating modes in a FeN6 coordination geometry exhibit two metal-centered visible electronic bands near 520 and 570 nm in MeCN. The complexes bind to calf thymus DNA giving an order: phen (1) < dpq (2) < dppz (3). Control DNA cleavage experiments using supercoiled (SC) pUC19 DNA and distamycin-A suggest major groove binding for the dppz and minor groove binding for the other complexes. The redox active complexes cleave SC DNA to its nicked circular (NC) form with H2O2 involving hydroxyl radical as the cleavage active species. The complexes show photo-induced DNA cleavage activity at UV light of 365 nm (12 W) in absence of H2O2 via singlet oxygen (1O2) mechanism. Complexes 2 and 3 having respective photoactive dpq and dppz ligands show relatively poor DNA cleavage activity at visible light.

IPC Code: Int. Cl.8 C07F15/02

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 238-246

 

QSAR modeling of thalidomide analogs as antiangiogenic and prostate cancer inhibitor using AM1 calculations

 

Monica Dua, S Revathi, Love Kumar Soni, Arun Kumar Gupta & S G Kaskhedikar*

Received 16 June 2006; revised 3 January 2007

Quantitative structure activity relationship studies have been made on thalidomide analogues acting as dual inhibitors of angiogenesis and prostrate cancer using a combination of various electronic, thermodynamic and spatial descriptors. The QSAR studies show that the presence of fluorine atom is essential for both activities. LUMO and partition coefficient play a significant role in antiangiogenic activity while repulsive energy and molar refractivity contribute to anticancer activity. The correlation of inhibitory activity with charge density at 6th, 8th and 16th position of template implies electronic interaction of the molecule with receptor site.

 

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 247-251

 

Synthesis, spectral studies, thermal decomposition kinetics, reactivity and antibacterial activity of some lanthanide(III) nitrate complexes of 2-(N-indole-2-one)amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene

M Thankamony & K Mohanan*

Received 2 March 2006; revised 2 January 2007

Complexes of La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(III), Dy(III), Yb(III) and Lu(III) with 2-(N-indole-2-one)amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene formed by the condensation of isatin and 2-amino-3-carboxyethyl-4,5,6,7-tetrahydrobenzo[b]thiophene have been synthesized and characterized on the basis of elemental analysis, molar conductance measurements, magnetic susceptibility data and UV-vis, IR and NMR spectral studies. The spectral data reveal that the ligand acts as neutral tridentate coordinating to the metal ion through the azomethine nitrogen, ester carbonyl and carbonyl oxygen of the isatin moiety. Coordination number nine has been proposed for the complexes. The XRD pattern of the lanthanum(III) complex shows that the metal complex possesses tetragonal crystal lattice. The lanthanum(III) complex undergoes facile transesterification reaction when refluxed in methanol for a long period. Studies on antibacterial activity show that the complexes are more potent bactericides than the ligand.

IPC Code: Int. Cl.8 C07F17/00

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 252-257

 

Investigation of molecular interactions in ternary liquid mixtures using ultrasonic velocity

 

R Palania, b,* & K Meenakshia

Received 19 April 2006; revised 6 December 2006

Ultrasonic velocity (U), density (ρ) and viscosity (h) measurement have been carried out in three ternary liquid mixtures of benzene, toluene and CCl4 with ethane 1,2 diol in a polar component of acetone at 303 K. The experimental data have been used to calculate adiabatic compressibility, free length, free volume, internal pressure, Gibb’s energy and available volume. The excess values of the above parameters and the ‘d’ parameter Grunberg and Nission equation have also been evaluated and discussed in the light of molecular interaction in the mixtures. An attempt has been made to evaluate the experimental ultrasonic velocity with that predicted on the basis of Nomotos’ Relations (NR), Ideal Mixing Relation (IMR), Free Length Theory (FLT) and Collision Factor Theory (CFT) with a view to compare the merits of the above three ternary liquid mixtures. The modulus of percentage deviation in ultrasonic velocity and the Chi-square test (c2) for goodness of fit is applied to check the validity of the theories.

IPC Code: Int. Cl.8 G01N11/00

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 258-262

 

Acrylic acid grafted PVC membrane based ion selective electrode for calcium and hardness measurement of water

D Nanda, M S Oak* & M Pravin Kumar

Received 27 January 2005; rerevised 2 January 2006

A poly(vinyl chloride) based membrane ion selective electrode has been developed in which acrylic acid has been grafted on poly(vinyl chloride) powder. The ion selective electrode system, prepared without an internal solution, contains DBP (plasticizer) and NaTPB (anion excluder), and shows near Nernstian response to Mg2+, Cu2+ and super-Nernstian response to Ca2+ in the concentration range 10-1 – 10-5 mol L-1. EDTA has been used to mask the interference of transition metal ions. The best performance of the electrode was obtained when it was stored in 10-2 mol/L Ca2+ solution when the electrode was not in use. The electrode, with response time ≤ 20 s, has been found useful in the determination of concentration of Ca2+ and hardness in river water.

IPC Code: Int. Cl.8 G01N27/333

 

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 263-265

 

Photochemical substitution reactions involving nitrosylpentacyanoferrate(II) iodide system using cadmium sulphide as semiconductor

Mahaveer Singh Chouhan, Sadhana Singh* & R C Khandelwal

Received 26 August 2005; revised 12 January 2007

Sodium nitroprusside contains cyanide ligands that are not easily replaced chemically. Studies on its substitution reaction with another anionic ligand `iodide’ are reported here. The rate of this photochemical reaction has been studied spectrophotometrically. The effect of different parameters like pH, intensity of light, [sodium nitroprusside] and [iodide] ion on the reaction has also been studied. The product has been isolated and characterized by different analytical methods. A tentative mechanism for the photochemical substitution reaction is also proposed.

IPC Code: Int. Cl.8 B01J19/12

 

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 266-268

 

Electrochemical reactions at sacrificial electrodes: Synthesis of zinc(II) alkoxides. Part XVII

J S Banait*, Baljit Singh & Harpreet Kaur

Received 17 July 2006; revised 21 December 2006

Electrochemical reactions of various alcohols have been carried out at sacrificial zinc anode and inert platinum cathode using tetrabutylammonium chloride as supporting electrolyte and acetonitrile as solvent. Solid products obtained from the anode compartment have been identified as zinc(II) alkoxides by elemental analysis and infrared spectral data. The current efficiencies of these systems have been found to be very high.

IPC Code: Int. Cl.8  C22B19/00; C25B1/18

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 269-272

 

Studies on hydrolysis of methyl parathion with Zr(IV), Hf(IV) and Cu(II) catalysts in acidic aqueous solutions

Tushar Amar Algiwale, C P Shinde* & Purnanand

Received 19 June 2006; revised 15 January 2007

Hydrolysis of O,O-dimethyl O-p-nitrophenyl phosphoro-thionate (Methyl Parathion) has been studied in acidic medium with catalysts such as Zr4+, Hf4+ and Cu2+ cations. In the case of Zr4+ and Hf4+ cations, the rate maxima were observed around pH 2.0. Since the metal bound water molecules (M-OH2) of octameric metal-complex are known to exist in equilibrium with metal-hydroxide ion (M-OHˉ), OHˉ nucleophiles are abundantly available from these cations even in acidic aqueous solutions. Therefore, an interaction of sulphur of P=S group with metal ion and an intramolecular nucleophilic attack of metal bound OHˉ at phosphorus atom results in P-O bond cleavage to liberate p-nitrophenol. The 3.2×104 fold rate enhancement with respect to uncatalyzed hydrolysis at pH 6.0 for Cu2+ catalysis, has been attributed to high reactivity of hexa-aquo copper complex (i.e., [Cu(H2O)6]2+), which is known to predominate at around pH 6.0.

IPC Code: Int. Cl.8 C07B41/00

Indian Journal of Chemistry A

Vol. 46A, February 2007, pp. 273-275

 

Catalysis by onium salts on the monochromate oxidation of benzhydrols in non-polar media — A kinetic study

K Muhammad Basheer, Joy Joseph & T D Radhakrishnan Nair*

Received 5 July 2006; revised 8 December 2006

Kinetic studies on the oxidation of benzhydrols with phase transferred monochromate in non-polar media have been carried out using tricaprylmethylammonium chloride, tetrabutyl-ammonium bromide and tetrabutylphosphonium bromide as phase transfer catalysts (PTC). The oxidation has been found to be selective with quantitative formation of benzophenone. The reaction is first order in the [oxidant] as well as the [substrate]. The specific rates and activation parameters have been evaluated. The oxidation takes place at fairly low activation energy with all the catalysts employed. Rates of oxidation decrease with increase in the dielectric constant of the non-polar media. A mechanism involving formation of a Huckel type transition state in the rate determining step is quite probable.

IPC Code: Int. Cl.8 C07B33/00

 

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 276-279

 

Ferrocene encapsulated lipid and surfactant film on electrode surface: A voltammetric sensor for the determination of trace amounts of thiourea

Rimki Bhattacharjya & Diganta Kumar Das*

Received 27 January 2006; revised 18 December 2006

Ferrocene gives well-defined reversible cyclic voltammograms (tris buffer, pH = 7.0), due to ferrocene/ferrocenium couple (inside the phosphatidylcholine and cetyltrimethylammonium­bromide film) on glassy carbon electrode surface. Both the cathodic and anodic peak currents decrease when thiourea is added to the electrolytic solution, which become undetectable at thiourea concentration 15 mM. The plot of cathodic and anodic current versus concentration of thiourea is linear. The decrease in peak current is proposed to be due to the formation of an electroinactive bridged adduct between thiourea and ferrrocene inside the film. The cyclic voltammogram of ferrocene can be recovered by just immersing the tip of the electrode in a 0.01 mM aqueous potassium ferricyanide solution.

IPC Code: Int. Cl.8  G01N27/00

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 280-283

 

Electrochemical determination of proteins using arsenazo I as voltammetric probe

Wei Sun* , Na Zhao & Kui Jiao

Received 22 June 2006; revised 18 November 2006

A new electrochemical method is proposed for the determination of trace amounts of proteins using arsenazo I as a voltammetric probe. At pH 1.5 Britton-Robinson buffer solution, arsenazo I has a sensitive second order derivative linear sweep voltammetric reductive peak at -0.23 V (vs. SCE). The addition of human serum albumin into the dye solution decreases the reductive peak current without change of peak potential, indicating that HSA can interact with arsenazo I to form a supramolecular complex. The decrease of peak current is proportional to the concentration of HSA, which can be further used for the HSA determination. The optimal conditions of the binding reaction and the electrochemical detection have been investigated. The binding constant (βs) and the binding number (m) of human serum albumin with arsenazo I have been calculated as βs= 3.9×1017 and m= 4. No changes are observed in the electrochemical parameters of the reaction system indicating that an electro-inactive complex is formed in the mixed solutions.

IPC Code: Int. Cl.8 G01N27/00

 

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 284-289

 

Biosorption of hexavalent chromium from aqueous solution by using prawn pond algae (Sphaeroplea)

Srinivasa R Popuri, Kalyani S, Suresh R Kachireddy & Krishnaiah A *

Received 21 July 2005; rerevised 17 December 2006

Biosorption of chromium (VI) on prawn pond biomass Sphaeroplea algae in natural and acid treated forms has been studied by using batch technique. The equilibrium biosorption level is a function of solution pH, agitation time, initial metal ion concentration and adsorbent dose at room temperature. Both Freundlich and Langmuir adsorption models are suitable for describing the biosorption of chromium (VI) on the two forms of algae while the adsorption process follows the Legergren kinetic model. The biomass has been characterized by FTIR spectra. Surface area values of the biomass are 0.9 and 2.1 m2/g for natural and acid treated forms respectively. At the optimum conditions, the maximum adsorption capacity is found to be 29.8 mg/g and 158.7 mg/g in natural and acid treated forms respectively.

IPC Code. Int. Cl.8 C02F1/28; C02F3/32

 

Indian Journal of Chemistry

Vol. 46A, February 2007, pp. 290-292

 

Use of 2,4-undecanedione as a liquid chelating ion exchanger for the recovery of various metal ions

Niki Vithlani & Anjali Patel*

Received 9 June 2006; revised 20 November 2006

A liquid chelating ion exchanger containing β-diketo group has been synthesized using octanoic acid and characterized by FTIR and UV visible spectroscopy. The synthesized ion exchanger has been used for the extraction of various metal ions such as Ni(II), Zn(II), Cd(II), Co(II), Hg(II) and Ce(II). The concentration of the extracted metal ions has been determined by AAS. The effect of different parameters have been studied and use of 2,4 undecanedione for the removal of mentioned metal ions from industrial effluents, and water from river and domestic water has been proposed.

IPC Code: Int. Cl.8 B01J39/00