Indian Journal of Chemistry

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

 

VOLUME 47A

NUMBER 12

December 2008

CONTENTS

 

1775

 

Conductimetric and amperometric study of the bromate-phenol-sulphuric acid oscillating reaction

 

 

 

 

 

 

 

 

 

 

 

Fernando Cortés-Salazar, Marco F Suárez &
Daniel Barragán*

 

 

 

 

The bromate-phenol-sulphuric acid chemical reaction that exhibits sequential oscillations has been studied by conductivity measurements and ultrasonically enhanced chronoamperometric methods. Oscillatory behavior is observed in conductivity and current on a working electrode at different potentials.

 

 

 

1780

 

Reactivity of metal (ZnII, RuII)-2,2'-bipyridyl with some bifunctional ligands

 

 

 

 

 

 

Rishikesh Prajapati, Vinod Kumar Yadav,
Santosh Kumar Dubey, Bill Durham &
Lallan Mishra*

 

 

 

 

 

 

 

1787

 

Synthesis, spectral, thermal and electrochemical studies of oxomolybdenum(V) and dioxo-molybdenum(VI) complexes of an azo dye derived from 4-amino-2,3-dimethyl-1-phenyl pyrazol-5-one

 

 

 

 

 

 

 

 

 

 

M L Harikumaran Nair* & A Sheela

 

 

 

 

Novel complexes of oxomolybdenum(V) and
dioxomolybdenum(VI) with an azodye derived from
4-aminoantipyrine and 3-methoxyphenol have been synthesised.

    

 

 

1793

 

Synthesis, spectroscopic and thermal studies of bivalent transition metal complexes with the hydrazone derived from 2-benzimidazolyl mercaptoaceto hydrazide and o-hydroxy aromatic aldehyde

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

V M Naik, M I Sambrani & N B Mallur*

 

 

 

 

Syntheses of complexes of a few first transition series bivalent metal ions like Co(II), Ni(II) and Cu(II) complexes with
2-benzimidazolyl mercaptoaceto hydrazone are reported. Co(II) and Ni(II) complexes have octahedral geometry, while Cu(II) complexes have square planar geometry.

 

 

 

1798

 

Pattern formation and oscillatory
electropolymerization of thiophene

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ishwar Das*, Namita R Agrawal, Shoeb A Ansari & Sanjeev Kumar Gupta

 

 

 

 

Polythiophenes with fibrillar and compact morphologies have been synthesized by electrochemical polymerization in the presence of oxidizing agents, 4-toluene sulphonic acid silver salt and perchloric acid, respectively. On addition of ZnSO4 the morphology changes from fibrillar to compact in the case of
4-TSS and from compact to branch, when HClO4 is used.

 

 

Notes

 

1804

 

Surface plasmon resonance based biosensor for
label free detection of cholesterol

 

 

 

 

Rakhee Gehlot, Kavita Sharma, Manoth Mathew & Sunita Kumbhat*

 

 

 

 

A cholesterol oxidase-bovine serum albumin conjugate based sensing element for a SPR based biosensor for cholesterol has been proposed. The surface morphology of biosensor has been recorded using atomic force microscopy. 

 

 

 

1809

 

Thermodynamic and transport properties of binary liquid mixtures of phenylacetonitrile with some aliphatic amines at 308.15 K

 

 

 

 

 

 

 

 

 

 

 

 

 

Ranjith Kumar Bachu, Murali Krishna Patwari, Asra Banu Syeda, Satyanarayana Boodida,
Savitha Jyostna Tangeda & Satyanarayana Nallani*

 

 

 

 

Excess molar volumes and deviations in viscosity have been calculated for some aliphatic amines, (diethyl amine, propyl amine, diisopropyl amine, butyl amine and t-butyl amine), in phenylacetonitrile from density and viscosity measurements at 308.15 K. The phenylacetonitrile + amines binary systems are characterized by negative values of excess molar volumes as well as deviations in viscosity across the composition range at the studied temperature. The values of VE are found to decrease in the following order: n-BA > t-BA > n-PA > DIPA > DEA. The negative Dh values at equimolar concentration of the binary systems vary as follows: t-BA > n-PA > n- BA > DEA > DIPA.

 

 

1814

 

Conductance and solvation behaviour of benzimidazolium dichromate in dimethyl sulphoxide-water mixture

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

V Radhika & P Manikyamba*

 

 

 

 

Conductance of benzimidazolium dichromate has been measured in dimethyl sulphoxide-water mixtures of varying compositions in the temperature range of 283-313K. The limiting molar conductance, Lo, increases with increase in the proportion of water in the solvent mixture, while the association constant of the ion pair, KA, is found to be maximum in the solvent containing 20-40%(v/v) water. The free energy of solvation, DGi-s, is maximum in 80% (v/v) water, suggesting that the ion-solvent interactions are maximum at this composition of solvent mixture.

 

 

1818

 

 

Synthesis, characterization and surface-active properties of surfactants having dipeptidyl linkage as hydrophilic group

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S S S Kushwaha * & Antima Katiyar

 

 

 

 

 

1823

 

Influence of template on synthesis and characterization of novel mesoporous silica nanosphere

 

 

 

 

 

 

 

 

 

 

 

 

 

N Venkatathri

 

 

 

 

A new method is reported for the synthesis of silica nanosphere using ultrasonic method. Characterization reveals that the material is mesoporous with small particle size.

 

 

 

1826

 

Influence of template on synthesis of silica nanosphere using CaCO3

 

 

 

 

 

 

 

 

 

 

N Venkatathri

 

 

 

 

Synthesis of silica nanosphere is reported using tetrapropylammonium bromide and calcium carbonate as template. The physicochemical characteristics of the sample have been compared with those of the sample synthesised using cetyltrimethylammonium bromide and calcium carbonate. The results show that both the materials are similar, although mesoporosity appears only in the latter. The hollow sphere property is observed in calcined and 10 % dil. HCl treated samples.

 

1829

 

Annual Index

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1775-1779

 

 

Conductimetric and amperometric study of the bromate-phenol-sulphuric acid oscillating reaction

 

Fernando Cortés-Salazar, Marco F Suárez & Daniel Barragán*

Received 9 June 2008; revised 23 October 2008

The bromate-phenol-sulphuric acid chemical reaction that exhibits sequential oscillations has been studied by conductivity measurements and ultrasonically enhanced chronoamperometric methods. Oscillatory behaviour is observed in conductivity and current on a working electrode at different potentials. The experimental results have been qualitatively analyzed and compared to a computer simulation using the GVKFR mechanism for uncatalyzed chemical reactions.

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1780-1786

 

 

Reactivity of metal (ZnII, RuII)-2,2'-bipyridyl with some bifunctional ligands

Rishikesh Prajapatia, Vinod Kumar Yadava, Santosh Kumar Dubeya, Bill Durhamb & Lallan Mishraa,*

Received 22 August 2008; revised 10 November 2008

Complexation of cis-bis(2,2'-bipyridyl)dichlororuthenium(II) dihydrate with carboxaldehyde and carboxylate bearing ligand (4-carboxybenzaldehyde; L1H) and with bis-acetyl and pyridine containing ligand (2,6-diacetylpyridine; L2) yields [Ru(bpy)3](PF6)2 (bpy = 2,2'-bipyridyl), as the major product in both reactions along with [Ru(bpy)2(L1)]PF6 (1) and [Ru(bpy)2(L2)](PF6)2 (2) as minor products. However, reaction of cis-bis(2,2'-bipyridyl)dichlororuthenium(II) dihydrate with ligand containing bis-triazolo and diimino donor sites [1,4-bis(1,2,4–triazolo-3-imino)benzene; L3H2] provides [Ru(bpy)2Cl2]PF6 (3) crystals characterized by its single crystal X-ray data along with some unidentified product. Similar to ruthenium bipyridyl, reaction of (2,2'-bipyridyl)dichlorozinc(II) monohydrate with L2 has also been carried out which yields [Zn(bpy)3](PF6)2 as a crystalline product along with a polymeric product with the composition [{Zn(bpy)(L2)Cl2}·DMSO]n.

IPC Code: C07F3/06; C07F15/00

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1787-1792

 

 

Synthesis, spectral, thermal and electrochemical studies of oxomolybdenum(V) and dioxomolybdenum(VI) complexes of an azo dye derived from 4-amino-2,3-dimethyl-1-phenyl pyrazol-5-one

 

M L Harikumaran Naira,* & A Sheelab

 

Received 21 May 2008; revised 11 November 2008

Some novel complexes of oxomolybdenum(V) and dioxomolybdenum(VI) with an azodye derived from 4-amino-antipyrine and 3-methoxyphenol have been synthesised and characterized by elemental analyses, molar conductance values, magnetic susceptibility measurements, IR, electronic, ESR, and 1H NMR spectra and cyclic voltammetric studies. The physico-chemical studies and spectral data indicate that the ligand acts as neutral bidentate. All the complexes are found to be monomeric and neutral with distorted octahedral geometry. The X-ray diffraction studies of [MoO(MOPAAP)Cl3] and [MoO2(MOPAAP)Cl2] indicate that the complexes are orthorhombic with the unit cell dimensions a = 7.3277 Å, b = 9.6663Å and c = 15.8897 Å; and a = 8.5534 Å, b = 9.5986 Å, c = 15.4056 Å respectively.. The CV profile of the complex [MoO(MOPAAP)Cl3] shows a quasireversible peak, which indicates that the metal-ligand linkage is more covalent in nature. The thermal stabilities of the complexes have been compared and show that [MoO(MOPAAP)Cl3] is more stable than [MoO2(MOPAAP)Cl2].

IPC Code: Int. Cl.8 C07F11/00; C09B27/00

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1793-1797

 

 

Synthesis, spectroscopic and thermal studies of bivalent transition metal complexes with the hydrazone derived from 2-benzimidazolyl mercaptoaceto hydrazide and o-hydroxy aromatic aldehyde

V M Naika, M I Sambrania & N B Mallurb, *

 

Received 10 December 2007; revised 29 October 2008

Syntheses of complexes of a few first transition series bivalent metal ions like Co(II), Ni(II) and Cu(II) complexes with 2-benzimidazolyl mercaptoaceto hydrazone have been reported. The complexes have been characterized on the basis of analytical, molar conductivity, magnetic susceptibilities, infrared, electronic, X-ray diffraction (powder) and ESR spectral data. Infrared spectral data show that the ligands behave in a monobasic tridentate manner in all the complexes except in Cu(II) complexes, where they act as dibasic tridentate ligands with ONO donor sequence. Co(II) and Ni(II) complexes have octahedral geometry, while Cu(II) complexes have square planar geometry. The thermal stabilities of the complexes have been studied by TGA. The  kinetic parameters has also been calculated.

IPC Code: Int. Cl.8 C07F1/08; C07F15/04; C07F15/06

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1798-1803

 

 

Pattern formation and oscillatory electropolymerization of thiophene

Ishwar Dasa,*, Namita Rani Agrawalb, Shoeb A Ansaria & Sanjeev Kumar Guptaa

Received 28 July 2008; revised 15 October 2008

Thiophene has been electrochemically polymerized using organic and inorganic oxidizing agents, 4-toluene sulphonic acid silver salt and perchloric acid, in the absence and presence of ZnSO4. Electropolymerized aggregates have been characterized by morphological studies, growth kinetics, powder X-ray diffraction, differential scanning calorimetry, thermogravimetry and direct analysis in real time mass spectroscopy measurements. It is found that physical characteristics and morphology of polythiophene depend on the nature and concentration of the anion and field intensity. Morphologies of polymer aggregates using the silver salt of 4-toluene sulphonic acid and HClO4 are fibrillar and compact respectively. Transitions in morphology have also been observed when doped with ZnSO4. Growth kinetics during electropolymerization of thiophene has also been studied at different thiophene concentrations, field intensity, and concentrations of oxidizing agents as well as in the presence of ZnSO4. Growth rate is found to be higher with HClO4 than with 4-toluene sulphonic acid silver salt. Polymer obtained by using the silver salt is thermally more stable and of low molecular weight (416) than that obtained with HClO4 (689). During electropolymerization, change in anode potential is observed and has been monitored as a function of time. Correlation between morphology and oscillatory behaviour has been studied.

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1804-1808

 

 

Surface plasmon resonance based biosensor for label free detection of cholesterol

Rakhee Gehlota, Kavita Sharmaa, Manoth Mathewb & Sunita Kumbhata, *

Received 2 July 2008; revised 12 November 2008

A surface plasmon resonance based biosensor has been proposed for a simple, label-free, highly selective and sensitive detection of cholesterol employing the flavoenzyme, cholesterol oxidase, as the sensing element. The immobilization of cholesterol oxidase conjugated with bovine serum albumin on to the gold sensor chip has been accomplished by covalent binding through an activated self-assembled 11-mercaptoundecanoic acid monolayers. The surface morphology of the biosensor has been recorded using atomic force microscopy. Sensitivity of 1.41mo/mg dl-1 of cholesterol has been achieved using the biosensor. The biosensor is highly specific for cholesterol and shows no significant interference from potent interferents such as ascorbic acid and uric acid.

IPC Code: Int. Cl.8 A61B5/145; G01N33/92; H01L31/14

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1809-1813

 

 

Thermodynamic and transport properties
of binary liquid mixtures of phenylacetonitrile with some aliphatic amines at 308.15 K

Ranjith Kumar Bachu, Murali Krishna Patwari, Asra Banu Syeda, Satyanarayana Boodida,
Savitha Jyostna Tangeda & Satyanarayana Nallani*

Received 15 July 2008; revised 10 November 2008

Excess molar volumes and deviations in viscosity have been measured for some aliphatic amines in phenylacetonitrile from density and viscosity measurements at 308.15 K. The amines chosen for present study are diethyl amine, propyl amine, diisopropyl amine, butyl amine and t-butyl amine. All properties are fitted to the Redlich-Kister type polynomial using multi-parametric non-linear regression analysis to estimate the binary coefficients and standard errors. Other parameters like excess Gibbs free energy of activation of viscous flow, and Grunberg-Nissan interaction parameter are also utilized in the qualitative analysis to elicit the specific interactions.

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1814-1817

 

 

Conductance and solvation behaviour of benzimidazolium dichromate in dimethyl sulphoxide-water mixture

V Radhika & P Manikyamba*

Received 1 January 2008; re- revised 19 November 2008

Conductance of benzimidazolium dichromate has been measured in dimethyl sulphoxide-water mixtures of varying compositions in the temperature range 283-313K. The limiting molar conductance, Lo, and the association constant of the ion pair, KA, have been computed using Shedlovsky equation. Lo increases with increase in the proportion of water in the solvent mixture. KA is found to be maximum in the solvent containing 20-40% (v/v) water. The free energy of solvation, DGi-s, is maximum in 80% (v/v) water suggesting that the ion-solvent interactions are maximum at this composition of solvent mixture.

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1818-1822

 

 

ynthesis, characterization and surface-active properties of surfactants having dipeptidyl linkage as hydrophilic group

S S S Kushwaha* & Antima Katiyar

Received 22 February 2008; revised 25 November 2008

A homologous series of surfactants, N-(phe-gly) glycerol ether, has been synthesized from phe-gly dipeptide and product of the reaction of epichlorohydrin and aliphatic alcohols with alkyl chains of 10-15 carbon atoms. Specifically, the critical micelle concentration, effectiveness of surface tension reduction, maximum surface excess, minimum surface area and standard free energies of micellization and of adsorbtion have been determined from aqueous surface tension measurements using the Wilhelmy plate technique. All the surfactants have good surface properties and wetting capability. They are slightly soluble in water and highly soluble in alkaline methanol and alkaline water. As compared to the tryptophan-based surfactants, the studied surfactants have low CMC.

IPC Code: Int. Cl.8 C11D; G01N13/00


 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1823-1825

 

 

Influence of template on synthesis and characterization of novel mesoporous silica nanosphere

 

N Venkatathri

 

Received 17 September 2008; revised 12 November 2008

A new method is reported for the synthesis of mesoporous silica nanosphere using ultrasonic method. Characterization reveals that the material is mesoporous with a small particle size. The template method gives spherical samples; uniform particle size is obtained when n-octylamine is used. Three stage weight loss occurs in cetyltrimethylammonium bromide samples, while the other templates show two stage weight loss. Amorphous and mesoporous silica samples have identical infrared spectra. The as-synthesized sample shows type II nitrogen adsorption curve, while the calcined samples show type IV adsorption curves.

IPC Code: Int. Cl.8 B82B1/00; C01B37/02

 

 

Indian Journal of Chemistry

Vol. 47A, December 2008, pp. 1826-1828

 

 

Influence of template on synthesis of silica nanosphere using CaCO3

N Venkatathri

Received 18 September; revised 14 November 2008

Synthesis of silica nanosphere is reported using tetrapropylammonium bromide and calcium carbonate as template for the first time. The physicochemical characteristics of the sample has been compared with the sample synthesized using cetyltrimethylammonium bromide and calcium carbonate. The results show that both the materials are similar, although mesoporosity appears only on the latter. The hollow sphere property is observed in calcined and 10 % dil. HCl treated samples. The weight loss due to calcium carbonate decomposition occurs at high temperature (800oC). Thermogravimetry/ differential thermal analyses show that there is no organic amine inside the TPABr morphology and only a small amount (5 %) in CTABr sample. FTIR spectroscopic analysis shows the peak responsible for CaO- in addition to the peak due to the T-O-T tetrahedral skeleton. Nitrogen adsorption does not show any significant result on the as-synthesized sample activated at 100 oC before adsorption.

IPC Code: Int. Cl.8 B82B1/00; C01B37/02