Indian Journal of Chemistry

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

 

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VOLUME 48A

NUMBER 11

November 2009

CONTENTS

 

1477

 

Designing model protein chains using bioinspired
ant algorithm

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Mohsineen Wazir & A K Bakhshi*

 

 

 

 

Ant algorithm has been applied in combination with the Simple Negative Factor Counting and Inverse Iteration methods for designing proteins with pre-specified conduction properties. Band structure results of polyglycine, polyanaline and polyserine, obtained on the basis of ab initio Hartree Fock crystal orbital method using minimal basis set, have been used as the input to obtain the electronic properties of the model peptide chain. Both the α-helical and β- pleated sheet configurations of the proteins have been investigated.

 

 

1484

 

Synthesis and characterization of  complexes of Fe(III), Co(III), Ni(II), Cu(II), Zn(II) and UO22+ with p-tert-butylcalix[4]arene bearing two imine
pendants linked through salicylyl moiety at the
lower rim

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Mishtu Dey,Jugun Prakash Chinta , Gary J Long & Chebrolu P Rao*

 

 

 

 

Complexes of the double-armed p-tert-butylcalix[4]arene derivative possessing imine functionality linked through salicylyl moiety at the lower rim are synthesized and characterized. The ligand exhibits variable coordination behavior, from tetradentate to hexadentate, depending upon the metal ion to which it is bound,  by always acting as di-anionic. While it uses both the ether oxygens of the pendants to coordinate in the case of Fe(III), Co(III) and Ni(II) complexes, it uses only the pendant salicylidene moieties in Cu(II) and Zn(II) complexes. The Zn(II) complex catalysis ester hydrolysis through the formation of Zn(II)-hydroxo species.

 

 

 

 

1492

 

Low temperature hydrothermal synthesis of calcium phosphate ceramics: Effect of excess Ca precursor on phase behavior

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Asep Sofwan Faturohman Alqap & Iis Sopyan*

 

 

 

 

Low temperature hydrothermal exchange reaction has been used to synthesize calcium phosphate materials comprising hydroxyapatite and β-tricalcium phosphate using CaO and NH4H2PO4 as calcium and phosphorus precursors, respectively. The effect of excess of calcium precursor on phase behavior of these materials has been investigated by varying CaO content  in the suspension. Excess of CaO shifts the balance to hydroxyapatite formation at the higher calcination temperature such that β-tricalcium phosphate, β-tricalcium phosphate + hydroxyapatite and hydroxyapatite of higher purity are obtained with 0, 10 and 20 mole% excess CaO, respectively.

 

 

1501

 

Studies of viscosities of dilute solutions of alkylamines in non-electrolyte solvents. V. Alkylamines in toluene and benzene at 303.15 K

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S L Oswal*& S P Ijardar

 

 

 

Viscosities, specific viscosities, viscosity deviations and excess Gibbs energy of activation of dilute solutions of alkylamines in toluene and benzene have been reported. The specific viscosities have been analyzed in terms of Herskovits and Kelly equation  and Nakagawa equation. The change in activation energy  and heat of solution  per mole of solute (alkylamine) in infinite dilute cyclohexane, benzene and toluene solutions have been calculated from Jones-Dole coefficient in terms of the transition state theory. Viscosity deviations are negative for all the amine solutions, and their magnitudes increase with increase in concentration of alkylamine. The specific viscosities and excess Gibbs energy of activation of viscous flow are of varying magnitude and sign, depending upon the viscosities and type and nature of solute and solvent molecules.

 

 

 

 

 

Notes

 

1510

 

Palladium assisted formation of arylselenoacetone from diaryldiselenides in methanol-acetone

 

 

 

 

 

 

 

 

 

 

 

 

 

Ninad Ghavale, Amey Wadawale, Sandip Dey &
Vimal K Jain*

 

 

 

 

Reaction of Na2PdCl4 with diaryldiselenide in methanol-acetone yields trans-[PdCl2{SeAr(CH2COMe)}2] (Ar = 2,4,6-Me3C6H2 and 2,4,6-iPr3C6H2) and [PdCl(SeAr)]n. The intermediate products have been characterized by analytical and spectroscopic data and by single crystal X-ray diffraction studies.

 

 

 

1515

 

Inclusion complexation of 3,5-dihydroxybenzoic acid with β-cyclodextrin at different pHs

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

S Siva, R K Sankaranarayanan,
A Antony Muthu Prabhu, V K Subramanian &
N Rajendiran*

 

 

 

 

Effect of b-cyclodextrin on the absorption and fluorescence spectra of 3,5-dihydroxy benzoic acid has been studied in buffer solutions of different pHs (1, 7, 10). The study reveals that in all the studied pHs, DHB forms 1:1 inclusion complex. The hydroxyl group is present in the interior part of the b-CD cavity and carboxyl group is present in the hydrophilic part of the b-CD cavity. Dual luminescence is observed in pH~1 and pH~7 solutions which shows that intramolecular charge transfer is present in these pHs. The broad spectral maximum at pH~10 indicates intramolecular proton transfer in DHB.

 

 

 

1522

 

Micellization behavior of [C16-4-C16], 2Br gemini surfactant in binary aqueous-solvent mixtures

 

 

 

 

 

 

 

 

 

 

 

 

Deepti & Kallol K Ghosh*

 

 

 

 

Micellar behavior of C16-4-C16, 2Br-  in binary aqueous mixtures of ethylene glycol, 1,4 dioxane, dimethyl sulphoxide, methanol and dimethyl formamide (20 and 40% v/v) has been studied by conductivity measurements. The cmc increases whereas Gibbs free energy decreases with increasing volume percentage of organic solvents in the organic solvent-water binary mixture. The negative value of enthalpy of micellization indicates that the micellization process is exothermic.

 

 

 

1527

 

Detection of tight ion-pair in some novel
lipopathic oxidants from the monolayer at
air-water interface

 

 

 

 

 

 

 

 

 

 

 

B K Mishra*, Sandhyamayee Sahu, S Pradhan &
Sabita Patel*

 

 

 

 

Monolayer of cetyltrimethylammonium permanganate/ dichromate/ ceric nitrate has been developed on water surface. The tight ion pairing of counter ions in the amphiphilic oxidants affects the solubility and NMR spectral characteristics of proximal protons and also the surface area/molecule on air-water interface.

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

Indian Journal of Chemistry

Vol. 48A, November 2009, pp. 1477-1483

 

Designing model protein chains using bioinspired ant algorithm

Mohsineen Wazir & A K Bakhshi*

Department of Chemistry, University of Delhi, Delhi 110 007, India

Email: akbakhshi2000@yahoo.com

Received 9 August 2009; revised and accepted 16 October 2009

Ant algorithms are bioinspired algorithms aimed at finding approximate solutions to hard combinatorial optimization problems through the use of artificial ants and their indirect communication via synthetic pheromones. In the present study, the algorithm has been applied in combination with the Simple Negative Factor Counting and Inverse Iteration methods to the problem of designing proteins with pre-specified conduction properties. Band structure results of polyglycine, polyanaline and polyserine, obtained on the basis of ab initio Hartree Fock crystal orbital method using minimal basis set, have been used as the input to obtain the electronic properties of the model peptide chain. Both the α-helical and
β- pleated sheet configurations of the proteins have been investigated using the ant algorithm. Optimum solutions have been obtained in both cases, giving the optimum percentage compositions of the constituent amino acids, viz., polyglycine, polyalanine and polyserine, which would give the most conducting protein (i.e., the one with minimum gap and maximum electronic delocalization).

Keywords: Theoretical chemistry, Artificial intelligence, Biopolymers, Ant algorithms, Proteins, Electronic properties, Band structures

 

Indian Journal of Chemistry

Vol. 48A, November 2009, pp. 1484-1491

 

Synthesis and characterization of  complexes of Fe(III), Co(III), Ni(II), Cu(II), Zn(II) and UO22+ with p-tert-butylcalix[4]arene bearing two imine pendants linked through salicylyl moiety at the lower rim

Mishtu Deya, Jugun Prakash Chintaa, Gary J Longb & Chebrolu P Raoa, *

aBioinorganic Laboratory, Department of Chemistry, Indian Institute of Technology Bombay, Powai, Mumbai 400 076, India

Email: cprao@iitb.ac.in

bDepartment of Chemistry, Missouri University of Science and Technology, Rolla, MO 65409-0010, USA

Received 22 September 2009; revised and accepted 21 October 2009

Metal ion complexes of the double-armed p-tert-butylcalix[4]arene derivative possessing imine functionality linked through salicylyl moiety  at the lower rim has been synthesized for the first time and characterized by analytical, spectral and magnetic methods. The 1, 3- di-calix[4]arene-imine conjugate exhibits variable coordination behavior, from tetradentate to hexadentate, depending upon the metal ion to which it is bound, by always acting as di-anionic. While it uses both the ether oxygens of the pendants to coordinate in the case of Fe(III), Co(III) and Ni(II) complexes, it uses only the pendant salicylidene moieties in the case of Cu(II) and Zn(II) complexes. The Zn(II) complex catalysis ester hydrolysis through the formation of Zn(II)-hydroxo species.

Keywords: Coordination chemistry, Calixarenes, Calix[4]arene-imine conjugates, Iron, Cobalt, Nickel, Copper, Zinc, Uranium, FAB mass spectrometry, Magnetic susceptibility, Electron paramagnetic resonance, Mossbauer spectroscopy

IPC Code: Int. Cl.9 C07F1/08; C07F3/06; C07F5/00; C07F15/00

Indian Journal of Chemistry

Vol. 48A, November 2009, pp. 1492-1500

Low temperature hydrothermal synthesis of calcium phosphate ceramics: Effect of excess Ca precursor on phase behaviour

Asep Sofwan Faturohman Alqapa, b & Iis Sopyana, *

aDepartment of Manufacturing and Materials Engineering, Faculty of Engineering, International Islamic University Malaysia (IIUM),
P O Box 10, Kuala Lumpur 50728, Malaysia

bMechanical Engineering Program, Faculty of Engineering, University of Bengkulu, Jalan Raya Kandang Limun,
Bengkulu 38000, Indonesia

Email: sopyan@iiu.edu.my

Received 31 July 2009; revised and accepted 20 October 2009

Low temperature hydrothermal exchange reaction has been used to synthesize calcium phosphate materials comprising hydroxyapatite and β-tricalcium phosphate using CaO and NH4H2PO4 as calcium and phosphorus precursors respectively. The effect of excess of calcium precursor on phase behaviour of these materials has been investigated by varying CaO content (0, 10 and 20 mole% excess of 0.1 mole CaO) in the suspension. The as-synthesized paste has been dried followed by calcination at 700-1200 ºC. Results show the formation of Ca-deficient apatite at the lower calcination temperature. Excess of CaO shifts the balance to hydroxyapatite formation at the higher calcination temperature such that β-tricalcium phosphate, β-tricalcium phosphate + hydroxyapatite and hydroxyapatite of higher purity are obtained with 0, 10 and 20 mole% excess CaO, respectively.

 

Keywords: Hydrothermal synthesis, Hydroxyapatites, Calcium deficient apatites, Calcination, Ceramics, Calcium phosphates

IPC Code: Int. Cl.9 C04B35/447

Indian Journal of Chemistry

Vol. 48A, November 2009, pp. 1501-1509

Studies of viscosities of dilute solutions of alkylamines in

non-electrolyte solvents. V. Alkylamines in toluene and benzene at 303.15 K

 

S L Oswala, * & S P Ijardarb

aBiochemistry Division, R&D Span Diagnostic Limited, 173-B, New Industrial Estate, Udhna, Surat 394 210, India

Email: oswalsl@yahoo.co.uk

 

bDepartment of Chemistry, S V National Institute of Technology, Surat 395 007, India

Received 27 July 2009; revised and accepted 19 October 2009

Viscosities of dilute solutions of n-propylamine, n-butylamine, di-n-propylamine, di-n-butylamine,
tri-n-propylamine and tri-n-butylamine in toluene, and of tri-n-butylamine in benzene, have been measured at 303.15 K. The values of viscosity deviations are negative for all the amine solutions and their magnitude increases with the increase in concentration of alkylamine. The specific viscosities and excess Gibbs energy of activation of viscous flow, based on Eyring's theory of absolute reaction rates, are of varying magnitude and sign depending upon the viscosities and type and nature of solute and solvent molecules. The specific viscosities have been analyzed in terms of Herskovits and Kelly equation and Nakagawa equation. The change in Gibbs activation energy and the heat of solution per mole of solute (alkylamine) at infinite dilution in cyclohexane, benzene and toluene solutions have been calculated in terms of the transition state theory.

Keywords:   Solution chemistry, Thermodynamics, Alkylamines, Hydrocarbons, Transition state treatment, Viscosities

Indian Journal of Chemistry

Vol. 48A, November 2009, pp. 1510-1514

Palladium assisted formation of arylselenoacetone from diaryldiselenides in methanol-acetone

Ninad Ghavale, Amey Wadawale, Sandip Dey &  Vimal K Jain*

Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India
Email: jainvk@barc.gov.in

Received 23 August 2009; accepted 16 October 2009

The reaction of Na2PdCl4 with diaryldiselenide in methanol-acetone yields
trans-[PdCl2{SeAr(CH2COMe)}2] (Ar = 2,4,6-Me3C6H2 and 2,4,6-iPr3C6H2) and [PdCl(SeAr)]n. The intermediate products in these reactions have been characterized by analytical and spectroscopic data and by single crystal X-ray diffraction studies. A plausible mechanism for the formation of arylselenoacetone in these reactions has been suggested.

Keywords: Coordination chemistry, Palladium, Selenium, Ketones, X-ray diffraction, Photoelectron spectroscopy

IPC Code: Int. Cl.9 C07F15/00

Indian Journal of Chemistry

Vol. 48A, November 2009, pp. 1515-1521

Inclusion complexation of 3,5-dihydroxybenzoic acid with
β-cyclodextrin at different pHs

S Siva, R K Sankaranarayanan, A Antony Muthu Prabhu, V K Subramanian & N Rajendiran*

Department of Chemistry, Annamalai University,
Annamalai Nagar 608 002, Tamilnadu, India

Email: drrajendiran@rediffmail.com

Received 7 September 2009; revised and accepted 21 October 2009

Effect of b-cyclodextrin on the absorption and fluorescence spectra of 3,5-dihydroxy benzoic acid has been studied in buffer solutions of different pHs (1, 7, 10). The study reveals that in all the studied pHs, DHB forms 1:1 inclusion complex. The hydroxyl group is present in the interior part of the b-CD cavity and carboxyl group is present in the hydrophilic part of the b-CD cavity. Dual luminescence is observed in pH~1 and pH~7 solutions which shows that intramolecular charge transfer is present in these pHs. The broad spectral maximum at pH~10 indicates intramolecular proton transfer in DHB.

Keywords: Fluorescence spectra, Luminescence, Inclusion       complexes, Intramolecular charge transfer

Indian Journal of Chemistry

Vol 48A, November 2009, pp. 1522-1526

Micellization behavior of [C16-4-C16], 2Br gemini surfactant in binary
aqueous-solvent mixtures

Deepti & Kallol K Ghosh*

School of Studies in Chemistry, Pt. Ravishankar Shukla University, Raipur (CG) 492 010, India
Email: kallolkghosh@yahoo.com

and

Pierluigi Quagliotto

Dipartimento di Chimica Generale ed Organica ApplicataeCentro di Eccellenza NIS, Università degli Studi di Torino,
Corso Massimo D’Azeglio 48, 10125, Torino, Italy

Received 17 June 2009; revised and accepted 5 October 2009

The micellization behavior of a bis cationic gemini surfactant, C16H33N+(CH3)2-(CH2)4-N+(CH3)2C16H33, 2Br-, has been studied in binary aqueous mixtures of dimethyl sulfoxide, methanol,
1, 4-dioxane, dimethyl formamide and ethylene glycol byconductivity measurements at 300-320 K. The critical micelle concentration, degree of micellar ionization and thermodynamic parameters, i.e, Gibbs free energy, enthalpy, and entropy of micellization of the gemini surfactant have also been determined. The cmc increases whereas Gibbs free energy decreases with increasing volume percentage of organic solvents in the organic solvent-water binary mixture. The negative value of enthalpy
of micellization indicates that the micellization process is exothermic.

Keywords: Thermodynamics, Surfactants, Gemini surfactants, Micellization, Solvent effect

Indian Journal of Chemistry

Vol. 48A, November 2009, pp. 1527-1531

Detection of tight ion-pair in some novel lipopathic oxidants from the monolayer at air-water interface

B K Mishraa, *, Sandhyamayee Sahua, S Pradhana & Sabita Patelb, *

aCentre of Studies in Surface Science and Technology, Department of Chemistry, Sambalpur University,
Jyoti Vihar  768 019, India

Email: bijaym@hotmail.com

b Department of Chemistry, National Institute of Technology, Rourkela 769 008, India

Email: sabita_patel@yahoo.com

Received 26 August 2009; revised and accepted 26 October 2009

From the isotherms of surface pressure and area of cetyltrimethylammonium dichromate, permanganate and ceric nitrate, the anchoring area on water-air interface for each oxidant has been determined by spreading as Langmuir monolayer. The area/molecule of these oxidants with a common amphiphilic counterion, i.e., cetyltrimethylammonium ion, depends on the size of the anion counterpart indicating the existence of contact ion pair between CTA+ and the anionic group in aqueous medium. However, in aqueous acetic acid subphase, the decrease in area/molecule of cetyltrimethylammonium dichromate indicates dissociation of the constituting ions.

Keywords: Solution chemistry, Ion pairs, Tight ion pairs, Water- air interface, Anchoring area, Monolayer properties