Indian Journal of Chemistry

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

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VOLUME 47A

NUMBER 6

June 2008

CONTENTS

 

803

 

Cyclic conjugation in mono- and dicyclopenta-derivatives of anthracene and phenanthrene

 

 

 

 

 

 

 

Ivan Gutman*, Jelena Đurđević, Boris Furtula & Bojana Milivojević

 

 

 

 

The energy effects of cycles and pairs of cycles in mono- and dicyclopenta-derivatives of anthracene and phenanthrene are computed by a graph-theoretical method.

 

 

 

808

 

Nitrogen-containing carbon nanotubes as a possible hydrogen storage medium

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M Sankaran & B Viswanathan*

 

 

 

 

Nitrogen containing carbon nanotubes have been synthesized and their hydrogen absorption capacity evaluated. The material is more amenable to hydrogen absorption as compared to pure carbon materials. The nitrogen atoms in carbon matrices act as the active centers.

 

 

815

 

Formation of mesopores in resorcinol-formaldehyde composite resin

 

 

 

 

 

 

 

 

 

 

Mahasweta Nandi, Krishanu Sarkar &
Asim Bhaumik*

 

 

 

A mesostructured resorcinol-formaldehyde material is synthesized by in-situ polycondensation of resorcinol and formaldehyde in the presence of a cationic surfactant in alkaline medium. The material exhibits photoluminescence at room temperature.

 

 

821

 

Vibrational spectroscopic studies supported by
HF/DFT calculations of
2,4,6-triaminopyrimidine

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

N Sundaraganesan *, B Dominic Joshua,
C Meganathan & S Sebastian

 

 

 

 

Laser Raman and Fourier transform infrared spectra of
2, 4, 6-triaminopyrimidine have been recorded in solid phase. The thermodynamic functions of the title compound have also been computed at HF/6-31G(d,p) and B3LYP/6-31G(d,p) levels. The scaled theoretical wave numbers show good agreement  with the experimental values.

 

 

 

 

830

 

Visible light induced heterogeneous advanced oxidation process to degrade pararosanilin dye in aqueous suspension of ZnO

 

 

 

 

 

 

 

 

Brijesh Pare*, Pardeep Singh & S B Jonnalagadda

 

 

 

 

Photocatalytic degradation of pararosanilin dye has been investigated under visible light in the presence of aqueous suspension of ZnO under different conditions. Absorbance of the dye is found to decrease in the presence of ZnO and visible irradiation. Kinetic analysis indicates the complex nature of heterogeneous photocatalytic process.

 

 

836

 

Synthesis, characterization and kinetic studies on complex formed between amantadine hydrochloride and sodium molybdate at physiological pH

 

 

 

 

 

 

N Sridevi* & K K Mohammed Yusuff

 

 

 

 

On mixing amantadine with molybdate in aqueous solutions of pH 1.5, 7.4 and 8.0, a single complex of the type, (C10H17N)2H2MoO4 with an octahedral geometry is formed. The amino group of amantadine, that is required to remain free for its antiviral function, is bound to molybdate in the complex suggesting possibility of interaction between amantadine and molybdenum supplements in vivo.

 

Notes

 

843

 

Fluorescence resonance energy transfer from a
b-carboline analogue to a cationic photosensitizer in aqueous solution

 

 

 

 

 

 

Paramita Das, Deboleena Sarkar &
Nitin Chattopadhyay*

 

 

 

 

Fluorescence resonance energy transfer from a potent bioactive non-ionic molecule, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-
[2,3-a]quinolizine, to a cationic fluorophore, phenosafranin, has been investigated using steady state absorption as well as steady-state and time-resolved fluorescence techniques. The energy transfer process follows a long range dipole-dipole interaction mechanism. The efficiency of energy transfer has been found to be less than 50%.

 

 

848

 

Synthesis, characterization and biological properties of ruthenium(III) Schiff base complexes derived from 3-hydroxyquinoxaline-2-carboxaldehyde and salicylaldehyde

 

 

 

 

 

 

 

Pearly Sebastian Chittilappilly &
K K Mohammed Yusuff*

 

 

 

 

 

854

 

Synthesis of organoheterobimetallic [Bu2Sn(IV)-Ti(IV)]-μ-oxoisopropoxide and its β-diketonates

 

 

 

 

 

 

 

 

 

 

 

 

 

H K Sharma* & Rajesh Kumar

 

 

 

 

A new organoheterobimetallic-μ-oxoisopropoxide of the type [Bu2SnO2Ti2(Opri)6] has been synthesized by thermal condensation of dibutyltin diacetate and titanium isopropoxide in 1:2 molar ratio in refluxing xylene. The isopropoxy substitution reactions of this compound with β-diketones in different molar ratios (1:1 to 1:4) gives compounds of the type [Bu2SnO2Ti2(Opri)6-nLn] (where n is 1-4 and L = acetylacetonate/ benzoylacetonate anion) respectively.

 

 

 

859

 

Kinetics and mechanism of electron transfer reactions: Oxidation of glyoxylic acid by peroxomonophosphoric acid in acid perchlorate medium

 

 

 

 

 

 

 

N Vijai, D Mala, C L Khandelwal & P D Sharma*

 

 

 

 

The kinetics of oxidation of glyoxylic acid by peroxomono-phosphoric acid in acidic medium is reported. The reaction is second order (first order with respect to each reactant).

 

 

 

 

863

 

Solvent effects and solvation models in the allylation of 2-mercaptobenzimidazole

 

 

 

 

 

 

 

 

 

 

 

T Devender, D Vijaya Bharathi & P Manikyamba*

 

 

 

The second order rate constants of allylation of 2-mercapto­benzimidazole are obtained conductometrically in different protic and aprotic solvents in the temperature range 303-318K.

 

 

 

867

 

Viscosity prediction for R32 and R143a at moderate density regimes via semi-empirically based assessment

 

 

 

 

 

 

 

 

Behzad Haghighi*, Fatemeh Heidari &
Mohammad Mehdi Papari

 

 

 

 

An efficient procedure for calculating transport properties, especially viscosity, at zero density is presented. The interaction potential energies from the inversion procedure reproduce the viscosity within the uncertainty of the best measurements.

 

 

875

 

Announcement

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 


Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 803-807

 

Cyclic conjugation in mono- and dicyclopenta-derivatives of anthracene and phenanthrene

 

Ivan Gutman*, Jelena Đurđević, Boris Furtula & Bojana Milivojević

Received 24 March 2008; revised 6 May 2008

The energy effects of cycles and pairs of cycles in mono- and dicyclopenta-derivatives of anthracene and phenanthrene are computed by a graph-theoretical method. Our results show that there is no significant difference between the extent of cyclic conjugation in anthracene and its cyclopenta-derivative (aceanthrylene) and phenanthrene and its cyclopenta-derivative (acephenanthrylene). In contrast to this, the presence of two cyclopentane rings causes drastic changes in the modes of cyclic conjugation. Our results provide an explanation for the peculiar stability order: dicyclopenta[de,mn] anthracene (never isolated) < dicyclopenta[de,kl]anthracene (stable) <dicyclopenta[jk,mn]phen­anthrene (stable even at >1000oC).

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 808-814

 

Nitrogen-containing carbon nanotubes as a possible hydrogen storage medium

M Sankaran & B Viswanathan*

Received 4 March 2008; revised 7 May 2008

Nitrogen containing carbon nanotubes have been synthesized using a variety of templates. The hydrogen absorption capacity of these materials has been evaluated. The study shows that it is necessary to stabilize nitrogen in the carbon nanotube framework for reproducible hydrogen uptake. The role of nitrogen is to activate gaseous molecular hydrogen and its subsequent transport to the carbon surface by “spill-over” process. Nitrogen sites, in addition to its catalytic role, can also contribute to net hydrogen storage.

IPC Code: Int. Cl.8 B01J20/20; B82B3/00; C01B31/02

 

Indian Journal of Chemistry

Vol. 47, June 2008, pp. 815-820

 

Formation of mesopores in resorcinol-formaldehyde composite resin

 

Mahasweta Nandi, Krishanu Sarkar & Asim Bhaumik*

Received 10 January 2008; revised 12 May 2008

A new nanostructured resorcinol-formaldehyde material has been synthesized by hydrothermal condensation of resorcinol and formaldehyde at 363 K under mild alkaline condition in the presence of supramolecular assembly of cationic surfactant, cetyltrimethylammonium bromide as structure directing agent. The material has been characterized by powderX-ray diffraction, N2 sorption, transmission and scanning electron microscopy , thermogravimetric and differential thermal analysis and UV-vis spectroscopy. The X-ray and TEM image analyses reveal disordered wormhole-like mesostructure with pores of ca. 2.5 nm. These composite materials exhibit photoluminescence property at room temperature, which may be utilized for the fabrication of novel organic optical devices.

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 821-829

 

Vibrational spectroscopic studies supported by HF/DFT calculations of
2,4,6-triaminopyrimidine

N Sundaraganesan*, B Dominic Joshua, C Meganathan & S Sebastian

Received 14 December 2006; revised 19 April 2008

Laser Raman and Fourier transform infrared spectra of 2,4,6-triaminopyrimidine (2,4,6-TAP) have been recorded in the solid phase. The equilibrium geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities, depolarization ratios, reduced masses are calculated by HF and density functional B3LYP method with the6-31G(d,p) basis set. The scaled theoretical wave numbers show good agreement with the experimental values. The thermodynamic functions of the title compound have also been computed at HF/6-31G(d,p) and B3LYP/6-31G(d,p) levels of theory. Detailed interpretation of infrared and Raman spectra of 2,4,6-triaminopyrimidine is reported. The theoretical IR and Raman spectra of the title molecule have been constructed.

IPC Code: Int. Cl.8 G01N21/35

 

Indian Journal of Chemistry

Vol. 47, June 2008, pp 830-835

 

Visible light induced heterogeneous advanced oxidation process to degrade pararosanilin dye in aqueous suspension of ZnO

 

Brijesh Pare*, Pardeep Singh & S B Jonnalagadda

Received 16 January 2008; revised 8 May 2008

The photocatalytic degradation of pararosanilin dye has been investigated under visible light in the presence of aqueous suspension of ZnO under different conditions. The reaction has been studied by monitoring the change in substrate concentration employing visible spectrophotometric analysis as a function of time. The absorbance of dye under investigation is found to decrease in the presence of ZnO and visible irradiation. The degradation of selected dye has been studied under different process variables such as reaction pH, catalyst loading, substrate concentration, light intensity and presence of electron acceptors, and hydroxyl radical scavengers. The rate degradation was strongly influenced by all the above-mentioned parameters. The estimated COD and CO2 values of treated dye sample indicate complete degradation of dye. A slight decrease in pH and gradual increase in conductivity has also been observed during the degradation process. ZnO has been found to be potentially efficient in solar irradiation for the degradation of dye. Kinetic analysis indicates the complex nature of heterogeneous photocatalytic process.

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 836-842

 

Synthesis, characterization and kinetic studies on complex formed between amantadine hydrochloride and sodium molybdate at physiological pH

N Sridevi* & K K Mohammed Yusuff

Received 6 February 2007; revised 12 May 2008

The title reaction was undertaken to establish the interaction between amantadine and molybdate at physiological pH. Identical FTIR spectra, TG-DTA curves and CHN data of the complexes formed from three solutions at pH 1.5, 7.4 and 8.0 indicate that the same complex was formed at all the three pHs. The FTIR spectrum shows shift in peaks corresponding to primary amino group of the drug due to coordination to molybdate. An octahedral geometry is assigned to the complex. The kinetics of the complexation has been studied at low concentrations of the reactants using UV-visible spectrophotometry.  At pH 7.4, the initial rate varies linearly with [molybdate].   A plot of initial rate versus [drug] is linear passing through origin. These results indicate that the drug and molybdate react at pH 7.4 even at low concentrations.  At pH 1.5, the rate increases linearly with increase in [drug] but decreases with [molybdate]. The effect of pH and ionic strength on the rate of the reaction has also been studied. A suitable mechanism has been proposed for the reaction. Reaction between the drug and molybdate even at low concentrations and the fact that the amino group of amantadine required to be free for its function as antiviral, is bound to molybdate in the complex suggests that simultaneous administration of the drug and molybdate supplements should be avoided.

IPC Code: Int. Cl.8  C07F11/00

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 843-847

 

Fluorescence resonance energy transfer from a b-carboline analogue to a cationic photosensitizer in aqueous solution

Paramita Das, Deboleena Sarkar & Nitin Chattopadhyay*

Received 25 January 2008; revised 1 April 2008

Fluorescence resonance energy transfer from a potent bioactive non-ionic molecule, 3-acetyl-4-oxo-6,7-dihydro-12H indolo-[2,3-a]quinolizine, to a cationic fluorophore, phenosafranin, has been investigated using steady state absorption as well as steady-state and time-resolved fluorescence techniques. From the quenching of the donor fluorescence by the acceptor, Stern- Volmer constant has been determined. The energy transfer process follows a long range dipole-dipole interaction mechanism. The energy transfer efficiency, the critical energy transfer distance and the distance between the acceptor and the donor have been determined for the fluorescence resonance energy transfer process.

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 848-853

 

Synthesis, characterization and biological properties of ruthenium(III) Schiff base complexes derived from 3-hydroxyquinoxaline-2-carboxaldehydeand salicylaldehyde

Pearly Sebastian Chittilappilly & K K Mohammed Yusuff*

Received 24 September 2007; revised 26 April 2008

Ruthenium(III) complexes of the Schiff bases derived from 3-hydroxyquinoxaline-2-carboxaldehyde and o-phenylenediamine, o-aminophenol or 2-aminobenzimidazole (qpd, qap and qab, respectively) and the Schiff bases derived from salicylaldehyde and o-phenylenediamine, o-aminophenol or 2-aminobenzi-midazole (salpd, salap and salab, respectively) have been prepared and characterized by elemental, spectral (FT IR, UV-vis, EPR and FAB mass), thermogravimetric, conductance and magnetic moment analyses. The complexes exhibit the following molecular formulae: [Ru2(qpd)Cl4(H2O)2].2H2O, [Ru2(qap)2Cl2(H2O)2].H2O, [Ru2(qab)2Cl4(H2O)2].3H2O, [Ru2(salpd)3Cl2(H2O)2], [Ru2(salap)4Cl2].H2O and [Ru(salab)(H2O)4]Cl2.H2O. An octahedral structure has been tentatively proposed for all the new complexes. The synthesized ligands and complexes have been tested for in vitro growth inhibitory activity against gram positive bacteria Klebsiella pneumoniae, gram negative bacteria Escherichia coli and Pseudomonas aeruginosa. The complexes are active while the ligands are inactive towards the bacteria under study.

IPC Code: Int.Cl.8 C07F15/00; C07C251/02

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 854-858

 

Synthesis of organoheterobimetallic
[Bu2Sn(IV)-Ti(IV)]-μ-oxoisopropoxide and its
β-diketonates

H K Sharma* & Rajesh Kumar

Received 8 October 2007; revised 2 May 2008

A new organoheterobimetallic-μ-oxoisopropoxide of the type [Bu2SnO2Ti2(OPri)6] has been synthesized by the thermal condensation of dibutyltin diacetate and titanium isopropoxide in 1:2 molar ratio in refluxing xylene. The isopropoxy substitution reactions of this μ-oxoisopropoxide compound with β-diketones in different molar ratios (1:1-1:4) gives compounds of the type [Bu2SnO2Ti2(OPri)6-nLn] (where n is 1-4 and L = acetylacetonate/ benzoylacetonate anion) respectively. The μ-oxoisopropoxide compound has been characterized by elemental, spectral analysis (IR, 1H , 13C, 119Sn NMR and mass) and molecular weight data. The β-diketonates of [Bu2SnO2Ti2(OPri)6] have been characterized by elemental, liberated isopropanol and spectral analysis (IR, 1H , 13C NMR).

IPC Code: Int. Cl.8 C07F7/22

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 859-862

 

Kinetics and mechanism of electron transfer reactions: Oxidation of glyoxylic acid by peroxomonophosphoric acid in acid perchlorate medium

N Vijai, D  Mala, C L Khandelwal & P D Sharma*

Received 15 October 2007; revised 11 April 2008

The kinetics of oxidation of glyoxylic acid by peroxomono-phosphoric acid in acidic medium is reported here. The stoichiometry corresponds to the reaction of one mole of peroxomonophosphate for one mole of glyoxylic acid. The reaction is second order (first order with respect to each reactant). The suggested rate law corresponds to the plausible reaction mechanism.

IPC Code: Int. Cl.8 C07B33/00

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 863-866

 

Solvent effects and solvation models in the allylation of 2-mercaptobenzimidazole

T Devender, D Vijaya Bharathi & P Manikyamba*

Received 1 January 2008; revised 7 May 2008

The second order rate constants of allylation of 2-mercapto­benzimidazole are obtained conductometrically in different protic and aprotic solvents in the temperature range 303-318K. Linear multiple regression analysis results in the LSER log kII = –8.633 + 11.032Y + 6.958P + 0.189a (n = 11, R = 0.931), suggesting that the transition state is more solvated than the reactants due to polarity, polarisability and hydrogen bond donor ability of the solvent.

 

Indian Journal of Chemistry

Vol. 47A, June 2008, pp. 867-874

 

Viscosity prediction for R32 and R143a at moderate density regimes via semi-empirically based assessment

 

Behzad Haghighi*, Fatemeh Heidari & Mohammad Mehdi Papari

Received 24 May 2007; re-revised 1 May 2008

An efficient procedure for calculating transport properties, especially viscosity, at zero density is presented. The extended corresponding states approach of Huber et al. [Huber M L, Laesecke A & Perkins R A, Ind Eng Chem Res, 42 (2003) 3163] has been used for evaluating the viscosity coefficients for gaseous state of R32 and R143a in moderate-density regime. The Lennard-Jones 12-6 (LJ 12-6) potential energy function has been used as the initial model potential required by the technique. The interaction potential energies from the inversion procedure reproduce the viscosity within the uncertainty of the best measurements.