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)

 

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VOLUME 50A

NUMBER 1

January 2011

CONTENTS

Papers

 

9

 

Electro-active ternary copolymer design using genetic algorithm

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Avneet Kaur & A K Bakhshi*

 

 

 

For designing low band gap conducting polymers, genetic algorithm, coupled with negative factor counting technique and inverse iteration method, has been used to optimize the properties of novel ternary copolymers.

 

15

 

A new electrochemical sensor based on W-doped titania-CNTs composite for detection of pentachlorophenol

 

 

 

 

 

 

 

 

 

 

 

 

 

 

W Q Zhang, G B Zhu, J Y Ma, X H Zhang* &
J H Chen
*

 

 

 

W-doped TiO2-CNTs composite based electrochemical sensor for determination of pentachlorophenol shows good analytical performance with the linear response range from 0.4-3.0 μM, detection limit of 0.011 μM, high sensitivity and good stability.

 

22

 

Synthesis, structure and reactivity of a
selenoxide derived from a bulky selenide:
Bis(2,4,6-trimethylphenyl) selenoxide

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ninad Ghavale, Prasad P Phadnis, Amey Wadawale & Vimal K Jain*

 

 

 

Bis(2,4,6-trimethylphenyl) selenoxide has been synthesized by oxidation of bis(2,4,6-trimethylphenyl) selenide with aqueous H2O2. Single crystal X-ray diffraction analysis reveals that the selenium atom adopts a trigonal pyramidal configuration.  Reaction of the selenoxide with thiols at room temperature regenerates the selenide.

 

 

27

 

Monodentate bulky trinaphthylphosphine as ligand in Rh, Co and Ru catalyzed hydroformylation of
1-hexene

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Aasif A Dabbawala, Dharmesh U Parmar,
Hari C Bajaj* & Raksh V Jasra

 

 

 

Catalytic application of Rh, Co, Ru complexes of a monodentate bulky phosphine ligand, trinaphthylphosphine, has been investigated for hydroformylation of 1-hexene.

 

 

33

 

Effect of calcination temperature on the catalytic activity of Pd/Ce0.8La0.2Oδ/cordierite monolithic catalyst for toluene combustion

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yongjiao Wang, Yiming He, Mengfei Luo, Lei Yue, Botao Teng & Leihong Zhao*

 

 

 

Pd/Ce0.8La0.2Oδ/cordierite monolithic catalyst calcined at 500 °C shows the highest activity for toluene combustion (up to 90 %)
at 210 °C.

 

Notes

 

38

 

Reactivity of Ru-edta complexes with
DNA fragments and thioaminoacids:
Kinetic and mechanistic studies

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Debabrata Chatterjee

 

 

 

Reaction of [RuIII(edta)SR]2- with 5˘ nucleotides shows the binding of nucleotides to the ruthenium centre by removing the coordinated thio molecules.

 

 

 

41

 

A novel route to size and shape controlled synthesis of DMSO capped ruthenium dioxide nanoparticles

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Geetika Borah* & Ponchami Sharma

 

 

 

 

Ruthenium dioxide nanoparticles are readily synthesized from RuCl3.xH2O via the formation of ruthenium acetylacetone.  Particle size increases with increase in calcination time at 800 °C with change of morphology. DMSO capped RuO2 nanoparticles have also been synthesized and found to be soluble in chloroform and acetone.

 

 

 

46

 

Experimental and theoretical studies on sensing adenine by Ag, Au and Ag-Au bimetallic nanoparticles

 

 

 

 

 

 

 

 

 

 

 

J Arikrishnan, S K Tabasum Sheerin,
M Murugavelu & B Karthikeyan
*

 

 

 

 

Sensing adenine by silver, gold and silver-gold bimetallic colloidal nanoparticles is due to the adsorption of adenine on the nanometallic surface through the chemisorption.

 

 

 

 

51

 

Three new inorganic-organic hybrid materials based on inorganic cluster, [(PO4)M12O36].nH2O
(M = Mo, W)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Mohammad Yousefi*, Hossein Eshtiagh-Hosseini, Masoud Mirzaei, Ali R Salimi & Mohsen Nikpour

 

 

 

 

Heteropolyoxometalates based inorganic-organic hybrids have been synthesized and characterized. These hybrids contain infinite planes of inorganic moiety. The van der Waals interactions hold the organic moieties in the vacancies in the polyoxometalates crystalline network.

 

 

 

55

 

Synthesis and characterization of metal and metal oxide sponges using Triton X–165 as sacrificial template

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Farid Khan* & Ruchi Bilgainya

 

 

 

Silver, gold and copper oxide monoliths have been prepared by the sacrificial template route using Triton X-165 as surfactant. Dextran, TMB and silica nanoparticles have also been encapsulated to design monoliths for diverse applications.

 

 

 

 

60

 

Guide to Authors

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

Indian Journal of Chemistry

Vol. 50A, January 2011, pp. 9-14

 

Electro-active ternary copolymer design using genetic algorithm

Avneet Kaur & A K Bakhshi*

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

Email: akbakhshi2000@yahoo.com

Received 22 September 2010; revised and accepted 20 December 2010

Genetic algorithm has been applied for obtaining the optimal solution for a copolymer with minimum band gap and maximum delocalization. The results for a case study of ternary copolymers belonging to type II staggered class are presented. A comparative study of the results obtained using two alternative definitions of fitness function has also been made. It is seen that the ionization potential of the homopolymers is the determining factor in the percentage ratios of the optimum solution. The results obtained by genetic algorithm constitute an informative set which the designer of conducting polymers can use for a more informed decision.

Keywords: Theoretical chemistry, Polymers, Conducting polymers, Copolymers, Electronic properties, Genetic algorithm

 

Indian Journal of Chemistry

Vol. 50A, January 2011, pp. 15-21

 

A new electrochemical sensor based on W-doped titania-CNTs composite for detection of pentachlorophenol

W Q Zhang, G B Zhu, J Y Ma, X H Zhang* & J H Chen*

State Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry and Chemical Engineering,
Hunan University, Changsha, 410082, PR China

Email: chenjinhua@hnu.cn/guoxin512@tom.com

Received 23 September 2010; revised and accepted 17 December 2010

W-doped titania-carbon nanotubes composites have been prepared by a modified sol-gel method and characterized by scanning electron microscopy, energy dispersive X-ray spectroscopy and X-ray diffraction spectroscopy. Based on these W-doped TiO2-CNTs composites, a new electrochemical sensor has been developed for determination of pentachlorophenol, which shows good analytical performance with the linear response range from 0.4-3.0 μM, detection limit of 0.011 μM, high sensitivity and good stability.

Keywords: Electrochemistry, Electrooxidation, Carbon nanotubes, Nanotubes, Sensors, Titania, Pentachlorophenol, Tungsten doping

 

Indian Journal of Chemistry

Vol. 50A, January 2011, pp. 22-26

 

Synthesis, structure and reactivity of a selenoxide derived from
a bulky selenide: Bis(2,4,6-trimethylphenyl) selenoxide

Ninad Ghavale, Prasad P Phadnis, Amey Wadawale & Vimal K Jain*

Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400 085, India

Email: jainvk@barc.gov.in

Received 3 November 2010 ; revised and accepted 22 December 2010

Bis(2,4,6-trimethylphenyl) selenoxide has been synthesized by oxidation of bis(2,4,6-trimethylphenyl) selenide with aqueous H2O2 and characterized by elemental analysis and NMR spectroscopy (1H, 13C{1H} and 77Se{1H}). The single crystal X-ray diffraction analysis reveals that the selenium atom adopts a trigonal pyramidal configuration. The reactions of bis(2,4,6-trimethylphenyl) selenoxide with various thiols and other proton donor species in CDCl3 have been studied by 77Se{1H}; NMR spectroscopy that with thiols at room temperature regenerated the selenide. The data indicate that the selenoxide acts as a hydrogen bond acceptor to give Mes2Se=OHX (Mes = 2,4,6-trimethylphenyl or mesityl) species.

Keywords: Coordination chemistry, Organometallic chemistry, Organoselenium compounds, Selenoxides, NMR spectroscopy, X-ray diffraction

 

Indian Journal of Chemistry

Vol. 50A, January 2011, pp. 27-32

 

Monodentate bulky trinaphthylphosphine as ligand in Rh, Co and Ru catalyzed hydroformylation of 1-hexene

Aasif A Dabbawala, Dharmesh U Parmar, Hari C Bajaj* & Raksh V Jasra

Discipline of Inorganic Materials and Catalysis, Central Salt and Marine Chemicals Research Institute,
Council of Scientific and Industrial Research (CSIR), G B Marg, Bhavnagar 364 021, Gujarat, India

Email: hcbajaj@csmcri.org

Received 20 September 2010; revised and accepted 14 December 2010

Rhodium, cobalt, and ruthenium complexes of monodentate bulky trinaphthylphosphine ligand, PNp3, have been synthesized and used as catalysts for the hydroformylation of 1-hexene. The catalyst, RhCl(PNp3)3 shows excellent hydroformylation activity as compared to the Co/PNp3 and Ru/PNp3 system. The high conversion (99 %) with high selectivity to aldehydes (97 %) is achieved by RhCl(PNp3)3 catalyst whereas RuCl2(PNp3)3 is more active toward hydrogenation rather than hydroformylation.

Keywords: Catalysis, Hydroformylation, Monodentate bulky phosphines, Phosphines, Rhodium, Cobalt, Ruthenium, Hexene, Aldehydes

 

Indian Journal of Chemistry

Vol. 50A, January 2011, pp. 33-37

 

Effect of calcination temperature on the catalytic activity of Pd/Ce0.8La0.2Oδ/cordierite monolithic catalyst for toluene combustion

 

Yongjiao Wanga, Yiming Heb, Mengfei Luoa, Lei Yuea, Botao Tenga & Leihong Zhao a, *

aZhejiang Key Laboratory for Reactive Chemistry on Solid Surfaces, Institute of Physical Chemistry,
Zhejiang Normal University, Jinhua 321004, PR China

Email: zhaoleihong@163.com

 bDepartment of Materials Physics, Zhejiang Normal University, Jinhua 321004, PR China

Received 20 July 2010; revised and accepted 14 December 2010

The effect of calcination temperature of the Pd/Ce0.8La0.2Oδ/cordierite monolithic catalysts, prepared by impregnation method, on the catalytic activity for toluene combustion has been investigated. The catalyst calcined at 500 °C exhibits the highest activity, with toluene conversion up to 90 % at 210 °C. All samples are characterized by XRD, BET, Raman, and H2-TPR techniques. The characterization results match the behavior of the catalytic activity well. The catalysts present high thermal stability due to the formation of CeO2-La2O3 solid solution. The PdO phase is stable at 1000 °C.

Keywords: Catalysts, Monolithic catalysts, Toluene combustion, Palladium catalysts, Ceria

 

Indian Journal of Chemistry

Vol. 50A, January 2011. pp. 46-50

 

Experimental and theoretical studies on sensing adenine by Ag, Au and Ag-Au bimetallic nanoparticles

J Arikrishnan, S K Tabasum Sheerin, M Murugavelu & B Karthikeyan*

Department of Chemistry, Annamalai University, Annamalainagar 608 002, India

Email: bkarthi_au@yahoo.com

Received 26 March 2010; re-revised and accepted 28 December 2010

Experimental and theoretical studies on sensing adenine by silver, gold and silver-gold bimetallic nanoparticles are reported. UV-visible spectroscopy has been used to study the surface plasmon resonance changes. The vibrational frequencies of adenine and silver complexed adenine have been compared with the HF theoretically calculated frequencies. It is demonstrated that adenine is adsorbed on the nanometallic surfaces through chemisorption and this property can be effectively used to sense adenine.

 

Keywords: Analytical chemistry, Theoretical chemistry, Adenine, Gold, Silver, Nanomaterials, Colloids, Bimetallic nanoparticles, Vibrational spectroscopy.

 

Indian Journal of Chemistry

Vol 50A, January 2011, pp. 51-54

 

Three new inorganic-organic hybrid materials based on inorganic cluster, [(PO4)M12O36].nH2O (M = Mo, W)

Mohammad Yousefia, *, Hossein Eshtiagh-Hosseinib, Masoud Mirzaeib &  Ali R. Salimib & Mohsen Nikpourc

aDepartment of Chemistry, Islamic Azad University,  Shahr-e Rey Branch, Tehran, Iran

Email: myousefi50@yahoo.com

bDepartment of Chemistry, School of Sciences, Ferdowsi  University of Mashhad, Mashhad, P.O. Box 917791436, Iran

Email: mirzaei487@yahoo.com

cDepartment of Chemistry, School of Sciences, Islamic Azad University, Ahvaz Branch, Ahvaz, 61349-68875, Iran

Received 5 July 2010, revised and accepted 20 December 2010

Three new inorganic-organic hybrid materials based on  heteropolyoxometalates,
[L-C6H14NO2]3[(PO4)Mo12O36].3H2O (1),
[L-C5H10NO2]3[(PO4)W12O36].H2O (2), and [C2H7N2O]3[(PO4)W12O36].4H2O (3), where C6H14NO2, C5H10NO2, and C2H7N2O are protonated
l-leucine, l-proline, and methyl urea, respectively, have been synthesized and structurally characterized by some physico-chemical methods. Elemental analyses, IR, Raman, mass, UV, and 1H NMR spectroscopies of the title hybrid materials indicate that there are van der Waals interactions between O atoms of the heteropolyoxometalates and water molecules, as well as the N and O atoms of the amino acids and methyl urea moieties.
The molecular structures of synthesized hybrid materials contain discrete entities of l-leucinium,  l-prolinium or methyluronium and water molecules that surround every [(PO4)M12O36]3- anion, over the extended crystalline  network. The observed bands in Raman spectra of (2) and (3) demonstrate that the [(PO4)W12O36]3- anion retains its “Keggin structure”. At pH = 4 – 7, the characteristic bands of the Keggin anion [(PO4)M12O36]3−(M = Mo, W) appear at 210 and 260 nm in the UV spectra, respectively.

 

Keywords: Polyoxometalates, Metalates, Hybrids, Inorganic-organic hybrids, Amino acids, l-Leucine, l-Proline, Methyl urea

 

Indian Journal of Chemistry

Vol. 50A, January 2011, pp. 55-59

 

Synthesis and characterization of metal and metal oxide sponges using Triton X-165 as sacrificial template

Farid Khan* & Ruchi Bilgainya

Nanomaterials Discovery Laboratory, Department of Chemistry, Dr. HariSingh Gour Central University, Sagar 470 003, India

Email: faridkhan58@yahoo.com/ farid.fk@rediffmail.com

Received 25 June 2010; revised and accepted 24 December 2010

Silver, gold and copper oxide sponges have been synthesized via thermal treatment using Triton X–165 as sacrificial template. Scanning electron microscopy, X-ray diffraction, Thermogravimetric analysis and Brunauer–Emmett-Teller adsorption isotherms techniques are used to characterize the monoliths. Additives like dextran, silica nanoparticles and 1,3,5 trimethylbenzene significantly affect the pore size of the monoliths from 50 nm to 50 µm. The surface area of Au/Triton X-165 / dextran monolith has been determined to be 8.26 m2/g, which is greater than that of any pure metal.

 

Keywords: Composites, Oxides, Sponges, Porous metals