Indian Journal of Chemistry

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

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VOLUME 48A

NUMBER 1

January 2009

CONTENTS

 

9

 

Synthesis, crystal structure and DNA cleavage activity of (aqua)bis(dipyridophenazine) copper(II) complex

 

 

 

 

 

 

 

 

 

 

 

M S Ameerunisha Begum, Sounik Saha,
Akhtar Hussain & Akhil R Chakravarty*

 

 

 

 

The dipyridophenazine complex, [CuII(dppz)2(H2O)](ClO4)2, is prepared and structurally characterized by X-ray crystallography. It binds at the DNA major groove and cleaves DNA by both hydrolytic and oxidative pathways under different reaction conditions.

 

 

15

 

Insight into bio-physiological functions of acid phosphatase from potatoes (Solanum tuberosum):
A bioanalytical approach

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sandhya Y Rane*, Kirti D Badave &
Khursheed Ahmed

 

 

 

 

Quantification of iron species of APase from Solanum tuberosum is investigated with (E2) and without (E1) Chelex-100 column treatment. Biphasic release of Fe2+ + Fe3+ from E1 and of Fe3+ species from E2 at co-catalytic and catalytic sites correlate metal constellation ratio with biological activity as (Fe2+/Mn2+/Zn2+/Cu2+) 70 %: Fe3+ 30 %:: 70:30 (BA). At the same time, decrease in cleavage activity on the pUC-19 plasmid DNA from 74 to 65 % after removal of M2+ ions shows a major role of Fe3+-Tyr function in the physiological activity of APase as compared to co-catalytic M2+ ions at its active site.

 

 

                             1          2          3          4         5

 

 

 

25

 

Cobalt and nickel complexes of a hypodentate ligand, 2-[3-(pyridylamino)phenylazo]pyridine: Synthesis, structure and properties

 

 

 

 

 

 

 

 

 

 

 

 

 

Priyabrata Banerjee, Shie-Ming Peng,
Gene Hsiang Lee & Sreebrata Goswami*

 

 

 

 

Reactions of MCl2.nH2O (M = Co, Ni), with the extended azoaromatic ligand, 2-[3-(pyridylamino)phenylazo]pyridine (HL1), afford the mononuclear complexes, [M(L1)2]m+ (M=Co, m=1 and M=Ni, m=0), in high yields.

 

 

30

 

A new chelating polymer with 2-methoxy-1-imidazolylazobenzene functionality for determination of lead(II) and iron(III)

 

 

 

 

 

 

 

 

 

 

S Pramanik, S Sarkar, H Paul &
P Chattopadhyay*

 

 

 

 

A new chelating polymer functionalized with 2-methoxy-1-imidazolylazobenzene has been synthesized and characterized and its sorption capacity towards Fe(III), Cu(II), Zn(II), Cd(II) and Pb(II) as a function of pH has been studied. The resin exhibits no affinity for alkali or alkaline earth metal ions. Estimation of lead in trace quantities in road dust and different biological samples, and, of iron in river water has been carried out successfully. The LOD (corresponding to 3s) for Fe(III) is
0.05 mg L–1 and that for Pb(II) is 0.08 mg L–1.

 

 

 

38

 

Coordination equilibria of mixed ligand complexes of CuII with glycylglycine and biguanide

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

T Roy Barman & G N Mukherjee*

 

 

 

 

Spectrophotometric and computer based pH metric investigations on the mixed ligand complex formation equilibria of CuII with glycylglycine (HGG±) and biguanide (Bg) in aqueous solution at 25±1°C and at fixed ionic strength, I = 0.1 mol dm-3 (NaNO3), in different molar proportions, indicate the formation
of [Cu(GG)(H2O)2], [Cu(GG-H)(H2O)], [Cu(Bg-H)(OH)],
[Cu(GG-H)(Bg)], [Cu(GG-H)(Bg-H)-], [Cu2(GG-H)2(Bg)], [Cu2(GG-H)2(Bg-H)-] and [Cu2(GG-H)2(Bg-2H)2-] complexes. Shifting of the electronic λmax of CuII with increase in
pH correlates with a meridonial-facial isomeric equilibrium in the coordination modes of amide deprotonated glycylglycinate dianion in [Cu(GG-H)(Bg)]. Existence of the binuclear mixed ligand complexes indicates basket-like bridging double bidentate [(H21N, =4NH), (=2NH, 5NH2)] mode of chelation by the biguanide species.

 

Notes

 

45

 

Structural volume change upon photoisomerization of  2,2´-furil: A photoacoustic calorimetric study

 

 

 

 

 

 

 

 

 

Deboleena Sarkar, Alok Chakrabarty &
Nitin Chattopadhyay*

 

 

 

 

The cis-skew trans-planar photoisomerization of
1, 2-di(furan-2-yl)ethane-1, 2-dione (2, 2´-furil) in the photoexcited triplet state has been investigated by photoacoustic calorimetry in a series of n-alkane solvents at room temperature. The photoisomerization process is associated with a structural volume change of the probe. The study reveals that an expansion in volume occurs during the photoinduced isomerization process. In low polarity alkane solvents, electrostrictional contribution to the estimated volume change has been argued to be negligible.

 

 

 

51

 

Sonochemical fabrication and optical properties of ZnO stelliform dendrites containing Bi2O3

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Zhifu Wu, Yuhua Shen*, Anjian Xie,
Fangzhi Huang, Yan Cai & Shikuo Li

 

 

 

 

Sonochemical synthesis and optical properties of the ZnO-Bi2O3 nanocomposite is reported. SEM and TEM studies show the morphology to be stelliform dendrite. Also, the presence of Bi3+ is vital for formation of the stelliform dentrites.

 

 

 

 

57

 

A comparative study of partial molar volumes of some hydrated and anhydrous salts of transition metal sulphates and magnesium sulphate in water at different temperatures

 

 

 

 

 

 

 

 

 

M L Parmar*, Praveen Sharma & M K Guleria

 

 

 

 

Partial molar volumes of some hydrated and anhydrous salts of cobalt sulphate, nickel sulphate, copper sulphate, zinc sulphate and magnesium sulphate have been determined in water at different temperatures (298.15, 303.15, 308.15, 313.15 and 318.15 K). The partial molar volumes and experimental slopes have been interpreted in terms of ion-solvent and ion-ion interactions, respectively. The partial molar volumes vary with temperature as a power series of temperature. The hydrated salts act as structure makers while anhydrous salts act as structure breakers in water.

 

 

63

 

 

Conductance studies on some alkali metal acetates in aqueous glycerol solutions

 

 

 

 

 

 

 

 

 

 

 

Bipul Kumar Sarkar, Mahendra Nath Roy* & Biswajit Sinha*

 

 

 

Molar conductances of lithium acetate, sodium acetate,
potassium acetate, sodium bromide, sodium tetraphenylborate and tetrabutylammonium bromide in a series of glycerol + water mixtures at temperatures from 298.15 to 318.15 K are reported. The small values of association constants for all the electrolytes studied indicate their weak association in aqueous glycerol mixtures, which is in line with the high dielectric constants of the solvent media.

 

 

69

 

Fabrication of Gd2O3Eu3+ nanofibers by electrospinning

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

X Y Zhang, C Z Zhao, L Y Chai & W Liu*

 

 

 

 

One-dimensional Gd2O3:Eu3+ nanofibers with cubic phase have been prepared as potential red phosphors by an electrospinning technique. The main emission position is centered at 611 nm
(5D0 7F2). Photoluminescence spectra indicate that fluorescence capability improves with increase in temperature.

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 9-14

 

 

Synthesis, crystal structure and DNA cleavage activity of (aqua)bis(dipyridophenazine)copper(II) complex

M S Ameerunisha Begum, Sounik Saha, Akhtar Hussain & Akhil R Chakravarty*

Department of Inorganic & Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India

Email: arc@ipc.iisc.ernet.in

Received 7 November 2008; accepted 3 December 2008

A copper(II) complex of dipyridophenazine, viz., [Cu(dppz)2(H2O)](ClO4)2 (1), has been prepared and structurally characterized by X-ray crystallography. The crystal structure of the complex shows a five-coordinate structure in which two N,N-donor dipyridophenazine (dppz) and one aqua ligand bind to the copper(II) center giving Cu-O and Cu-N bond distances in the range of 1.981(6) to 2.043(6) Å. The ESI-MS spectrum of 1 in MeCN shows a peak at m/z value of 313 (100%) indicating the dissociation of the aqua ligand in the solution phase. The complex is one-electron paramagnetic (meff, 1.86 mB). It displays a quasi-reversible Cu(II)/Cu(I) redox process at 0.096 V. The complex is an avid binder to CT DNA giving a binding constant value of 3.5 × 105 M -1. It shows significant hydrolytic cleavage of supercoiled pUC19 DNA in dark in the absence of any external agents. The complex exhibits chemical nuclease activity on treatment with 3-mercaptopropionic acid as a reducing agent forming hydroxyl radicals. Complex 1 is a model synthetic nuclease and hydrolase showing both modes of DNA cleavage under different reaction conditions. The DNA cleavage activity of 1 is significantly better than its phen analogue but similar to that of the bis-dpq complex.

Keywords: Bioinorganic chemistry, Hydrolytic cleavage, DNA cleavage, DNA binding, Crystal structure, Copper

IPC code: Int. Cl.8  C07F1/08; C12N15/00

 

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 15-24

 

 

Insight into bio-physiological functions of acid phosphatase from potatoes (Solanum tuberosum): A bioanalytical approach

 

Sandhya Y Rane*, Kirti D Badave & Khursheed Ahmed

Department of Chemistry, University of Pune, Pune 411 007, India

Email: syrane@chem.unipune.ernet.in

Received 16 September 2008; revised 5 December 2008

The molecular mass of acid phosphatase (APase) from Solanum tuberosum is estimated as 111 kDa using denaturing SDS-PAGE. The prime catalytic di-iron Fe2+/Fe3+ site (1.62 ± 0.2 mole) together with the co-catalytic sites of manganese, zinc and trace copper (0.397 ± 0.135 mole) in the enzyme have been determined by the GF-AAS technique. The quantitation of the biphasic release of iron species from the enzyme has been carried out spectrophotometrically. The reduction (~70-72%) in biological activity of APase after removal of the divalent metal constellation of co-catalytic site made up of Fe2+, Mn2+, Cu2+ and Zn2+ is established after duplicate treatment of enzyme from a Chelex-100 column. The significance of redox active Fe2+/Fe3+ metal cofactors at the active site of the enzyme correlates well with the affinity of substrate binding towards the di-iron site in terms of kinetic parameters. A physiological defense activity of APase is established in terms of its quantitative pUC-19 plasmid DNA cleavage activity.

Keywords:     Bioinorganic chemistry, Enzyme activity, Enzyme catalysis, DNA cleavage, Acid phosphatase, Copper, Iron, Manganese, Zinc

IPC Code:      Int. Cl.8 C07F15/02; C12N9/00; C12N15/00

 

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 25-29

 

 

Cobalt and nickel complexes of a hypodentate ligand,
2-[3-(pyridylamino)phenylazo]pyridine: Synthesis, structure and properties

Priyabrata Banerjeea, Shie-Ming Pengb, Gene Hsiang Leeb & Sreebrata Goswamia,*

aDepartment of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata 700 032, India

Email: icsg@iacs.res.in

bDepartment of Chemistry, National Taiwan University, Taipei, Taiwan, Republic of China

Received 7 November 2008; accepted 3 December 2008

Reactions of the salts MCl2∙nH2O (M = Co, Ni), with the extended azoaromatic ligand, 2-[3-(pyridylamino)- phenylazo]pyridine (HL1) afford the mononuclear complexes, [M(L1)2]m+ ( M=Co, m=1 and M=Ni, m=0) in high yields. X-ray structure of the nickel complex is reported. The structural analysis has revealed that two monoanionic ligands [L1]- bind the metal centre in a N6-fashion using pairs of pyridyl-N, azo-N and deprotonated arylamido-N atoms. The two N(py) atoms (of the 3-amino pyridyl function) remain as pendents and unused. Positive ion ESI mass spectra of the complexes provide evidence for the integrity of the complexes in solution. Their UV-visible spectra consist of intense transitions in the low energy area of the visible region. Cyclic voltammetry of these complexes displays multiple reversible waves. The Co(III)/Co(II) reduction and Ni(II)/Ni(III) oxidation in their respective complexes appear at - 0.24 and 0.57V, respectively.

Keywords: Cobalt, Nickel, Hypodentate ligands, Azo compounds, X-ray structure

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

 

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 30-37

 

 

A new chelating polymer with 2-methoxy-1-imidazolylazobenzene functionality for determination of lead(II) and iron(III)

S Pramanika, S Sarkarb, H Paulb & P Chattopadhyayb,*

aHooghly Women’s College, Pipulpati, Hooghly 712 103, India

bDepartment of Chemistry, The University of Burdwan, Burdwan 713 104, India

Email: pabitracc@yahoo.com

Received 3 October 2008; revised 10 December 2008

A new chelating polymer functionalized with 2-methoxy-1-imidazolylzobenzene has been synthesized and characterized by elemental analysis, infrared spectra, thermogravimetric analysis, hydrogen ion capacity and sorption capacity for different metal ions. The sorption capacity of the resin towards Fe(III), Cu(II), Zn(II), Cd(II) and Pb(II) as a function of pH has been studied. The resin exhibits no affinity for alkali or alkaline earth metal ions. Separation and estimation of lead in trace quantities in road dust and different biological samples at pH 3.0 by AAS has been carried out. Determination of iron in river water at pH 5.0 and removal of Fe(III) from well-water spiked with 59Fe as tracer have been successfully performed using this resin. LOD (corresponding to 3s) for Fe(III) is 0.05 mg L-1 and that for Pb(II) is 0.08 mg L-1.

Keywords: Analytical chemistry, Ion exchange, Azo compounds, Chelating polymers, Sorption capacity, Lead, Iron

IPC Code: Int. Cl.8 B01J39/00; C07C245/08; C08G18/85

 

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 38-44

 

 

Coordination equilibria of mixed ligand complexes of CuII with glycylglycine and biguanide

T Roy Barman & G N Mukherjee*

Department of Chemistry, University of Calcutta, University College of Science

92, Acharya Prafulla Chandra Road, Kolkata 700 009, India

Email: gmchem@rediffmail.com

Received 28 May 2008; revised and accepted 17 December 2008

Spectrophotometric and computer based pH metric investigations on the mixed ligand complex formation equilibria of CuII with glycylglycine [(H3+NCH2CONHCH2COO-), HGG±] and biguanide [(H21N C(=2NH) 3NH C(=4NH) 5NH2), Bg] in aqueous solution at 25±1°C at a fixed ionic strength, I = 0.1 mol dm-3 (NaNO3) in different molar proportions, indicate the formation of [Cu(GG)(H2O)2], [Cu(GG-H)(H2O)], [Cu(Bg-H)(OH)], [Cu(GG-H)(Bg)], [Cu(GG-H)(Bg-H)-], [Cu2(GG-H)2(Bg)], [Cu2(GG-H)2(Bg-H)-], [Cu2(GG-H)2(Bg-2H)2-] complexes. Shifting of electronic spectral λmax of CuII with increase in pH correlates with a meridonial-facial isomeric equilibrium in the coordination modes of amide deprotonated glycylglycinate dianion, GG-H2-, in [Cu(GG-H)(Bg)]. Existence of the binuclear mixed ligand complexes indicates basket-like bridging double bidentate [(H21N, =4NH), (=2NH, 5NH2)] mode of chelation by the biguanide species.

Keywords: Solution chemistry, Coordination equilibria, Mixed ligand complexes, Copper, Glycylglycine, Biguanide

 

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 45-50

 

 

Structural volume change upon photoisomerization of 2,2´-furil:
A photoacoustic calorimetric study

Deboleena Sarkar, Alok Chakrabarty & Nitin Chattopadhyay*

Department of Chemistry, Jadavpur University, Kolkata 700 032, India

Email: nitin.chattopadhyay@yahoo.com

                                                  Received 8 September 2008; revised 15 December 2008

The cis-skew trans-planar photoisomerization of 1, 2-di(furan-2-yl)ethane-1, 2-dione (2, 2´-furil), a 1,2-dicarbonyl compound, in the photoexcited triplet state has been investigated by photoacoustic calorimetry in a series of n-alkane solvents at room temperature. The photoisomerization process is associated with a structural volume change of the probe. This has been evaluated and compared with the theoretically calculated volumes of cis and trans geometries of furil. The study reveals that an expansion in volume occurs during the photoinduced isomerization process. In low polarity alkane solvents, electrostrictional contribution to the estimated volume change has been argued to be negligible.

 

Keywords: Photochemistry, Photoisomerization, Photoacoustic calorimetry, Structural volume change. Furil,   Dicarbonyls

 

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 51-56

 

 

Sonochemical fabrication and optical properties of ZnO stelliform dendrites containing Bi2O3

Zhifu Wua, b, Yuhua Shena,c,*, Anjian Xiea, c, Fangzhi Huanga, Yan Caia & Shikuo Li a

aSchool of Chemistry and Chemical Engineering, Anhui University, 230039, Hefei, PR China

Email: s_yuhua@163.com / zhifuwu2005@yahoo.com.cn

bDepartment of Chemistry, Anyang Normal College, 455 002, Anyang, PR China

cState Key Laboratory of Coordination Chemistry,
Nanjing University, Nanjing, 210093, PR China

Received 5 July 2008; revised and accepted 23 December 2008

Sonochemical synthesis and optical properties of the ZnO-Bi2O3 nanocomposite materials have been reported. SEM and TEM studies show the morphology to be stelliform dendrite. The sonication time appears to be a critical parameter for shape determination. Also, the presence of Bi3+ is vital to the formation of the stelliform dentrites. UV and photoluminescence spectra at room temperature of the products show that the synthesized materials possess good optical properties. The mechanism of the stelliform dendrite growth has also been discussed.

 

Keywords:  Luminiscence, Photoluminescence, Sonication, Ceramics, Nanocomposites, Composites, Dendrites, Stelliform dendrites, Oxides, Zinc, Bismuth

IPC Code: Int. Cl.8 B01J19/10; C04B35/71; C04B35/453

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 57-62

 

A comparative study of partial molar volumes of some hydrated and anhydrous salts of transition metal sulphates and magnesium sulphate in water at different temperatures

M L Parmar*, Praveen Sharma & M K Guleria

Department of Chemistry, Himachal Pradesh University, Summer Hill, Shimla 171 005, India

Received 28 July 2008; accepted 14 December 2008

Partial molar volumes of some hydrated and anhydrous salts of transition metal sulphates, viz., cobalt sulphate, nickel sulphate copper sulphate, zinc sulphate and magnesium sulphate have been determined in water at five equidistant temperatures (298.15, 303.15, 308.15, 313.15 and 318.15 K). The density data have been analysed by means of Mason’s equation. The partial molar volumes () and experimental slopes () have been interpreted in terms of ion-solvent and ion-ion interactions, respectively. The partial molar volumes vary with temperature as a power series of temperature. Structure-making/breaking capacities of hydrated and anhydrous salts have been inferred from the sign of , i.e., the second derivative of partial molar volume with respect to temperature at constant pressure. The hydrated salts act as structure makers while anhydrous salts act as structure breakers in water, i.e., the behaviour is reversed on removal of water of crystallization.

 

Keywords: Solution chemistry, Electrolytes, Partial molar volume, Cobalt, Nickel, Copper, Zinc, Manganese

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 63-68

 

 

Conductance studies on some alkali metal acetates in aqueous glycerol solutions

 

Bipul Kumar Sarkar, Mahendra Nath Roy a, * & Biswajit Sinhab, *

Department of Chemistry, University of North Bengal, Darjeeling 734 013, India

Email: amahendraroy2002@yahoo.co.in, bbiswachem@gmail.com

 

Received 21 July 2008; revised and accepted 11 December 2008

Molar conductance of lithium acetate, sodium acetate, potassium acetate, sodium bromide, sodium tetraphenylborate and tetrabutylammonium bromide in a series of glycerol + water mixtures at temperatures from 298.15 K to 318.15 K has been reported. The limiting polar conductances, association constants and cosphere diameter have been derived from the Lee-Wheaton conductivity equation. The limiting ionic conductivities have been calculated by reference electrolyte method. Ionic conductivities of cations and anions are discussed in terms of solvent viscosity, the Stokes radii and ion-ion and ion-solvent interactions. The small values of association constants for all the electrolytes studied indicate their weak association in aqueous glycerol mixtures, which is in line with the high dielectric constants of the solvent media.

 

Keywords: Conductivity, Ionic conductivity, Transport properties

 

 

Indian Journal of Chemistry

Vol. 48A, January 2009, pp. 69-72

 

 

Fabrication of Gd2O3Eu3+ nanofibers by electrospinning

X Y Zhang, C Z Zhao, L Y Chai & W Liu*

College of Materials Science and Engineering, Shandong University of Technology, Zibo, 255049,

PR China

Email: wliu7777@sdut.edu.cn

Received 12 May 2008; revised and accepted 12 December 2008

One-dimensional Gd2O3:Eu3+ nanofibers with cubic phase have been prepared as potential red phosphors by an electrospinning technique, and characterized by scanning electron microscopy, X-ray diffraction, FT-IR, TGA-DTA and photoluminescence spectra. The effect of annealing temperature on the crystallization and luminescence properties has been studied. The main emission position is centered at 611nm (5D07F2). Photoluminescence spectra indicate that fluorescence capability improves with increase in temperature.

 

KeywordsNanofibers; Electrospinning; Photoluminescence, Red phosphors, Phosphors, Gadolinium, Europium

IPC Code: Int. Cl.8 B82B1/00