Indian Journal of Chemistry

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

http://www.niscair.res.in; http://nopr.niscair.res.in

Total visitors: 3310 since 15-04-2013

CODEN: ICACEC; ISSN: 0376-4710 (Print), 0975-0975 (Online)

 

 

 

 

 

VOLUME 52A

NUMBER 4

APRIL 2013

 

CONTENTS

 

 

459

 

Mg/La mixed oxide as catalyst for the synthesis
of dimethyl carbonate from cyclic carbonates
and methanol

 

 

 

 

 

 

 

 

 

 

 

 

 

C Murugan & H C Bajaj*

 

 

 

Highly basic Mg/La mixed oxide is used as catalyst in the synthesis of dimethyl carbonate from cyclic carbonates and methanol. The catalyst exhibits very high TON (~719 mmol DMC/gcat) under optimized conditions. The effect of water content in the reaction mixture is also investigated. Active sites of the reused catalysts can be regenerated by simple calcination process.

 

 

 

 

467

 

Conductivity, structural and electrochemical behavior of plasticized polymer electrolytes for dye-sensitised solar cell

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

C Menaka, K Sakthi Velu, P Manisankar & T Stalin*

 

 

 

Plasticized polymer electrolyte film with molar ratio of PMMA:KI:I2::25:2.5:0.25 (PPE1) shows the highest ionic conductivity of ~8.177 × 10-4 S cm-1 at room temperature.

 

 

 

Fig. 2.tif

 

 

473

 

Characterization and thermal properties of 2-(dinitro-methylene)-1,3-diazacyclopentane guanidine salt

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hang Zhang, Kang-zhen Xu*, Shuai Gao, Xiao-Lei Ren, Ji-rong Song, Bo-zhou Wang & Feng-qi Zhao

 

 

 

The thermal behavior of G(DNDZ) presents a melting decomposition process and an intense exothermic decomposition process. The self-accelerating decomposition temperature and critical temperature of thermal explosion are 181.2 and 201.3 ºC respectively. G(DNDZ) has lower thermal stability than DNDZ.

 

 

 

IC3595-2.tif

 

 

 

480

 

DFT and TD-DFT studies on copper(II) complexes with tripodal tetramine ligands

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Duran Karakaş* & Koray Sayin

 

 

 

Copper(II) complexes, containing aliphatic tripodal tetramine ligand, [Cu(trpn)(NH3)]2+, [Cu(tren)(NH3)]2+, [Cu(332)(NH3)]2+ and [Cu(322)(NH3)]2+ are optimized at B3LYP/ LANL2DZ and B3LYP/GEN levels of theory in gas phase. The optimization results show that the copper(II) center is trigonal bipyramidal for the studied complexes. Charge distribution indicates that on complexation the ligands transfer their negative charges to copper(II) ions.

 

 

image description

image description

 

 

Notes

 

486

 

Spectroscopic studies on the binding properties of
Zn-PP with various human telomeric G-quadruplex DNA and ct-DNA

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yu-Lan Li, Xu-Jian Luo, Qi-Pin Qin, Yan-Cheng Liu* & Zhen-Feng Chen

 

 

 

The binding property of the cationic zinc(II) porphyrin (Zn-PP) with three types of human telomeric G-quadruplex DNA and
ct-DNA is studied. Zn-PP exhibits higher binding affinity for human telomeric G-quadruplex DNA than for ct-DNA, since the expanded planar aromatic structure of the former facilitates
π-π stacking with Zn-PP.

 

 

 

 

 

492

 

Estimation of speed of sound in binary mixtures
of cyclohexane with benzene, benzaldehyde or cyclohexylamine, and, cyclohexylamine with benzene in the temperature range (293.15–323.15) K employing empirical and theoretical models

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Shantilal B Oswal* , Naved I Malek &
Sushma P Ijardar

 

 

 

 

Speed of sound in the binary mixtures of cyclohexane with benzene, benzaldehyde or cyclohexylamine, and, that of cyclohexylamine with benzene has been estimated from several models. The estimating ability of the Impedance model is the highest followed by the Nomoto model, Ernst model, Prigogine-Flory-Patterson theory, Collision factor theory, Van Dael model, Junjie model and Intermolecular free length theory.

 

 

 

 

Book Review

 

498

 

Inorganic Chemistry (A Modern Treatise)
by D Banerjea

 

 

 

 

 

V K Jain

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

Indian Journal of Chemistry

Vol. 52A, April 2013, pp. 459-466

 

 

Mg/La mixed oxide as catalyst for the synthesis of dimethyl carbonate
from cyclic carbonates and methanol

C Murugan & H C Bajaj*

Discipline of Inorganic Materials and Catalysis, CSIR-Central Salt and Marine Chemicals Research Institute (CSIR-CSMCRI),
G B Marg, Bhavnagar 364 002, Gujarat, India

Email: hcbajaj@csmcri.org

Received 5 February 2013; revised and accepted 25 March 2013

The Mg/La mixed oxide catalyst with varied molar ratio has been synthesized by co-precipitation method and characterized using various analytical techniques. The catalytic activity of the prepared catalysts is studied for synthesis of dimethyl carbonate from cyclic carbonates and methanol. Various reaction parameters such as temperature, reactant ratio and catalyst amount have been studied to optimize the yield of the product. The catalyst shows very high turnover number (719 mmol/gcat.) among other reported heterogeneous catalysts. The effect of water content in the reaction mixture has also been investigated. The active sites of the reused catalysts can be regenerated by simple calcination process.

Keywords: Catalysts, Mixed oxides, Oxides, Solid base catalysts, Transesterification, Dimethyl carbonate, Propylene carbonate, Ethylene carbonate, Carbonates, Cyclic carbonates, Magnesium oxide, Lanthanum oxide

 

Indian Journal of Chemistry

Vol. 52A, April 2013, pp. 467-472

 

 

Conductivity, structural and electrochemical behavior of plasticized
polymer electrolytes for dye-sensitised solar cell

C Menaka, K Sakthi Velu, P Manisankar & T Stalin*

Photoelectrochemistry Laboratory, Department of Industrial Chemistry, Alagappa University,
Karaikudi 630 003, India

Email: tstalinphd@rediffmail.com

Received 3 December 2012; revised and accepted 19 March 2013

Plasticized polymer electrolyte films, of three different compositions containing poly (methyl methacrylate) (PMMA) as polymer, propylene carbonate (PC) as plasticizer, and potassium iodide and iodine as salt, have been prepared by solvent casting technique. The PMMA/PC mole ratio has been fixed as 25:75. Of the three, the sample with the polymer salt composition of 25:2.5:0.25 (PPE1) shows the highest ionic conductivity of ~ 8.177 × 10-4 S/cm at room temperature. Amorphous nature, complexation and surface morphology of the polymer electrolytes have been confirmed by X-ray diffraction analysis, Fourier transform infrared analysis and scanning electron microscopy, while the electrochemical behaviour of PPE has been studied by cyclic voltammetry.

Keywords: Poly(methylmethacrylate), Electrochemical analysis, Differential scanning calorimetry, Conductivity, Plasticized polymer electrolytes, Polymer electrolytes

 

 

 

Indian Journal of Chemistry

Vol. 52A, April 2013, pp. 473-479

 

 

Characterization and thermal properties of
2-(dinitromethylene)-1,3-diazacyclopentane guanidine salt

Hang Zhanga, Kang-zhen Xua, *, Shuai Gaoa, Xiao-Lei Rena,
Ji-rong Songa, Bo-zhou Wangb &
Feng-qi Zhaob

aSchool of Chemical Engineering, Northwest University, Xi’an 710069, People’s Republic of China
Email: xukz@nwu.edu.cn

bXi’an Modern Chemistry Research Institute, Xi’an 710065, People’s Republic of China

Received 20 October 2012; revised and accepted 20 March 2013

2-(Dinitromethylene)-1,3-diazacyclopentane guanidine salt [G(DNDZ)] is synthesized by reaction of
2-(dinitromethylene)-1,3-diazacyclopentane
(DNDZ) and guanidine hydrochloride in sodium hydroxide aqueous solution
. Theoretical investigations on G(DNDZ) have been carried out by B3LYP/6-311+G* method. The thermal behavior of G(DNDZ) has been studied by DSC and TG-DTG, and presents a melting decomposition process and an intense exothermic decomposition process. The kinetic equation of the exothermic decomposition process obtained is . The self-accelerating decomposition temperature and critical temperature of thermal explosion are 181.2 and 201.3 ºC, respectively. Specific heat capacity of G(DNDZ) has been studied by micro-DSC method and by theoretical calculations. The molar heat capacity is found to be 312.9 J mol-1 K-1 at 298.15 K. Adiabatic time-to-explosion of [G(DNDZ)] is estimated to be ~ 200 s. G(DNDZ) is found to have lower thermal stability than DNDZ.

Keywords: Theoretical chemistry, Thermal studies, FOX-7, Nitro-enamine compounds, Guanidine salt,
High-energy compounds

 

Indian Journal of Chemistry

Vol. 52A, April 2013, pp. 480-485

 

 

DFT and TD-DFT studies on copper(II) complexes with
tripodal tetramine ligands

Duran Karakaş* & Koray Sayin

Department of Chemistry, Faculty of Science, Cumhuriyet University, Sivas 58140, Turkey
Email: drnkarakas@gmail.com

Received 6 December 2012; revised and accepted 18 March 2013

Copper(II) complexes, containing aliphatic tripodal tetramine ligand, [Cu(trpn)(NH3)]2+ (1), [Cu(tren)(NH3)]2+ (2), [Cu(332)(NH3)]2+ (3) and [Cu(322)(NH3)]2+ (4) are optimized at B3LYP/ LANL2DZ and B3LYP/GEN levels of theory in gas phase (where (trpn), (tren), (332) and (322) are N(CH2CH2CH2NH2)3, N(CH2CH2NH2)3, N[(CH2CH2CH2NH2)2(CH2CH2NH2)] and N[(CH2CH2CH2NH2)(CH2CH2NH2)2], respectively). The optimization results show that the copper(II) center is trigonal bipyramidal for the studied complexes. Charge distributions on the donor and acceptor atoms are evaluated by natural population analysis. The charge distribution indicates that the ligands transfer their negative charges to copper(II) ions during formation of the complexes. Electronic excitation energies of copper(II) complexes are calculated with time dependent density functional theory in gas phase. It is found that the most intense bands at electronic spectra of complexes stem from dxz, dyzdz2 or dx2-y2, dxydz2 transitions.

Keywords: Theoretical chemistry, Density functional calculations, Time dependent density functional calculations, Tripodal tetramine ligands, Copper

 

Indian Journal of Chemistry

Vol. 52A, April 2013, pp. 486-491

 

 

Spectroscopic studies on the binding properties of Zn-PP with various
human telomeric G-quadruplex DNA and ct-DNA

Yu-Lan Lia, Xu-Jian Luoa,b, Qi-Pin Qina, Yan-Cheng Liua, * & Zhen-Feng Chena

aState Key Laboratory Cultivation Base for the Chemistry and Molecular Engineering of Medicinal Resources,
School of Chemistry & Chemical Engineering of Guangxi Normal University, Guilin 541 004, PR
, China

bCollege of Chemistry and Chemical Engineering, Central South University, Changsha,Hunan 410 083, PR China

Email: ycliugxnu@yahoo.cn

Received 8 January 2013; revised and accepted 14 March 2013

The binding property of Zn-PP with human telomeric G-quadruplex DNA as compared to binding with ct-DNA
is examined by UV-vis, fluorescence and CD spectroscopic methods. UV-vis absorption spectral analysis in the presence of K+, shows that addition of three types of human telomeric G-quadruplex DNA (Htel-G4, Htel-1-G4 and Htel-2-G4) in the Zn-PP solution induces moderate hypochromicity with intrinsic binding constants of (3.13±0.45)×105, (1.47±0.12)×105 and (2.51±0.16)×105 M-1, respectively, while for ct-DNA, the
Kb value is (9.94±0.32)×104 M-1. In the fluorescence emission spectral analysis, the addition of G-quadruplex DNA induces significant quenching of the fluorescence emission of Zn-PP with total quenching ratios of 26.31–36.84%, while the addition of ct-DNA under the same conditions induces only 17.33% of the quenching ratio of Zn-PP. Both the UV-vis and fluorescence spectral analysis indicate that Zn-PP exhibits higher binding affinity to human telomeric G-quadruplex DNA than to ct-DNA. In the CD spectral analysis, the interaction with Zn-PP does not disturb the characteristic absorption of G-quadruplex at 290 nm corresponding to its antiparallel conformation, and only slightly decreases the positive absorption at 270 nm as a shoulder peak. In comparision, the addition of Zn-PP induces significant spectral changes on the CD absorption of double helix ct-DNA, with a 22.2% increase on the positive peak absorption, along with a 9.63% decrease on the negative peak absorption, which suggests that the antiparallel structure of G-quadruplex is stable in the presence of Zn-PP.

Keywords: Bioinorganic chemistry, Zinc, DNA binding, G-quadruplex DNA, ct-DNA, Binding properties,
Spectral studies, DNA interactive drugs

 

Indian Journal of Chemistry

Vol. 52A, April 2013, pp. 492-497

 

 

Estimation of speed of sound in binary mixtures of cyclohexane with benzene, benzaldehyde or cyclohexylamine, and, cyclohexylamine with benzene in the temperature range (293.15–323.15) K employing empirical and theoretical models

 

Shantilal B Oswala, * , Naved I Malekb & Sushma P Ijardar

aR&D, Biochemistry, Span Diagnostics Ltd., 173-B,
New Industrial Estate, Udhna, Surat 394 210, India

Email: oswalsl@yahoo.co.uk

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

cSalt and Marine Chemicals Division, Central Salt and Marine Chemicals Research Institute (CSMCRI), G B Marg,
Bhavnagar 364 002, India

Received 27 December 2012: revised and accepted 22 March 2013

Speed of sound in the binary mixtures of cyclohexane with benzene, benzaldehyde or cyclohexylamine, and, that of cyclohexylamine with benzene over the entire composition range and at (293.15, 303.15, 313.15 and 323.15) K has been estimated employing several models, viz., Nomoto model (NM), Van Dael model (VM), Junjie model (JM), Ernst et al. model (EM), Impedance model (IM), Collision factor theory (CFT), Intermolecular free length theory (FLT), and, Prigogine-Flory-Patterson theory (PFPT). The maximum deviations between estimated and experimental speed of sound by different models NM, VDM, JM, EM, IM, CFT, FLT, and PFPT are –24.5, –23.0, 20.2, –48.3, –22.1, –24.9, 25.0, and 24.4 m s-1, respectively.The values of standard percentage deviations for NM, VDM, JM, EM, IM, CFT, FLT, and PFPT models are in the range of 0.3–1.4, 0.3–1.4, 0.3–1.1, 0.3–2.7, 0.5–1.2, 0.2–1.4, 0.4–1.2, and 0.4–1.2%, respectively. Considering the overall results, the FLT model predicts the most accurate values for speed of sound while the EM model gives the least accurate values.

Keywords: Speed of sound, Nomoto model, Van Dael model, Junjie model, Ernst model, Impedance model, Collision factor theory, Intermolecular free length theory, Prigogine-Flory-Patterson theory

 

Indian Journal of Chemistry

Vol. 52A, April 2013, pp. 498-499

 

Book Review

 

                Inorganic Chemistry (A Modern Treatise)” by D Banerjea (formerly Sir Rashbehary Ghose Professor of Chemistry, Calcutta University, Kolkata), 2012, pp. xi + 1779, Asian Books Pvt. Ltd., New Delhi

 

 

Reviewed by

V. K. Jain

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