††††††††††††† Indian Journal of Chemistry

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

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VOLUME 48A

NUMBER 12

December 2009

CONTENTS

 

1627

 

1,3-Dipolar cycloadditions. Part XVII: Experimental and theoretical spectroscopic investigations of
C-aryl-N-methyl nitrones

 

 

 

 

 

 

 

 

 

 

 

 

Nivedita Acharjee, Avijit Banerji*, Manas Banerjee & Tapas K Das

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Detailed experimental and theoretical spectroscopic studies of C-aryl-N-methyl nitrones have been reported. The optimized geometries have been calculated by DFT/B3LYP level of theory with 6-31+G(d,p) basis set. The theoretically computed frontier orbital energy gaps and TDDFT calculations (calculated at B3LYP level with 6-31+G(d,p) basis set) of C-phenyl-N-methyl nitrone in different solvents are in good agreement with the UV spectral absorptions.

 

 

 

1638

 

Synthesis, characterization and DNA binding and cleavage properties of copper(II)-tryptophan-tryptophan complex

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Pulimamidi R Reddy*, Nomula Raju &
Karnati V Reddy

 

 

 

 

The copper-dipeptide complex, Cu(II)-tryptophan-tryptophan, has been synthesized and characterized. It exhibits square pyramidal geometry. The complex binds to calf thymus DNA and converts the supercoiled plasmid pUC19 DNA to the nicked circular form at physiological conditions.

 

 

 

1644

 

Selective binding of benzoquinone with a
PtII-cyclophane constructed on the skeleton of
N,N'
-bis(salicylidene)-p-phenylenediamine: Synthesis and spectroscopic studies

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Niraj Kumari, Rishikesh Prajapati, Mudit Dixit &
Lallan Mishra*

 

 

 

 

The Schiff base, N,N'-bis(salicylidene)-p-phenylenediamine, has been complexed with Pt(en)Cl2 and the resulting PtII-cyclophane, [Pt(en)L]2∑4PF6, reacted with phenol, resorcinol, hydroquinone or benzoquinone in DMSO solution. A few solid adducts of phenol and benzoquinone with the PtII-cyclophane complex and hydroquinone as well as that of resorcinol with the Zn-cyclophane have also been synthesized and characterized.

 

 

Notes

 

1652

 

Designing of type-I polymeric superlattices using genetic and ant algorithms: A comparative study

 

 

 

 

 

 

Avneet Kaur, Mohsineen Wazir, Aparna Garg &
A K Bakhshi*

 

 

 

Genetic and ant algorithms, a class of metaheuristic algorithms, have been applied in combination with the negative factor counting method to the designing of copolymers to find the optimum concentrations of the constituent homopolymers which would give the most conducting copolymer (with minimum band-gap and maximum delocalization). Quasi-one dimensional model ternary polymeric superlattices belonging to type-I have been investigated using both genetic and ant algorithms and a comparative study of the results has been made.

 

1657

 

Pairwise energy effects of rings in benzo-annelated perylenes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Slavko Radenković*, Wolfgang Linert,
Ivan Gutman & Svetlana Jeremić

 

 

 

 

DFT calculations have been used to corroborate two regularities resulting from the analysis of cyclic conjugation in benzo-annelated perylenes. A new method for assessing the pairwise energy effect is used to rationalize the obtained results. In the case of benzo-annelated perylenes, the pairwise energy effect is found to be related to the total π-electron energy of the two-ring-deleted conjugated fragment.

 

 

 

1662

 

First alkaline earth 2-carbamoyl-4-nitrobenzoate: Synthesis and supramolecular structure

 

 

 

 

 

 

 

 

 

 

 

 

Bikshandarkoil R Srinivasan*,
Santosh Y Shetgaonkar & Pallepogu Raghavaiah

 

 

 

 

The synthesis and supramolecular structure of 2-carbamoyl-4-nitrobenzoate of Mg(II) is reported.

 

 

1667

 

Effect of temperature on the partial molar volumes of some bivalent transition metal
nitrates and magnesium nitrate in the
water-rich region of binary aqueous
mixtures of dimethyl acetamide

 

 

 

 

 

 

 

 

 

 

M L Parmar* & D S Banyal

 

 

 

 

Partial molar volumes of some bivalent transition metal nitrates, viz., manganese nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate and magnesium nitrate, have been determined in the water-rich region of binary aqueous mixtures of N,N-dimethylacetamide from solution density measurements at 303.15 K, and in 5% w/w DMA + H2O at five equidistant temperatures (298.15, 303.15, 308.15, 313.15 and 318.15 K). The density data have been analysed by Massonís equation. The partial molar volumes and experimental slopes have been interpreted in terms of ion-solvent and ion-ion interactions, respectively.

 

1673

 

 

Annual Index

 

 

 

†††††††††††††††††††††††††††††† ††††††††††††††††††††††††††††††Authors for correspondence are indicated by (*)

 

 

 

 

Indian Journal of Chemistry

Vol. 48A, December 2009, pp. 1627-1637

 

 

1,3-Dipolar cycloadditions. Part XVII: Experimental and
theoretical spectroscopic investigations of C-aryl-N-methyl nitrones

Nivedita Acharjeea, Avijit Banerji*, a, Manas Banerjeeb & Tapas K Dasb

aCentre of Advanced Studies on Natural Products including Organic Synthesis, Department of Chemistry,
University College of Science, University of Calcutta, 92, Acharya Prafulla Chandra Road, Kolkata 700 009, India
bDepartment of Chemistry, University of Burdwan, Burdwan 713 104, India
Email: ablabcu@yahoo.co.uk

Received 17 March 2009; revised and accepted 9 November 2009

Detailed experimental and theoretical spectroscopic studies of C-aryl-N-methyl nitrones have been reported. The optimized geometries have been calculated by DFT/B3LYP level of theory with
6-31+G(d,p) basis set. The theoretically computed frontier orbital energy gaps and TDDFT calculations (calculated at B3LYP level with 6-31+G(d,p) basis set) of C-phenyl-N-methyl nitrone in different solvents are in good agreement with the UV spectral absorptions. This agreement reveals that the FMO energies can be well utilized to rationalize the observed regioselectivities of this and related nitrones in 1,3-dipolar cycloadditions and also their relative reactivities compared to other 1,3-dipoles. The fundamental vibrational modes ofC-phenyl-N-methyl nitrone have been assigned by comparing the theoretical (calculated at B3LYP level with 6-311++G(d,p) basis set) and experimental frequencies. The thermodynamic parameters (which are generally used to rationalize the observed
stereo- and regioselectivities of 1,3-dipolar cycloadditions of nitrones) have been calculated for C-phenyl-N-methyl nitrone at 6-311++G(d,p) level of theory. The preferred configuration and conformation predicted by theoretical 1H NMR studies of C-aryl-N-methyl nitrones coincides with that obtained from the dipole moment measurements and experimentally recorded 1H NMR chemical shifts.

Keywords: Theoretical chemistry, Dipolar cycloadditions, Cycloadditions, NMR spectroscopy, Nitrones

 

 

 

Indian Journal of Chemistry

Vol. 48A, December 2009, pp. 1638-1643

 

 

Synthesis, characterization and DNA binding and cleavage properties
of copper(II)-tryptophan-tryptophan complex

Pulimamidi R Reddy*, Nomula Raju & Karnati V Reddy

Department of Chemistry, Osmania University, Hyderabad 500 007, India

Email: rabi_pr@rediffmail.com

Received 22 April 2009; revised and accepted 16 November 2009

Reaction of copper(II) with tryptophan-tryptophan yields a 1:2 chloro bis(trp-trp) cuprate(II) complex. The complex exhibits absorption band at 620 nm (ε = 130 M-1 cm-1), which suggests a square pyramidal geometry at Cu(II) as observed for other Cu(II)-peptide complexes. The giso value of 2.09 for the complex agrees with a Cu(II) environment of distorted square pyramidal geometry. The mononuclear complex binds to calf thymus DNA through moderate intercalative and weak covalent interactions. It converts the supercoiled plasmid pUC19 DNA to the nicked circular form under physiological conditions.

Keywords: Coordination chemistry, Copper, Amino acids, Metallopeptides, Thermal denaturation, DNA quenching, DNA cleavage

IPC Code: Int. Cl.9 C07C229/76; C07F1/08

 

 

 

Indian Journal of Chemistry

Vol. 48A, December 2009, pp. 1644-1651

 

 

Selective binding of benzoquinone with a PtII-cyclophane constructed on the skeleton of N,N'-bis(salicylidene)-p-phenylenediamine:
Synthesis and spectroscopic studies

Niraj Kumaria, Rishikesh Prajapatia, Mudit Dixitb & Lallan Mishraa,*

aDepartment of Chemistry, Faculty of Science, Banaras Hindu University, Varanasi 221 005, India

Email: lmishrabhu@yahoo.co.in

bElectronic Structure and Theory Group, National Chemical Laboratory, Pune 411 008, India

Received 17 March 2009; re-revised and accepted 13 November 2009

The Schiff base N,N'-bis(salicylidene)-p-phenylenediamine has been complexed with Pt(en)Cl2 and the resultingPtII-cyclophane, [Pt(en)L]2∑4PF6, reacted with phenol, resorcinol, hydroquinone or benzoquinone in DMSO solution. Their binding has been monitored by the variation in the corresponding UV-visible and emission spectral patterns. The binding properties are compared with the earlier reported ZnII-cyclophane [Zn(bpy)L]2 (bpy = 2,2'-bipyridine). A few solid adducts of phenol and benzoquinone with the PtII-cyclophane complex and hydroquinone as well as that of resorcinol with the Zn-cyclophane have also been synthesized and characterized.

Keywords: Coordination chemistry, Metallocyclophanes, Cyclophanes, Schiff bases, Platinum

IPC Code: Int. Cl.9 CO7F15/00; CO7C251/02

 

 

 

Indian Journal of Chemistry

Vol. 48A, December 2009, pp. 1652-1656

 

 

Designing of type-I polymeric superlattices using genetic and ant algorithms: A comparative study

Avneet Kaur, Mohsineen Wazir, Aparna Garg & A K Bakhshi*

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

Email: akbakhshi2000@yahoo.com

Received 25 June 2009; revised and accepted 6 November 2009

Genetic and ant algorithms, a class of metaheuristic algorithms, have been applied in combination with the negative factor counting method to the designing of copolymers to find the optimum concentrations of the constituent homopolymers which would give the most conducting copolymer (with minimum band-gap and maximum delocalization). Quasi-one dimensional model ternary polymeric superlattices belonging to type-I have been investigated using both genetic and ant algorithms and a comparative study of the results has been made. Further the dependence of the optimized results on factors like the random sequence generated (depending on the seed used) has been investigated. It has been found that the band gap, of the copolymers studied, lies close to that of the constituent lowest band gap homopolymer. The optimized solutions are nearly seed independent. Also, the results obtained from both the algorithms are found to be more or less the same.

Keywords: Theoretical chemistry, Copolymers, Conducting polymers, Ant algorithm, Genetic algorithm

 

 

 

Indian Journal of Chemistry

Vol. 48A, December 2009, pp. 1657-1661

 

 

Pairwise energy effects of rings in benzo-annelated perylenes

Slavko Radenkovića,*, Wolfgang Linertb, Ivan Gutmana
& Svetlana Jeremića

aFaculty of Science, PO Box 60, 34000 Kragujevac, Serbia

bInstitute of Applied Synthetic Chemistry, Vienna University of Technology, Getreidemarkt 9/163-AC, A-1060 Vienna, Austria

Email: slavko.radenkovic@gmail.com

 

Received 17 August 2009; revised and accepted 26 October 2009

DFT calculations have been used to corroborate two regularities resulting from the analysis of cyclic conjugation in benzo-annelated perylenes reported earlier, viz., (a) the annelation of a benzene ring in angular position increases the extent of cyclic conjugation in the central ring, and, (b) the annelation of a benzene ring in linear position decreases the extent of cyclic conjugation in the central ring of benzo-annelated perylenes [Gutmanet al., Mon Chem, 135 (2004) 1389]. In addition, a new method for assessing the pairwise energy effect is used to rationalize the obtained results. In the case of benzo-annelated perylenes, the pairwise energy effect is found to be related to the total π-electron energy of the two-ring-deleted conjugated fragment.

Keywords: Theoretical chemistry, Graph theory, Cyclic conjugation, Pairwise energy, Perylenes,
Benzo-annelated perylenes

 

 

 

Indian Journal of Chemistry

Vol. 48A, December 2009, pp. 1662-1666

 

 

First alkaline earth 2-carbamoyl-4-nitrobenzoate: Synthesis and
supramolecular structure

Bikshandarkoil R Srinivasana, *, Santosh Y Shetgaonkara & Pallepogu Raghavaiahb

aDepartment of Chemistry, Goa University, Goa 403 206, India

bSchool of Chemistry, University of Hyderabad, Hyderabad 500 046, India

Email: srini@unigoa.ac.in

Received 30 September 2009; accepted 17 November 2009

2-Carbamoyl-4-nitrobenzoic acid (2-ca-4nbaH) has been prepared by alkaline hydrolysis of 4-nitrophthalimide. Aqueous reaction of MgCO3 with 2-ca-4nbaH results in the formation of [Mg(H2O)6](2-ca-4nba)2, which crystallizes in the centrosymmetric monoclinic space group P21/c with Mg(II) situated on an inversion center. The crystal structure consists of a distorted octahedral hexaaquamagnesium(II) cation and a free uncoordinated 2-ca-4nba anion. The cation and anion are involved in three varieties of H-bonding interactions, resulting in a supramolecular bilayer of 2-ca-4nba anions sandwiched between layers of [Mg(H2O)6]2+ cations.

Keywords: Coordination chemistry, Magnesium, Crystal structure, Supramolecular bilayer

IPC Code: Int. Cl.9 C07F3/02

 

 

 

Indian Journal of Chemistry

Vol. 48A, December 2009, pp. 1667-1672

 

 

Effect of temperature on the partial molar volumes of some bivalent transition metalnitrates and magnesium nitrate in the water-rich region of binary aqueous mixtures of dimethyl acetamide

M L Parmar* & D S Banyal

Department of Chemistry, Himachal Pradesh University

Summer Hill, Shimla 171 005, Himachal Pradesh, India

Email: hb_kutlehria@yahoo.co.in

Received 8 July 2009; revised and accepted 17 November 2009

Partial molar volumes of some bivalent transition metal nitrates, viz., manganese nitrate, cobalt nitrate, nickel nitrate, copper nitrate, zinc nitrate and magnesium nitrate have been determined in binary aqueous mixtures of N,N-dimethylacetamide (DMA) in the water-rich region (5, 10, 15, 20 and 25% by weight) of DMA from solution density measurements at 303.15 K, and in 5% w/w DMA + H2O at five equidistant temperatures (298.15, 303.15, 308.15, 313.15 and 318.15 K). The density data have been analysed by Massonís 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 electrolytes have been inferred from the sign of the second derivative of partial molar volumes with respect to temperature at constant pressure. All the electrolytes have been found to act as structure breakers in binary aqueous mixtures of dimethyl acetamide.

Keywords: Solution chemistry, Partial molar volumes, Electrolytes, Ion solvent interactions, Ion-ion interactions, Structure breakers