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)

 

 

 

 

VOLUME 56A

NUMBER 8

AUGUST 2017

 

CONTENTS

 

 

805

 

Vitamin-B6 Schiff base dioxovanadium(V) complex for targeted visible light-induced anticancer activity

 

 

 

 

 

 

 

 

 

 

Arun Kumar, Samya Banerjee, Sanjoy Mukherjee & Akhil R Chakravarty*

 

 

 

The structurally characterized dioxovanadium(V) vitamin-B6 Schiff base complex with a cis-oriented VO2+ moiety, [VO2L] (1), where H2L·HCl is 3-hydroxy-5-(hydroxymethyl)-4-(((2-hydroxyphenyl)-imino)-methyl)-2-methylpyridin-1-ium chloride, shows cancer cell targeting and significant photo-cytotoxicity in visible light by ROS-mediated apoptosis with low dark toxicity. The photocytotoxicity is significantly more in the HeLa and MCF-7 cancer cells in comparison with 3T3 normal cells.

 

 

 

 

814

 

DFT study of the mechanism and stereochemistry of
electrophilic transannular addition reaction of bromine to 6-oxa-heptacyclo[9.6.2.23,9.113,16.02,10.04,8.012,17]docosan-14,18,20-triene-12,17-dicarboxylic anhydride

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rza Abbasoglu* & Abdurrahman Atalay

 

 

 

The nucleophilic attack of bromide anion (Br–) on the cation centre of U-N-type ion occurs on the endo face. As a result the exo,endo-dibromide isomer of U-N-type product, which is 6.913 kcal mol-1 more stable than the exo,exo-isomer, is obtained.

 

 

 

Notes

 

821

 

Single walled carbon nanotubes decorated vanadyl phthalocyanine composite for electrochemical oxygen reduction in fuel cells

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Piyush Kumar Sonkar, Vellaichamy Ganesan*,
Ravi Kant Singh, Dharmendra Kumar Yadav,
Rupali Gupta & Mamta Yadav

 

 

 

GC/SWCNTs-VOPc electrode exhibits a pair of peaks at –265 and
–97 mV (at 20 mV s-1 in 0.1 M H2SO4) due to the characteristic redox process, VIV/III, of VOPc. It efficiently reduces oxygen in
 0.1 M H2SO4 with a low onset potential of 0.16 V. It also exhibits significant storage stability, retaining 91% of its original catalytic reduction current after 10 days storage at room temperature in air under dry conditions.

 

 

 

 

826

 

A supramolecular microporous network of zinc(II) coordination polymer for highly selective fluorescent detection of Pb2+

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ling-Yun Xin, Yun-Ping Li, Feng-Yang Ju,
Xiao-Ling Li & Guang-Zhen Liu
*

 

 

 

A hydrogen bonded microporous network with Lewis basic N sites has been hydrothermally prepared by dual ligand synthetic strategy. With fast detection time, excellent selectivity and high sensitivity, this microporous network is capable of detecting trace Pb2+ ions
(10-3–10-5mol L-1) in biological and environmental materials.

 

graphic Abstract.tif

 

 

 

 

832

 

Schiff base modified Pt electrode as sensor for detecting Al(III) and Pb(II)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Kangkana Deka & Diganta Kumar Das*

 

 

 

The square wave voltammogram of the Pt electrode with
its surface modified with the condensation product of
p-phenylenediamine and acetylferrocene (PPDA-AcFc) in aqueous medium gradually shifts by 0.440 V in the positive direction and by 0.090 V in negative direction on interaction with Al3+ and Pb2+ respectively. EIS study shows that its charge transfer resistance increases in the case of Al3+, while it decreases in the case of Pb2+. The linear range of detection is 0-12
mM and 0-6 mM for Al3+ and Pb2+ respectively.

 

 

 

 

838

 

Self-assembly of tetradecyltrimethylammonium bromide in long chain alcohols

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Neelima Dubey

 

 

 

The effect of organic additives, C8-OH and C9-OH, on the micellar behavior of the cationic surfactant, tetradecyltrimethylammonium bromide is reported.

 

 

 

 

843

 

Synthesis of silver nanocatalyst in presence of poly(ethylene glycol) and its application for electrocatalytic reduction of hydrogen peroxide

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Samira Ghasemi, Jahan Bakhsh Raoof*,
Fereshteh Chekin & Reza Ojani

 

 

 

Synthesis of Ag NPs in presence of poly(ethylene glycol) as reducing agent and stabilizer in aqueous medium is reported. The catalytic activity of the nanocrystalline AgNPs, for reduction of H2O2 is studied at the surface of glassy carbon electrode modified with Ag NPs and poly(methyl methacrylate) prepared by casting of the AgNPs-PMMA solution on GCE. The sensor responds to H2O2 with high selectivity, good reproducibility and stability, over a linear range of 22–1700 µM with a detection limit of 4.8 µM.

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 


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Indian Journal of Chemistry

Vol. 56A, August 2017, pp. 805-813

 

Vitamin-B6 Schiff base dioxovanadium(V) complex for targeted visible light-induced anticancer activity

Arun Kumar, Samya Banerjee, Sanjoy Mukherjee & Akhil RChakravarty*

Department of Inorganic and Physical Chemistry, Indian Institute of Science,
Sir CV Raman Avenue, Bangalore 560 012, India

Email: arc@ipc.iisc.ernet.in

Received 23 May 2017; revised and accepted 24 July 2017

A dioxovanadium(V) complex of vitamin-B6 Schiff base [VO2L] (1) (where H2L·HCl is 3-hydroxy-5-(hydroxymethyl)-4-(((2-hydroxyphenyl)imino)methyl)-2-methylpyridin-1-ium chloride) has been prepared and structurally characterized. Its photo-induced cytotoxicity and mechanism of cell death has been studied. Single crystal X-ray structure shows five-coordinate square-pyramidal geometry of the complex having the dianionic O,N,O-donor tridentate vitamin-B6 Schiff base and two cis-oriented oxo ligands bound to V(V). DFT study shows the HOMO located on the amino-phenolic moiety, while the LUMO is on the protonated aromatic unit, i.e., the pyridiniumphenolate moiety. Vitamin-B6 transporting membrane carrier (VTC) pathway seems to be responsible for the higher cellular uptake and activity of the complex into the cervical HeLa and breast cancer MCF-7 cells in preference to the normal embryonic fibroblast 3T3 cells. The complex exhibits reactive oxygen species (ROS) mediated apoptotic photocytotoxicity in visible light of 400–700 nm in the cancer cells
(IC50: ~16 μM), while being essentially non-toxic in the dark. Alkaline Comet assay shows damage of the nuclear DNA.

Keywords: Bioinorganic chemistry, Photocytotoxicity, Crystal structure, Cell apoptosis, Schiff base,
Vitamin-B6 Schiff base, Vanadium

 

Indian Journal of Chemistry

Vol. 56A, August 2017, pp. 814-820

 

DFT study of the mechanism and stereochemistry of electrophilic transannular addition reaction of bromine to 6-oxa-heptacyclo[9.6.2.23,9.113,16.02,10.04,8.012,17]docosan-
14,18,20-triene-12,17-dicarboxylic anhydride

Rza Abbasoglu* & Abdurrahman Atalay

Department of Chemistry, Karadeniz Technical University, 61080 Trabzon, Turkey

Email: rabbas@ktu.edu.tr

Received 10 February 2017; revised and accepted 31 July 2017

The geometry and the electronic structure of 6-oxa-heptacyclo[9.6.2.23,9.113,16.02,10.04,8.012,17] docosan-14,18,20-triene-12,17-dicarboxylic anhydride (HDTD) have been investigated by DFT methods. The study shows that the norborneyl double bond of the HDTD molecule is endo pyramidalized and the central and bicyclo[2,2,2]octenyl double bonds are exo pyramidalized. The structure and stability of the cation intermediates and products of the reaction have been investigated by DFT methods. The most stable cation intermediate is U-N-type ion and the reaction takes place over this cation. The cation centre of U-N-type ion mutually interacts with the unshared electron pair of the oxygen atom of the tetrahydrofuran ring on the exo face and is sterically hindered by the tetrahydrofuran ring. The nucleophilic attack of bromide anion (Br–) on the cation centre of U-N-type ion occurs on the endo face and as a result the exo,endo-dibromide isomer of
U-N-type product is obtained, which is 6.913 kcal mol-1 more stable than the exo,exo-isomer.

Keywords: Theoretical chemistry, Density functional calculations, Electrophilic transannular addition, Transannular addition, Juxtaposed double bonds, Intramolecular skeletal rearrangement

 

 

Indian Journal of Chemistry

Vol. 56A, August 2017, pp. 821-825

 

Single walled carbon nanotubes decorated vanadyl phthalocyanine composite for electrochemical oxygen reduction in fuel cells

Piyush Kumar Sonkar, Vellaichamy Ganesan*, Ravi Kant Singh, Dharmendra Kumar Yadav,
Rupali Gupta & Mamta Yadav

Department of Chemistry, Institute of Science, Banaras Hindu University, Varanasi 221 005, UP, India

Email : velganesh@yahoo.com; velgan@bhu.ac.in

Received 8 May 2017; revised and accepted 20 July 2017

Vanadyl phthalocyanine (VOPc) has been immobilized on single walled carbon nanotubes by the adsorption process and characterized using UV-vis spectroscopy, infrared spectroscopy and X-ray diffraction techniques. Electrochemical characterization of VOPc immobilized SWCNTs (SWCNTs-VOPc) has been done by coating an aqueous colloid of SWCNTs-VOPc on glassy carbon electrode (represented as GC/SWCNTs-VOPc). GC/SWCNTs-VOPc exhibits a pair of peaks at –265 and –97 mV (at 20 mV s-1 in 0.1 M H2SO4) due to the characteristic redox process, VIV/III of VOPc. Further, electrocatalytic reduction of oxygen is analysed using GC/SWCNTs-VOPc electrode by cyclic voltammetry. GC/SWCNTs-VOPc electrode efficiently reduces oxygen in 0.1 M H2SO4 with a low onset potential of 0.16 V. Also, GC/SWCNTs-VOPc exhibits significant storage stability, retaining 91% of its original catalytic reduction current after 10 days storage at room temperature in air and dry conditions.

 Keywords: Electrochemistry, Electrocatalysis, Oxygen reduction, Fuel cells, Cyclic voltammetry, Single walled carbon nanotubes, Vanadyl phthalocyanine

 

Indian Journal of Chemistry

Vol. 56A, August 2017, pp. 826-831

 

A supramolecular microporous network of zinc(II) coordination polymer for highly selective fluorescent detection of Pb2+

Ling-Yun Xina, Yun-Ping Lia, Feng-Yang Jub, Xiao-Ling Lia & Guang-Zhen Liua, *

aCollege of Chemistry and Chemical Engineering, and Henan Key Laboratory of Function-Oriented
Porous Materials, Luoyang Normal University, Luoyang 471934, China

Email: gzliuly@126.com

bSchool of Food and Drug, Luoyang Normal University, Luoyang Normal University,
Luoyang, 471934, China

Received 30 March 2017; revised and accepted 14 August 2017

A hydrogen bonded microporous network with Lewis basic N sites, viz., {[Zn(TZ-HIP)(HPYTZ)(H2O)2]·3H2O}n [TZ-HIP = 5-(tetrazol-5-yl)isophthalic acid, HPYTZ = 3,5-di(4-pyridyl)-1H-1,2,4- triazolate ligand] has been obtained from the dual ligand system of polydentate N-heterocyclic carboxylate and dipyridyl-type ligands. Single crystal X-ray diffraction analysis shows that the adjacent Zn(II) centers are bridged by HTZ-H2IP ligand to form 1D chain with HPYTZ molecules as free lateral arms. The paralleled chains are connected by H-bonding interactions to produce the 3D microporous network with 1D pores. It is interesting that the uncoordinated N atoms (Lewis base sites) pores cause Pb2+ ions to produce a remarkably enhancing effect on the luminescent intensity of the zinc complex with high sensitivity in the detection range of 10-3-10-5mol L-1 concentration limit. This coordination polymer may be used as a sensing material for developing a highly selective and sensitive Pb2+ sensor in the biological and environmental materials.

 Keywords: Coordination polymers, Dual ligand systems, Microporous networks, Fluorescence,
S
ensing materials, Zinc, Lead

 

 

Indian Journal of Chemistry

Vol. 56A, August 2017, pp. 832-837

 

Schiff base modified Pt electrode as sensor for detecting
Al(III) and Pb(II)

Kangkana Deka & Diganta Kumar Das*

Department of Chemistry, Gauhati University, Guwahati 781 014, India

Email: diganta_chem@gauhati.ac.in

Received 5 April 2017; revised and accepted 27 July 2017

A platinum electrode with its surface modified with the condensation product of p-phenylenediamine and acetylferrocene (PPDA-AcFc) has been fabricated by cyclic voltammetry. The square wave voltammogram of the modified electrode, PPDA-AcFc/Pt, in aqueous medium gradually shifts by 0.440 V and 0.090 V in the positive direction on interaction with Al3+ and Pb2+ respectively. Electrochemical impedance spectroscopy shows the charge transfer resistance value of PPDA-AcFc/Pt electrode increases in the case of Al3+ while it decreases in the case of Pb2+. The linear range of detection is 0-12 mM and 0-6 mM for Al3+ and
Pb2+ respectively.

 Keywords: Electrochemistry, Electrodes, Modified electrodes, Electrochemical impedance spectroscopy, Voltammetry, Aluminium, Lead

 

Indian Journal of Chemistry

Vol. 56A, August 2017, pp. 838-842

 

Self-assembly of tetradecyltrimethyl-ammonium bromide in
long chain alcohols

Neelima Dubey

Department of Chemistry, Kurukshetra University, Kurukshetra 136 119, India

Email: drneelimadubey@gmail.com

Received 5 October 2016; revised and accepted 31 July 2017

The effect of organic additives, C8-OH and C9-OH (octan-1-ol and nonan-1-ol),on the micellar behavior of cationic surfactant, tetradecyltrimethylammonium bromide (TTAB) has been studied by fluorescence and NMR techniques. Fluorescence spectroscopy has been used to obtain critical micelle concentration values as well as the aggregation number of TTAB in the presence of the studied alcohols. The decrease in cmc of aqueous TTAB is observed in the presence of long chain alcohols. The alcohols form additive-TTAB mixed micelles and micellar growth takes place. The structural transformation is explained by hydrophobic interactions and electrostatic effects between the additive and TTAB micelle. The locus of solubilization of alcohols and consequent changes in structure of the micelles is inferred from NMR measurements. The unique role of long chain alcohols in changing properties of aqueous surfactant systems is demonstrated.

 Keywords: Solution chemistry, Surfactants, Micelles, Self-assembly, Fluorescence spectroscopy,
NMR spectroscopy, Tetradecyltrimethylammonium bromide, Alcohols

 

Indian Journal of Chemistry

Vol. 56A, August 2017, pp. 843-847

 

Synthesis of silver nanocatalyst in presence of poly(ethylene glycol) and its application for electrocatalytic reduction of hydrogen peroxide

Samira Ghasemia, Jahan Bakhsh Raoofa,*, Fereshteh Chekinb & Reza Ojania

aElectroanalytical Chemistry Research Laboratory, Department of Analytical Chemistry, Faculty of Chemistry,
University of Mazandaran, Babolsar, Iran

Email: j.raoof@umz.ac.ir

bDepartment of Chemistry, Ayatollah Amoli Branch, Islamic Azad University, Amol, Iran

Received 29 January 2017; revised and accepted 31 July 2017

The synthesis of powdered Ag nanoparticles in presence of poly(ethylene glycol) as reducing agent and stabilizer in aqueous medium is reported. The structure and properties of the Ag nanoparticles have been characterised by X-ray diffraction, transmission electron microscopy and energy dispersive X-ray data. XRD study shows that the particles are crystalline in nature with face centered cubic geometry. Formation of stable silver nanoparticles gives mostly spherical particles with diameter in the range of 12–30 nm. The catalytic activity of the nanocrystalline AgNPs, for the reduction of hydrogen peroxide has been studied at the surface of glassy carbon electrode modified with Ag nanoparticles and poly(methyl methacrylate) (AgNPs-PMMA/GCE) prepared by casting of the AgNPs-PMMA solution on GCE. The sensor responds to H2O2 with high selectivity, good reproducibility and stability, over a linear range of 22–1700 µM with a detection limit of 4.8 µM using amperometry.

 Keywords: Electrochemistry, Electrodes, Modified electrodes, Silver nanoparticles, Nanoparticles, Nanocatalysts, Poly(ethylene glycol), Hydrogen peroxide reduction