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 57A

NUMBER 04

APRIL 2018

 

CONTENTS

 

 

469

 

Hydrogen bonded supramolecular architecture of a copper(II)-citrate coordination building block: Synthesis and crystal structure with theoretical insight

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sougata Sarkar*, Dibakar Deb*, Avijit Sarkar*, Shouvik Chattopadhyay*, Bipan Dutta &
Soumen Khanra

 

 

 

 

A metal-organic hybrid material of Cu(II) unit has been designed employing citrate and 1,10-phenanthroline, where the carboxylate acts as the bridging ligand and phenanthroline as chelator. The dimeric unit has been transformed into a supramolecular architecture through hydrogen bonding and other non-covalent interactions (like π-π interactions) and water of crystallization. Additional support to the solid state structure has been obtained through DFT based calculations and Hirshfeld surface analysis.

 

 

 

 

477

 

Kinetic and mechanistic studies of oxidation of chloramphenicol by sodium metaperiodate using Rh(III)-chloride as homogeneous catalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ranju Pradhan, Jaya Srivastava, Ritu Swamini Bala, Rupam Yadav, Shahla Rahmani &
Ashok Kumar Singh
*

 

 

 

 

The kinetics of oxidation of the antibiotic drug, chloramphenicol,  by NaIO4 in the presence of Rh(III) catalyst in alkaline medium is investigated at 35 °C. The most probable reaction mechanism of Rh(III)-catalyzed oxidation of chloramphenicol by NaIO4 in alkaline medium is proposed.

 

Fig. 6.tif

 

 

NOTES

 

485

 

Silver nanoparticle modified Pt electrode as voltammetric and electrochemical impedance sensor for hydrogen peroxide in live biological cells

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Kangkana Deka, Jutika Kumar, Ananya Bhowmick, Sofia Banu & Diganta Kumar Das*

 

 

 

A non-enzymatic electrochemical sensor for hydrogen peroxide based on silver nanoparticle (AgNP) modified platinum electrode has been fabricated by multiple cyclic voltammetric scan of platinum electrode in AgNP solution in aqueous medium. The modified electrode (Pt/AgNP) can detect hydrogen peroxide in aqueous medium, bovine serum albumin  and live L6 rat myoblast cells with high sensitivity and selectivity by cyclic voltammetry and electrochemical impedance spectroscopy. The limit of detection of Pt/AgNP towards H2O2 is 5.4×10-7 M.

 

 

 

 

 

 

490

 

Highly selective colorimetric schiff base chemosensor for detection of Cu2+

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Dan Liu, Hua Zhu* & Li Yang

 

 

 

A highly selective colorimetric chemosensor for Cu2+ using a novel Schiff base based on 2-hydroxy-1-naphthaldehyde is reported. On addition of Cu2+ to the sensor L1, intramolecular proton transfer takes place, leading to keto-enol tautomerization. Cu2+ conjugates with N and O atom on the keto form of L1, to generate a small conjugation length, which leads to the blue shift and fading of color. The sensor L1 may be utilized as a colorimetric sensor for monitoring Cu2+.

 

 

 

 

 

 

495

 

Volumetric and acoustic studies of
binary liquid mixtures containing diisopropylamine and alcohols at different temperatures

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Seema Rani & Gyan Prakash Dubey*

 

 

 

 

A study on the intermolecular interactions of diisopropylamine with 1-propanol, 2-propanol, 1-butanol, 1-pentanol including the effect of temperature, chain length of alcohol, and position of functional group is reported.

 

 

 

 

503

 

DFT study on ammonium perchlorate bond activation by Pt clusters supported by carbon nanotubes and graphene

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hosseini, Seyed Ghorban* & Mohammad Hossein Zanghenehnejad

 

 

 

 

The N–H bond breaking on Pt4 clusters supported by carbon nanotubes and graphene has been investigated by the density functional theory method. In this study, comparison of (10-10),
(8-8), (10-0) and (5-5) carbon nanotube models in zigzag and armchair forms is presented. The results show that opportune selection of size and chirality of carbon nanotubes supports can provide stable support for Pt clusters and improve their catalytic activity.

 

 

IJCA-2012_Fig. 5.tif

 

 

 

507

 

Guide to Authors

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

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Indian Journal of Chemistry

Vol. 57A, April 2018, pp. 469-476

 

Hydrogen bonded supramolecular architecture of a copper(II)-citrate coordination building block: Synthesis and crystal structure with theoretical insight

Sougata Sarkara, *, Dibakar Debb,*, Avijit Sarkarc, *,
Shouvik Chattopadhyayd, *, Bipan Duttae & Soumen Khanraa

aDepartment of Chemistry, Ramakrishna Mission Vivekananda Centenary College,
Rahara, Kolkata 700 118, India

Email: sougata.sarkar81@gmail.com

bDepartment of Chemistry, Techno India, Agartala 799 004, India

 Email: debdibakar@gmail.com

cDepartment of Chemistry, Bhairab Ganguly College, Kolkata 700 056, India

Email: rite2avijit@gmail.com

dDepartment of Chemistry (Inorganic Section) Jadavpur University, Kolkata 700 032, India

 Email: shouvik.chem@gmail.com

eDepartment of Physics, Sammilani Mahavidyalaya, Kolkata 700 094, India

 Email: bipan.dutta@yahoo.com

A tricarboxylate supported binuclear metal organic hybrid of Cu(II), [Cu2(µ-cit)(phen)4]·9H2O (1) has been synthesized using the well known pyridyl based N,N′ linker, 1,10-phenanthroline and structurally characterized. The use of the flexible hydroxyl tricarboxylate citrate, in designing such a framework has created a marked diversity in the topology. The structural and topological diversity has been analyzed from the single crystal X-ray structure. Here, in a unit, each of the two Cu(II) centres is chelated by two phenanthroline ligands and citrate (cit4–) serves the role of a bridging ligand. Furthermore, the carboxylate moiety/hydroxyl oxygen sites of citrate and the aromatic chelating ligands promote supramolecular recognition through hydrogen bonding and other non-covalent interactions (like π-π interaction) and water of crystallization, thereby resulting in a higher dimensional architecture. The oxygen atoms of the carboxylate moiety involve in both inter and intra-molecular hydrogen bonding with the water molecules resulting in a hydrogen bonded helical supramolecular solid. Theoretical study is performed to analyze the structure and the role of non-covalent interactions through DFT based calculations and Hirshfeld surface analysis.

Keywords: Supramolecular architectures, Density functional calculations, Crystal structure, Hydrogen bonding, π-π interactions, Copper, Citrate

 

Indian Journal of Chemistry

Vol. 57A, April 2018, pp. 477-484

 

Kinetic and mechanistic studies of oxidation of chloramphenicol by
sodium metaperiodate using Rh(III)-chloride as homogeneous catalyst

Ranju Pradhan, Jaya Srivastava, Ritu Swamini Bala, Rupam Yadav,
 Shahla Rahmani & Ashok Kumar Singh*

Department of Chemistry, University of Allahabad,
Allahabad, 211 002, India

Email: ashokeks@rediffmail.com; ashok_au2@yahoo.co.in/ neelranju@gmail.com

The kinetics of oxidation of an antibiotic drug, chloramphenicol (CHP) by NaIO4 in the presence of Rh(III) catalyst has been investigated in alkaline medium at 35 °C. The reaction shows first order kinetics with respect to [IO4-] and [Rh(III)]. The fractional positive order kinetics in [OH-] and [CHP] throughout their variations are observed. Ionic strength and dielectric constant of the medium show no effects on the reaction rates. No effect of [Cl-] is observed in the presence of Rh(III) chloride. The values of rate constants observed at four different temperatures have been utilized to calculate various activation parameters. The species IO4- and [RhCl3(H2O)2OH]- are proposed as the reactive species of NaIO4 and Rh(III) respectively in alkaline medium. On the basis of kinetic results, spectroscopic information and activation parameters, a suitable mechanism and rate law for the oxidation of CHP has been proposed.

Keywords: Kinetics, Reaction mechanism, Oxidation, Rhenium, Chloramphenicol

 

Indian Journal of Chemistry

Vol. 57A, April 2018, pp. 485-489

 

Silver nanoparticle modified Pt electrode as voltammetric and electrochemical impedance sensor for hydrogen peroxide
in live biological cells

Kangkana Dekaa, Jutika Kumara, Ananya Bhowmickb, Sofia Banub & Diganta Kumar Dasa, *

aDepartment of Chemistry, Gauhati University,
Guwahati 781 014, Assam, India

Email: diganta_chem@gauhati.ac.in

bDepartment of Bio-engineering and Technology, Institute of Science and Technology,
Gauhati University, Guwahati 781 014, Assam, India

A non-enzymatic electrochemical sensor for hydrogen peroxide based on silver nanoparticle (AgNP) modified platinum electrode has been fabricated by multiple cyclic voltammetric scan of platinum electrode in AgNP solution in aqueous medium. The modified electrode (Pt/AgNP) can detect hydrogen peroxide in aqueous medium, bovine serum albumin  and live L6 rat myoblast cells with high sensitivity and selectivity by cyclic voltammetry and electrochemical impedance spectroscopy. The limit of detection of Pt/AgNP towards H2O2 is 5.4×10-7 M. The detection of H2O2 by Pt/AgNP is free of interference from Na+, K+, Ca2+, Mg2+, dopamine and ascorbic acid.

Keywords: Electroanalytical chemistry, Sensors, Nanoparticles, Silver nanoparticles, Hydrogen peroxide,Cyclic voltammetry, Electrochemical impedance spectroscopy

 

Indian Journal of Chemistry

Vol. 57A, April 2018, pp. 490-494

 

Highly selective colorimetric schiff base chemosensor for
detection of Cu2+

Dan Liu, Hua Zhu* & Li Yang

School of Chemistry and Chemical Engineering, Sichuan University of Arts and Science,
Dazhou, 635000, PR China

Email: zhuhua2006@163.com

Received 27 November 2017; revised and accepted 31 March 2018

A highly selective colorimetric chemosensor for Cu2+ has been designed using a novel Schiff base based on 2-hydroxy-1-naphthaldehyde. On addition of Cu2+, the color of Schiff base solution changes from yellow to colorless, which can be viewed with the naked eye. The proposed chemosensor is sensitive to Cu2+ with the detection limit of 1.3×10-7 mol L-1. The mechanism of the colorimetric chemosensor for the detection of Cu2+ has been investigated in detail through UV-vis, Job plot, 1H NMR and FT-IR data. The results show that a stoichiometric complex (1:1) is formed between Schiff base and Cu2+, based on the molecular proton transfer process. The selectively of the chemosensor for detection of Cu2+ over common cations has been investigated by UV-vis spectroscopy. The test strip for Cu2+ prepared according to the principle of colorimetric chemosensor illustrates the advantages of this method in terms of convenience and effectiveness.

Keywords: Analytical chemistry, Colorimetric recognition, Selectivity, Copper, Schiff Base

 

Indian Journal of Chemistry

Vol. 57A, April 2018, pp. 495-502

 

Volumetric and acoustic studies of binary liquid mixtures containing diisopropylamine and alcohols at different temperatures

Seema Rani & Gyan Prakash Dubey*

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

Email: gyan.dubey@rediffmail.com/ seemasuryavansi@gmail.com

Received 2 August 2017; revised and accepted 28 March 2018

The experimental density and speed of sound of pure diisopropylamine, 1-propanol, 2-propanol, 1-butanol, 1-pentanol and their binary mixtures with diisopropylamine as the common component are reported in the temperature range 293.15–313.15 K and at atmospheric pressure. Thermodynamic properties like excess molar volume, excess molar isentropic compressibility, deviation in speed of sound, apparent molar volume, partial molar volume, excess partial molar volume, and excess partial molar volume at infinite dilution have been calculated using the experimental density and speed of sound data for the studied mixtures at varying temperatures. Thermoacoustic parameters like excess intermolecular free-length and excess acoustic impedance have been calculated and analysed in terms of the effects of chain length, position of functional group and temperature on intermolecular interactions. Experimental results for speed of sound have been compared with those calculated using theoretical approaches of Nomoto, Van Dael, Jacobson’s free length theory and Schaaff’s collision factor theory. The calculated excess and deviation properties have been correlated with the composition of the binary mixtures using the Redlich-Kister type polynomial. The Jouyban-Acree model has also been used to correlate the density and speed of sound of all the binary mixtures. The binary coefficients of the Redlich-Kister polynomial along and Jouyban-Acree model have been estimated using the method of least squares. The correlating ability of both the approaches was tested by calculating the standard deviations. PFP theory was also applied to estimate the excess molar volume of the studied binary mixtures.

Keywords: Thermodynamic properties, Binary mixtures, Density, Speed of sound, Amines, Alcohols, Excess properties

 

Indian Journal of Chemistry

Vol. 57A, April 2018, pp. 503-506

 

DFT study on ammonium perchlorate bond activation by Pt clusters supported by carbon nanotubes and graphene

Hosseini, Seyed Ghorban* & Mohammad Hossein Zanghenehnejad

Department of Chemistry, MalekAshtar University of Technology,
 P.O.Box 16765-3454, Tehran, Iran

Email: hoseinitol@yahoo.com

Activation of the N–H bond of ammonium perchlorate is a vital channel for thermal decomposition mechanism. The N–H bond breaking on Pt4 clusters supported by carbon nanotubes and graphene has been investigated by the density functional theory method. In this study, comparison of (10-10), (8-8), (10-0) and (5-5) carbon nanotube models in zigzag and armchair forms is presented. The results show that opportune selection of size and chirality of carbon nanotubes supports can provide stable support for Pt clusters and improve their catalytic activity.

Keywords: Theoretical chemistry, Density functional calculations, Ammonium perchlorate, Platinum clusters, Carbon nanotubes, Graphene, Transition metals