Indian Journal of Chemistry

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

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

Total visitors: 449 since 17-05-2018

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

 

 

 

 

VOLUME 57A

NUMBER 05

MAY 2018

 

CONTENTS

 

Rapid Communication

 

 

605

 

Unusual redox activity of composite alkaline earth metal oxides and reduced graphene oxide system

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sudip Majumder*, Shilpa Sharma, Debasree Ghosh, Pretty Joon & Chittaranjan Sinha*

 

 

 

Reduced graphene oxide (rGO) impregnated on Group 2 alkaline earth oxides (CaO, SrO, BaO) matrix by mechanical mixing, thermal annealing and subsequent cold shock, yields new electrochemical materials, which exhibit unexpected inherent redox activity with amazing chemical reversibility. These characteristics become more prominent on moving down the group. Thermal stability of these coupled systems also increases down the group.

 

 

 

Papers

 

 

610

 

Photoinduced pyrene degradation in contaminated soils by polyaniline coated photocatalysts

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

F Shahrezaei, A Hemati Azandaryani,
A M Mansourie, A Akhbari & P Pakravan
*

 

 

 

Polyaniline coated TiO2 and ZnO nanoparticles, with improved photocatalytic efficiency for pyrene degradation, have been prepared by the interfacial polymerization method. The nanocomposites, are characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The pyrene removal efficiency is more than 95% on the polymer coated photocatalysts surface.

 

 

 

 

619

 

Fluoride selective chemosensor derived from
vitamin B6 cofactor pyridoxal

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Suban K Sahoo*, Darshna Sharma,
Anuradha Moirangthem, Anupam Basu*,
Ashok Kumar S K & Umesh D Patil

 

 

 

An easy-to-prepare, non-cytotoxic Schiff base receptor (L) is synthesized by condensation of pyridoxal with aniline. The sensor shows both naked-eye detectable color change and significant ‘turn-on’ fluorescence at 550 nm in the presence of F- with the detection limit as low as 0.4 mM. The sensor L has been successfully applied for the intracellular detection of fluoride in live cancer cell through bio-imaging technique.

 

 

 

 

 

626

 

Thermodynamic characteristics of L-arginine oscillating system catalyzed by tetraazamacrocyclic nickel(II) complex

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Lijun Ren* & Chunlan Yuan

 

 

 

A novel oscillating system comprising Arg as organic substrate and catalyzed by NiL(ClO4)2 exhibits a periodic change in the concentration of the reduced and oxidized forms of NiL22+ and NiL33+. The chemical oscillation system is a non-equilibrium system due to its negative entropy. Furthermore, the two active groups of Arg oscillating system can be activated at higher acidity.

 

Graphical abstract12

 

 

 

 

 

633

 

Interactions between N-tetradecyl-N,N-dimethyl-N-(2,3-epoxypropyl) ammonium chloride and some surfactants

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Jialin Zheng, Jing Zhao, Yan Li*, Zhen Chen,
Ling Wang, Xiaodeng Yang* & Guoqin Li

 

 

 

The interactions between TDEAC and SDS (AS, DTAC or C12DMAO) are reported. A very strong synergistic effect is observed between oppositely charged surfactants, like TDEAS and SDS (or AS) as compared to the weak interaction of TDEAC with DTAC (or C12DMAO). The micellization of the TDEAS/SDS (or AS) mixed system is a spontaneous and exothermic process. The strong synergistic effect is confirmed by steady-state fluorescence, dynamic light scattering and Rubingh regular solution approaches.

 

IJCA-2047_GA.tif

 

 

Notes

 

643

 

Role of hydrogen bonding in conformational energies of hexachlorophene and its derivatives - A theoretical study

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

C Prathipa, P Kalpana & L Akilandeswari*

 

 

 

Conformational space around two dihedral angles (viz., θ and φ) in hexachlorophene and its derivatives result in four notable minimum energy conformers (viz., a,g+; a,a; g-,a; g+,g+). Existence of  LP → σ* interactions evidenced by E(2) energies of NBO analysis and support the presence of hydrogen bonding and its role in conformational stability.

 

 

 

 

649

 

Metal supported and metal ion exchanged catalysts from palygorskite for acetylation reaction

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Dhanya Balan A P & Pushpaletha P*

 

 

 

Solid acid catalysts from palygorskite developed by three modification methods, viz., acid activation, metal salt support (with FeCl3, MnCl2, CoCl2, SnCl2, ZnCl2 and AlCl3) and metal ion exchange (exchange with Fe3+, Mn2+, Co2+, Sn2+, Zn2+ and Al3+) are found to be efficient catalysts for acetylation of alcohols with no loss of catalytic activity even after four cycles. The iron exchanged palygorskite is found to be most active.

 

IJCA-1483-ga.tif

 

 

 

655

 

Guide to Authors

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

                                   Text Box: Now Subscription Payment Made Easy

Indian Journal of Chemistry, Sec A Subscribers
You can now pay through ECS /NEFT /RTGS

Following are the details:

Bank Name: SYNDICATE BANK
Address: PUSA CAMPUS, IARI, NEW DELHI 110 012
Branch: PUSA CAMPUS, IARI, NEW DELHI
A/C No.: 90292160000079
A/C Name: NISCAIR, NEW DELHI 110 012
IFSC Code: SYNB0009029
MICR Code: 110025041
Branch Code: 9029
SWIFT Code: SYNBINBB019

Please send UTR no. with full postal address by e-mail
after payment through ECS/NEFT/RTGS to:
sales@niscair.res.in

 

Indian Journal of Chemistry

Vol. 57A, May 2018, pp. 605-609

 

Unusual redox activity of composite alkaline earth metal oxides and reduced graphene oxide system

Sudip Majumdera, b,*, Shilpa Sharmaa, Debasree Ghosha,b, Pretty Joona & Chittaranjan Sinhac, *

aDepartment of Chemistry, Amity School of Applied Sciences, Amity University Haryana

Email: sudip22m@gmail.com/ smajumder@ggn.amity.edu

bCentre for Nanoscience and Technology, Amity University Haryana

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

Email: crsjuchem@gmail.com

Received 24 March 2018; revised and accepted 26 April 2018

Reduced graphene oxide (rGO) impregnated on Group 2 alkaline earth oxides (CaO, SrO, BaO) matrix following mechanical mixing, thermal annealing and subsequent cold shock has yielded a new electrochemical material. Material characterization has been done by Fourier transform infrared spectroscopy, scanning electron microscopy and powder X-ray diffraction patterns in micrometer dimension. Thermal stability has been checked by thermal gravimetric analysis and differential scanning calorimetry. Cyclic voltammetry of the composites shows anodic peak potential in the order –0.6 V (rGO-CaO) <–0.4 V (rGO-SrO) < –0.3 V (rGO-BaO), which also follows the ordering of ionic size, Ca2+ (100 pm) < Sr2+ (118 pm) < Ba2+ (135 pm). They exhibit unexpected inherent redox activity with an amazing chemical reversibility. This characteristic becomes more prominent on moving down the group. Thermal stability of these coupled systems also increases down the group.

Keywords: Coupled systems, Composites, Reduced graphene oxide, Oxides, Metal oxides, Alkaline earth metal oxides, Electrochemical activity, Redox activity

 

Indian Journal of Chemistry

Vol. 57A, May 2018, pp. 610-618

 

Photoinduced pyrene degradation in contaminated soils by
polyaniline coated photocatalysts

F Shahrezaeia, A Hemati Azandaryanib, A M Mansouriec, A Akhbarid & P Pakravane, *

aAcademic Center for Education, Culture & Research (ACECR), Kermanshah, Iran

bNano Drug Delivery Research Center, Kermanshah University of Medical Sciences, Kermanshah, Iran

cResearch Center for Environmental Determination of Health (RCEDH),
 Kermanshah University of Medical Sciences, Kermanshah, Iran

dDepartment of Civil Engineering, Faculty of Engineering, University of Malaya,
 Kuala Lumpur, Malaysia

eDepartment of Chemistry, Zanjan Branch, Islamic Azad University, Zanjan, Iran

Email: pakravanparvaneh@iauz.ac.ir

Received 11 February 2018; revised and accepted 20 April 2018

     Polyaniline (PA) coated TiO2 and ZnO nanoparticles have been used to improve the photocatalytic efficiency of pyrene degradation in soil samples. The interfacial polymerization method is used to prepare the polyaniline coated ZnO and TiO2 nanocomposites, which are characterized by scanning electron microscopy, Fourier transform infrared spectroscopy, and X-ray diffraction. The SEM images and the SPSS analysis demonstrate the particle size distribution in the range of 100–400 nm. The surface charge of the polyaniline coated TiO2 and ZnO nanocomposites are found to be 19.5 and 21.2 mV, respectively. The pyrene removal efficiency is more than 95% on the polymer coated photocatalysts surface. The high degradation efficiency of the polyaniline coated ZnO and TiO2 nanocomposites is probably due to the high capacity of polyaniline for the adsorption of pollutants from the contaminated soils; the semiconducting behavior is reflected in the chain structure of the polymer under both ultraviolet and visible irradiation. Enhanced photocatalytic activity for degradation of pyrene under UV and visible light, is possibly due to the synergistic effect of PA and NPs.

Keywords: Photocatalysts, Photodegradation, Nanocomposites, Pyrene degradation, Soil contamination, Polyaniline, Titanium, Zinc oxide

 

Indian Journal of Chemistry

Vol. 57A, May 2018, pp. 619-625

 

Fluoride selective chemosensor derived from vitamin B6 cofactor pyridoxal

Suban K Sahooa, *, Darshna Sharmaa, Anuradha Moirangthemb, Anupam Basub, *,
Ashok Kumar S Kc & Umesh D Patild

aDepartment of Applied Chemistry, SV National Institute of Technology (SVNIT), Surat 395 007, Gujarat, India

Email: suban_sahoo@rediffmail.com

bMolecular Biology and Human Genetics Laboratory, Department of Zoology,
The University of Burdwan, Burdwan 713 104 West Bengal, India

Email: abasu@zoo.buruniv.ac.in

cSchool of Advanced Sciences, Vellore Institute of Technology University, Vellore 632 014, Tamilnadu, India

dDepartment of Chemistry, SSVPS's L K Dr P R Ghogrey Science College,Dhule 424 001, Maharashtra, India

An easy-to-prepare and non-cytotoxic Schiff base receptor (L) is synthesized by condensation of pyridoxal with aniline. The anion sensing ability of L is explored by naked-eye, UV-vis and fluorescence methods. The receptor L shows a high selectivity and sensitivity for the sensing of fluoride anion among the other tested competitive anions. The sensor L shows both naked-eye detectable color change and significant ‘turn-on’ fluorescence at 550 nm in the presence of F- with the detection limit as low as 0.4 mM. The fluoride recognition by L is supported by 1H NMR and DFT data. The detection of cytoplasmic fluoride was tested in human cancer cell HeLa through fluorescence imaging.

Keywords: Chemosensors, Anion sensors, Anion recognition, Fluoride sensor, Fluorescent turn-on, Schiff base receptors, Vitamin B6 cofactor, Pyridoxal

 

Indian Journal of Chemistry

Vol. 57A, May 2018, pp. 626-632

 

Thermodynamic characteristics of L-arginine oscillating system catalyzed by tetraazamacrocyclic nickel(II) complex

Lijun Ren* & Chunlan Yuan

College of Chemistry and Chemical Engineering, Key Laboratory of Phytochemistry,
Baoji
University of Arts and Sciences, Baoji, 721013, PR China

Email: renlijun.wind@163.com

Received 21 July 2017; re-revised and accepted 26 April 2018

A novel oscillating system with L-arginine (Arg) as organic substrate, catalyzed by a tetraazamacrocyclic nickel(II) complex (NiL(ClO4)2, (L: 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazabutadecacyclo-7,14-diene) is reported for the first time. The system has been quantitatively characterized by kinetic parameters, including the rate constants (kin, kp), the apparent activation energies (Ein, Ep), the pre-exponential constants (Ain, Ap), and the thermodynamic functions (Hin, ∆Gin, ∆Sin, ∆Hp, ∆Gp, ∆Sp). The results indicate that the NiL(ClO4)2 can catalyze the Arg oscillating reaction, exhibiting features of irreversible thermodynamics as shown by the negative entropy of the oscillating system. Further, the two active groups of the Arg oscillating system can be activated at higher acidity. A possible mechanism is also proposed for the Arg oscillating system catalyzed by NiL(ClO4)2.

Keywords: Oscillatory systems, Chemical oscillating reactions, Amino acids, Arginine oscillatory system, Induction period, Oscillating period, Irreversible chemical reactions, Kinetic parameters, Thermodynamic parameters, Nickel

 

Indian Journal of Chemistry

Vol. 57A, May 2018, pp. 633-642

 

Interactions between N-tetradecyl-N,N-dimethyl-N-(2,3-epoxypropyl)
ammonium chloride
and some surfactants

Jialin Zhenga, Jing Zhaoa, Yan Lia, *, Zhen Chenb, Ling Wangb, Xiaodeng Yanga, * & Guoqin Lib

aKey Laboratory of Fine Chemicals (Shandong Province), Qilu University of Technology,
Shandong Academy of Science, Ji’nan 250353, PR China

bThe 1st Industrial Research Laboratory, Shandong Economy and Information Technology Institute,
Ji’nan 250013, PR China

Email: liyan2554666@163.com (YL)/ yangxiaodeng@qlu.edu.cn (XY)

Received 31 January 2018; revised and accepted 18 April 2018

The interactions between the reactive cationic surfactant, N-tetradecyl-N,N-dimethyl-N-(2,3-epoxy propyl) ammonium chloride (TDEAC) and common surfactants, i.e., sodium dodecyl sulfate (SDS) sodium dodecyl sulfonate (AS), dodecyltrimethylammonium chloride (DTAC) and N, N-dimethyldodecylamine oxide (C12DMAO) are studied through surface tension, conductivity, steady-state fluorescence and dynamic light scattering as well as Rubingh regular solution methods. The calculated values of cmc, γcmc, pc20, πcmc, Гmax, and Amin indicate a strong synergistic effect between TDEAC and SDS (and AS) as compared with the relatively weak interaction of TDEAC with DTAC (and C12DMAO). The cmcs of the mixed surfactant systems vary with temperature. Thermodynamic parameters calculated from conductivity data show that the micellization of TDEAC/SDS (AS) mixed systems is a spontaneous and exothermic process. Data from steady-state fluorescence, dynamic light scattering and Rubingh’s regular solution approach, confirm the strong interaction between surfactants.

Keywords: Solution chemistry, Surface properties, Thermodynamic parameters, Surfactants, Cationic surfactants, Mixed surfactants

 

Indian Journal of Chemistry

Vol. 57A, May 2018, pp. 643-648

 

Role of hydrogen bonding in conformational energies of
hexachlorophene and its derivatives - A theoretical study

C Prathipa, P Kalpana & L Akilandeswari*

Department of Chemistry, Sri Sarada College for Women (Autonomous),
Salem 636 016, India

Email: akilchem@gmail.com

Received 11 October 2017; re-revised and accepted 25 April 2018

Conformational space around two dihedral angles (viz., θ and φ) in hexachlorophene (HCP), dimethylhexachlorophene (DMHCP) and diphenylhexachlorophene (DPHCP), has been scanned at the AM1 level and further the minima optimized at DFT(B3LYP)/6-31G(d) level. All possible hydrogen bonds that may exist in these molecules in different conformations, have been explored. NBO analyses have been carried out to establish the role of hydrogen bonds in resolving the energies of conformers.

Keywords: Theoretical chemistry, Density functional calculations, Conformational energy, Intramolecular hydrogen bonding, Hexachlorophene

 

Indian Journal of Chemistry

Vol. 57A, May 2018, pp. 649-654

 

Metal supported and metal ion exchanged catalysts
from palygorskite for acetylation reaction

Dhanya Balan A P & Pushpaletha P*

Department of Chemistry, Govt. College Kasaragod,
Kannur University, Kerala, India

Email: ppletha@rediffmail.com

Efficient solid acid catalysts from palygorskite have been developed by three modification methods, viz., acid activation, metal salt support (with FeCl3, MnCl2, CoCl2, SnCl2, ZnCl2 and AlCl3) and metal ion exchange (exchange with Fe3+, Mn2+, Co2+, Sn2+, Zn2+ and Al3+) for acetylation reaction in the liquid phase. The prepared catalysts are characterized by XRD, SEM, FTIR, NH3-TPD, cation exchange capacity, and BET surface area, and their catalytic activity tested by acetylation of primary and secondary alcohols using acetic acid. The modified palygorskites are found to be efficient catalysts for acetylation of alcohols with no loss of catalytic activity even after four cycles. The iron exchanged palygorskite is found to be most active.

Keywords: Catalysts, Supported catalysts, Solid catalysts, Cation exchange capacity, Acid activation, Acetylation, Palygorskite, Acetic acid, Alcohols