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 7

JULY 2017

 

CONTENTS

 

 

747

 

Solvent-free facile synthesis of di-octyl phthalate over heterogeneous sulfated zirconia acid catalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ajay M Parmar, K Saravanan, Beena Tyagi* & Kannan Srinivasan

 

 

 

The re-usable SZr solid acid catalyst exhibits activity similar to that of H2SO4 and p-TSA for synthesis of DOP as plasticizer via esterification of phthalic acid and n-octanol.

 

Fig-ga.tif

 

 

756

 

Effect of charge and spin multiplicity on hyperpolarizabilities of donor-acceptor substituted polyenes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Subhadip Ghosh, Ria Sinha Roy, Paramita Banerjee, Avijit Mondal, K Hatua & Prasanta K Nandi*

 

 

 

Theoretical studies on the ground state structure and nonlinear optical properties of donor-acceptor substituted singlet and triplet (neutral) and doublet (mono-positive and mono-negative) polyenes have been carried out. Isotropic polarizability and the second-hyperpolarizability are predicted to be larger for the doublet anions in which the NH2 group is pyramidal. The position of nitrogen atom in the p-conjugative path strongly modulates the magnitudes of both the first- and second-hyperpolarizabilities of the investigated polyenes.

 

 

 

 

767

 

Layer-by-layer synthesis of nano Prussian blue electrochromic thin film modified electrodes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Shaza Al Shaal*, Francois Karabet & Hasan Kellawi

 

 

 

A novel simple non-electrical method has been developed for synthesis of modified electrodes comprising Prussian blue
nano thin film on indium tin oxide substrates
, by layer-by-layer assembly method combined with sacrificial Ag anode. The
nano thin film shows excellent stability and acceptable electrochromic properties.

 

GA.jpg

 

 

Notes

 

774

 

Geminally biotinylated cyclotriphosphazenes as molecular binding probe

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Xuebin Ma, Tingting Xu, Wei Chen, Rui Wang,
Zheng Xu, Bo Chi
* & Zhiwen Ye*

 

 

 

Biotinylated cyclotriphosphazene with geminal octopus-like molecular shape has been prepared by stepwise substitution of cyclotriphosphazene with hydrophilic MPEG and biotin moieties. Geminal biotinylated cyclotriphosphazene polymer, g-BTP, shows higher binding affinity to avidin and is polydispersed as compared to the random coil biotinylated linear polymer, BLP.

 

 

Fig-4.tif

 

 

 

780

 

Sulphur and cerium co-doped mesoporous titanium dioxide photocatalysts and their photocatalytic activity in the degradation of methylene orange

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Zelin Niu, Zhanping Song*, Jingping Qiu,
Xiaogang Sun & Jun Xing

 

 

 

Sulphur and cerium co-doped mesoporous titanium dioxide photocatalysts have been synthesized and characterised. Higher degradation of methyl orange has been achieved with the doped photocatalysts with 2 mol% S and 1 mol% Ce co-doped MTiO2 catalysts showing the highest activity.

 

 

 

 

 

 

786

 

DFT calculations of effective reactive sites of inositol

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

D Jeevitha, K Sadasivam* & R Praveena

 

 

 

The 2-OH site has been found to be the most reactive site of inositol by the DFT method. These results have been supported by results obtained from BDE, HOMO-LUMO and MEP methods. The strong and weak intramolecular interactions have also been identified by NBO analysis.

 

 

 

791

 

 

Guide to Authors

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

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Indian Journal of Chemistry

Vol. 55A, July 2017, pp. 747-755

 

Solvent-free facile synthesis of di-octyl phthalate over heterogeneous sulfated zirconia acid catalyst

Ajay M Parmara,b, K Saravanana,b, Beena Tyagia,b, * & Kannan Srinivasana,b

aInorganic Materials and Catalysis Division, bAcademy of Scientific and Innovative Research (AcSIR),
CSIR-Central Salt and Marine Chemicals Research Institute (CSIR-CSMCRI), GB Marg, Bhavnagar 364 002, India

Email: btyagi@csmcri.res.in

Received 1 April 2017; revised and accepted 20 June 2017

The present study reports the synthesis of di-octyl phthalate (DOP), widely used as a plasticizer, via solvent-free esterification of phthalic acid and n-octanol over sulfated zirconia (SZr) heterogeneous acid catalyst.
A comparison with other heterogeneous acid catalysts such as K-10 acid activated clay, zeolites (β and Y), Amberlyst-15 resin shows the superior activity of SZr, exhibiting maximum conversion of n-octanol (88%) with 93% DOP selectivity at 160 °C in 6 h. The rate of the reaction for SZr catalyst is computed as
17.3 mmol h−1 g−1. The catalyst activity is stable upon recycling for up to five cycles. The weak acid sites of the catalyst are postulated as the responsible active centres involved in the reaction. The reaction has been successfully scaled up over twenty five times; and
the product DOP (67 g, 99% by GC) isolated and characterized by FT-IR and 1H NMR spectroscopy. It is noteworthy that the activity of SZr catalyst is comparable with that of H2SO4 and p-toluene sulphonic acid (p-TSA), which clearly suggets its potential as an efficient alternative to conventional commercial homogeneous acid catalysts for the synthesis of DOP.

Keywords: Heterogeneous catalysts, Acid catalysts, Esterification, Sulfated zirconia, Di-octyl phthalate, Phthalic acid

 

Indian Journal of Chemistry

Vol. 56A, July 2017, pp. 756-766

 

Effect of charge and spin multiplicity on hyperpolarizabilities of
donor-acceptor substituted polyenes

Subhadip Ghosh, Ria Sinha Roy, Paramita Banerjee, Avijit Mondal, K Hatua & Prasanta K Nandi*

Department of Chemistry, Indian Institute of Engineering Science and Technology, Shibpur, Howrah 711 103, India

Email: nandi_pk@yahoo.co.in

Received 13 April 2017; revised and accepted 22 June 2017

Theoretical studies of the ground state structure and nonlinear optical (NLO) properties of a number of donor-acceptor substituted singlet and triplet (neutral) and doublet (mono-positive and mono-negative) polyenes have been carried out. The variation of NLO property of the investigated molecules has been explained by using previously derived relationships between the different order polarizabilities and ground state dipole moment obtained in the framework of the standard sum-over-state expressions of Orr-Ward-Bishop and the generalized Thomas-Kuhn sum rule. The effect of charge and spin multiplicity on the molecular hyperpolarizabilities have been discussed in terms of relative changes of polarizability and ground state dipole moment. Among the investigated polyenes, the isotropic polarizability and the second-hyperpolarizability are predicted to be larger for the doublet anions in which the NH2 group is pyramidal. The position of nitrogen atom in the p-conjugative path strongly modulates the magnitudes of both the first- and second-hyperpolarizabilities of the investigated polyenes.

Keywords: Theoretical chemistry, Ground state structure, Nonlinear optical properties, Hyperpolarizabilities, Charge, Spin multiplicity, Sum-over-state expressions, Polyenes

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 56A, July 2017, pp. 767-773

 

Layer-by-layer synthesis of nano Prussian blue electrochromic
thin film modified electrodes

Shaza Al Shaal*, Francois Karabet & Hasan Kellawi

Department of Chemistry, Faculty of Sciences, Damascus University, Damascus, Syria

Email: shazamalshaal@gmail.com

Received 3 June 2016; revised and accepted 28 June 2017

A novel simple non-electrical fully controlled method has been developed for synthesis of modified electrodes by Prussian blue thin film on indium tin oxide substrates. The method comprises a tiny spot of silver as a sacrificed anode applied on one corner of the substrate by using layer-by-layer method for deposition nano Prussian blue thin film layers of electrodes (LBL/Ag), from a solution of equal concentrations of ferric chloride and potassium ferricyanide. The morphology of Prussian blue nanoparticles has been investigated by scanning electron microscopy and atomic force microscopy. The Prussian blue thin film thickness has been calculated. The Prussian blue film exhibits linear increase in the UV-vis light absorbance with the number of deposited layers, indicating that well organized lamellar systems are involved, which is consistent with the results based on the cyclic voltammetry measurements. These results show excellent electrochemical and reversible stable thin films, favorable for various applications such as electrochromic devices.

 

Indian Journal of Chemistry

Vol. 56A, July 2017, pp. 774-779

 

Geminally biotinylated cyclotriphosphazenes as molecular binding probe

Xuebin Maa, Tingting Xub, Wei Chenb, Rui Wangb, Zheng Xub, Bo Chib, * & Zhiwen Yea, *

aShoool of Chemical Engineering, Nanjing University of Science and Technology, Nanjing, China

bState Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing, China

Email: yezw@njust.edu.cn (YE)/ chibo@njtech.edu.cn (BC)

Received 19 July 2016; revised and accepted 30 June 2017

Biotinylated cyclotriphosphazenes polymer (g-BTP) with geminal octopus-like molecular shape has been prepared and characterized by 31P-NMR, 1H-NMR and Matrix-assisted laser desorption ionization-time of flight-mass spectrometry (Maldi-Tof-Ms). Analysis of the size distribution of the complexes showed that the aggregated g-BTP/avidin complexes were rather polydispersed and uniform as compared to complexes formed by random coil biotinylated linear polymer (BLP) and avidin. Binding kinetics studies show that both of g-BTP and BLP can bind avidin very quickly. The binding ability as evaluated by Scatchard plot indicates the binding ability of g-BTP to be about 5.5 times that of BLP.

 

Indian Journal of Chemistry

Vol. 56A, July 2017, pp. 780-785

 

Sulphur and cerium co-doped mesoporous titanium dioxide photocatalysts and their photocatalytic activity in the degradation of methylene orange

Zelin Niua, Zhanping Songa, *, Jingping Qiub, Xiaogang Sunb & Jun Xingb

aCollege of Civil Engineering, Xi’an University of Architecture and Technology, Xi’an 710055, China

Email: szp1916@sina.com

bKey Laboratory of Ministry of Education on Safe Mining of Deep Metal Mines, Northeastern University, Shenyang 110819, China

Received 20 April 2016; revised and accepted 30 June 2017

A series of sulphur and cerium co-doped mesoporous titanium dioxide photocatalysts have been prepared by a template method using thiourea, ammonium ceric nitrate and tetrabutyl titanate as precursors and Pluronic P123 as a template. The morphology, crystal structure, surface structure and optical absorption properties of the prepared samples are characterized by scanning electron microscopy, X-ray diffraction, N2 adsorption-desorption measurements and UV-vis absorption spectra. The microcrystal of the co-doped photocatalyst comprises the anatase­ phase. Compared with mesoporous titanium dioxide, the co-doped samples extends the photoabsorption edge into the visible light region. The photocatalytic activities of the obtained photocatalysts under UV and visible light have been estimated by measuring the degradation rate of methylene orange in aqueous solution. Results show that the co-doped mesoporous titanium dioxide exhibits higher photocatalytic activity than mesoporous titanium dioxide under light irradiation. The synergistic effect of sulphur and cerium co-doping plays an important role in improving the photocatalytic activity.

Keywords: Photocatalysts, Mesoporous catalysts, Doping, Co-doping, Cerium doping, Sulphur doping, Degradation, Methylene orange degradation, Titanium dioxide

 

 

Indian Journal of Chemistry

Vol. 56A, July 2017, pp. 786-790

 

DFT calculations of effective reactive sitesof inositol

D Jeevithaa, K Sadasivama, * & R Praveenab

aDepartment of Physics, bDepartment of Chemistry, Bannari Amman Institute of Technology (Autonomous), Sathyamangalam, Erode 638 401, Tamil Nadu, India

Email: dftsada@gmail.com

Received 21 February 2017; revised and accepted 28 June 2017

Computational investigation of the naturally occurring compound, inositol, is evaluated to find the most reactive site and also its electron donating ability. Structural and molecular characteristics of inositol are analyzed using DFT/B3LYP/6-311G(d.p). Radical 2-OH is found to be the appropriate reactive site for hydrogen abstraction which is supported by the computed values of bond dissociation enthalpy, HOMO-LUMO and molecular electrostatic potential. Molecular descriptors like ionization potential, electron affinity, hardness, softness, electronegativity and electrophilic index are also calculated. Natural bond orbital analysis is carried out to identify the strong and weak intramolecular hyperconjugative interactions.

Keywords: Theoretical chemistry, Density functional calculations, Bond dissociation enthalpy,
HOMO-LUMO, Natural bond orbitals, Inositol