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 55A

NUMBER 10

OCTOBER 2016

 

CONTENTS

 

 

1167

 

Ionically crosslinked core-shell particles for waterborne humidity-sensitive coatings

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yusheng Wang, Chen Li, Wenzhong Zhai, Yu-Feng He*, Pengfei Song, Yubing Xiong & Rong-Min Wang*

 

 

 

Using zinc ion as ionic crosslinker, a novel self-crosslinked core-shell styrene-acrylic ionomer latex (PSA-Zn) has been prepared and characterized. The adhesive force, hardness and thermal stability of PSA-Zn film are better than that of PSA and emulsifier-free acrylate copolymer film coatings. Also, PSA-Zn coating significantly decreases or increases relative humidity in response to environmental humidity in the artificial climate.

 

 

 

 

1174

 

Synthesis, characterization and photocatalytic activity studies of tellurium containing defect pyrochlores, MSn0.5Te1.5O6 (M = K, Ag, Cu0.5 and Sn0.5)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ravinder Guje, Ravi Gundeboina,
Ramaswamy Kadari, Sreenu K, CH. Sudhakar Reddy, M Malathi, Radha Velchuri & Muga Vithal
*

 

 

 

The AgSn0.5Te1.5O6 photocatalyst exhibits higher photocatalytic activity than MSn0.5Te1.5O6 (M = K, Cu0.5 and Sn0.5) for photodegradation of methylene blue and methyl violet. The higher photocatalytic of AgSn0.5Te1.5O6 is due to its low band gap energy, which endows a very strong photooxidation ability to produce OH and O2●- radicals as active species.

 

 

 

1164

 

1182

 

Molecular adsorption study of nicotine on the nitrogen doped TiO2 anatase nanoparticles: Insights from van der Waals corrected DFT computations

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Amirali Abbasi* & Jaber Jahanbin Sardroodi

 

 

Interaction between nicotine and N-doped TiO2 nanoparticles is stronger than that between nicotine and pristine TiO2 nanoparticles. The nitrogen atom of nicotine molecule tends to be strongly adsorbed on the five-fold coordinated titanium site of
N-doped anatase nanoparticles.
Due to the van der Waals interactions between nicotine molecule and TiO2, the adsorption on the N-doped TiO2 is energetically more favorable than that on the pristine one.

 

 

Graphical.tif

 

 

 

 

1192

 

Experimental and theoretical studies on the
structure, electronic and vibrational spectra of
o/p-hydroxybenzylidene-o/p-toluidines

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

P Suna, P Hota & P K Misra*

 

 

 

The theoretical geometry optimization coupled with vibrational and electronic spectral studies of some tailor made aldimines reveal that the two benzene rings of the aldimines are out-of-plane with respect to azomethine linkage. The possible bonding sites of aldimines have been predicted by molecular electrostatic potential analysis.

 

 

 

1165

 
Notes

 

1202

 

 

Quantum mechanical study of carbon nanotubes functionalized with drugs pentoxifylline and lysofylline

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Elham Jalayeri, Ali Morsali* &
Mohammad R Bozorgmehr

 

 

 

Noncovalent interactions of pentoxifylline with (5, 5) pristine and COOH functionalized-CNTs and the mechanisms of covalent functionalization of lisofylline with (5, 5) COOH and COOCl functionalized CNTs have been studied by DFT calculations. Binding of PTX with COOH functionalized CNT is thermodynamically favorable. COOH and COCl functionalized CNT can bind to lysofylline via OH (COOH mechanism) and
Cl (COCl mechanism). The COOH mechanism has higher activation energy than the COCl mechanism, and hence the COCl pathway is suitable for covalent functionalization.

 

 

 

 

1209

 

 

Charge transfer interaction of 8-hydroxyquinoline with DDQ: Spectrophotometric, thermodynamic and molecular modeling studies

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Baindla Naveen, Lakkadi Arunapriya &
Tigulla Parthasarathy
*

 

 

 

The absorption spectra of DDQ, 8HQ and their CTC solutions in acetonitrile medium confirms the formation of the charge transfer complex. Multi-charge transfer bands are observed at 456, 548 and 588 nm in the spectra of the CT complex. KCT increases and εCT decreases as the temperature decreases, which gives an indication of the relative strength of the donor.

 

IJCA-426_GA.tif

 

 

 

 

Authors for correspondence are indicated by (*)

1166

 
 

 

 

 


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Indian Journal of Chemistry

Vol. 55A, October 2016, pp. 1167-1173

 

 

Ionically crosslinked core-shell particles for waterborne
humidity-sensitive coatings

Yusheng Wang, Chen Li, Wenzhong Zhai, Yu-Feng He*, Pengfei Song,
Yubing Xiong & Rong-Min Wang*

Key Laboratory of Eco-Environment-Related Polymer Materials of Ministry of Education,
Institute of Polymer, College of Chemistry & Chemical Engineering, Northwest Normal University,
Lanzhou 730070, China

Email: heyufeng@nwnu.edu.cn (YFH); wangrm@nwnu.edu.cn (RMW)

Received 18 April 2016; revised and accepted 23 September 2016

Using conventional functional monomers, such as methylacrylic acid (MAA), styrene (St), methyl methacrylate (MMA) and butyl acrylate (BA), the core-shell styrene-acrylic ionomer particles (PSA) are prepared by two-step emulsion polymerization. Then, using zinc ion as ionic crosslinker of the carboxylate groups from the shell layer, a novel self-crosslinked core-shell ionomer latex (PSA-Zn) has been successfully prepared and characterized by dynamic light scattering and transmission electron microscopy, whose components were also confirmed by FT-IR and TGA. After mixing pigments and porous fillers, the cheap, readily available and environment friendly coatings (PSA-Zn-C) has been prepared. Compared to PSA and
EF-AAC coatings, the adhesive force, hardness and thermal stability of PSA-Zn film are better.
Moreover, the core-shell ionomer coating (PSA-Zn-C) can significantly decrease or increase relative humidity in response to environmental humidity in the artificial climate box, and this is a promising candidate for development of waterborne humidity-sensitive coatings.

Keywords: Polymer, Ionomers, Emulsion polymerization, Core-shell ionomers latex, Zinc crosslinking particles, Smart coatings, Humidity-sensitive coatings

 

Indian Journal of Chemistry

Vol. 55A, October 2016, pp. 1174-1181

 

 

Synthesis, characterization and photocatalytic activity studies
of tellurium containing defect pyrochlores, MSn0.5Te1.5O6
(M = K, Ag, Cu0.5 and Sn0.5)

Ravinder Guje, Ravi Gundeboina, Ramaswamy Kadari, Sreenu K, CH. Sudhakar Reddy,
M Malathi, Radha Velchuri & Muga Vithal*

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

Email: mugavithal@gmail.com

Received 22 August 2016; accepted 16 September 2016

Four new metal tin tellurites, MSn0.5Te1.5O6 (M = K, Ag, Cu0.5 and Sn0.5), have been synthesized by standard solid-state and facile ion exchange reactions and characterized by powder X-ray diffraction, FTIR, SEM-EDS and UV-vis diffuse reflectance spectroscopic techniques. All the compositions crystallize in cubic lattice with  space group, and are isomorphous with KTi0.5Te1.5O6. The photocatalytic activity of the as prepared materials for methylene blue and methyl violet degradation has been investigated under visible light irradiation. The AgSn0.5Te1.5O6 photocatalyst exhibits higher photocatalytic activity than MSn0.5Te1.5O6
(M = K, Cu0.5 and Sn0.5) for photodegradation of methylene blue and methyl violet. The higher photocatalytic performance of AgSn0.5Te1.5O6 is ascribed to its low band gap energy, which endows it with a very strong photooxidation ability to produce OH and O2●- radicals as active species. The catalyst stability and mechanism of photocatalysis is also discussed.

Keywords: Catalysts, Catalytic activity, Degradation, Photocatalysis, Solid state reaction,
Ion exchange reaction, Tellurites, Pyrochlores, Defect pyrochlores

Indian Journal of Chemistry

Vol. 55A, October 2016, pp. 1182-1191

 

 

Molecular adsorption study of nicotine on the nitrogen doped
TiO2 anatase nanoparticles: Insights from
van der Waals
corrected
DFT computations

Amirali Abbasi* & Jaber Jahanbin Sardroodi

Molecular Simulation laboratory (MSL), Computational Nanomaterials Research Group (CNRG),
Department of Chemistry, Azarbaijan Shahid Madani University, Tabriz, Iran

Email: a_abbasi@azaruniv.edu

Received 5 July 2016; revised and accepted 21 September 2016

The interaction of nicotine with undoped and nitrogen-doped TiO2 anatase nanoparticles is investigated by density functional theory studies. The results indicate that the interaction between nicotine and N-doped TiO2 nanoparticles is stronger than that between nicotine and pristine TiO2 nanoparticles, which suggests nitrogen doping helps to strengthen the interaction of nicotine with TiO2 nanoparticles. In other words, the doping of nitrogen atom promotes the interaction of nicotine with TiO2 nanoparticles. It is found that the nitrogen atom of nicotine molecule tends to be strongly adsorbed on the five-fold coordinated titanium site of N-doped anatase nanoparticles. By including van der Waals interactions between nicotine molecule and TiO2, it is found that the adsorption on the N-doped TiO2 is energetically more favorable than that on the pristine one. The projected density of states analysis indicates the formation of chemical bond between nitrogen atom of nicotine and titanium atom of nanoparticle. These results offer a theoretical basis and general understanding of the interaction of TiO2 nanoparticles with nicotine, suggesting potential applications of N-doped TiO2 nanoparticles in designing of novel sensors and removers for nicotine detection.

Keywords: Density functional calculations, Nanoparticles, Nicotine, Density of states, Titania, Doped titania,
Nitrogen doping, van der Waals interactions

 

Indian Journal of Chemistry

Vol. 55A, October 2016, pp. 1192-1201

 

 

Experimental and theoretical studies on the structure, electronic and
vibrational spectra of o/p-hydroxybenzylidene-o/p-toluidines

P Suna, P Hota & P K Misra*

Centre of Studies in Surface Science and Technology, School of Chemistry,
Sambalpur University, Jyoti Vihar 768019, Odisha, India

Email: pramilamisra@rediffmail.com

Received 14 February 2016; revised and accepted 30 September 2016

The experimental and theoretical analyses of the electronic and vibrational spectra of four biologically active aldimines, i. e., o/p-hydroxybenzylidene-o/p-toluidines, using experimental techniques and semiempirical calculations are reported. Theoretical geometry optimization, and vibrational and electronic spectral studies have been computed in the gaseous phase at the PM3 and AM1 levels. The theoretical vibrational frequency data obtained from PM3 and AM1 level calculations are close to the experimental values. Geometrical optimization reveals that the two benzene rings of the aldimines are out-of-plane with respect to azomethine linkage (–C=N-). The electronic transitional energies of highest occupied molecular orbital and the lowest unoccupied molecular orbital energies calculated by FMO analysis predict the high reactivity of the molecules. The possible bonding sites of aldimines have been predicted by molecular electrostatic potential analysis. Various characteristics parameters such as electron affinity, ionization energy, hardness, softness, chemical potential and electrophilicity index of the focused aldimines are determined.

Keywords: Theoretical chemistry, Electronic spectra, Vibrational spectra, Geometry optimization,
Azomethine linkage, Aldimines, Molecular electrostatic potential, Frontier molecular orbitals

 

Indian Journal of Chemistry

Vol. 55A, October 2016, pp. 1202-1208

 

 

Quantum mechanical study of carbon nanotubes functionalized
with drugs, pentoxifylline and lysofylline

Elham Jalayeri, Ali Morsali* & Mohammad R Bozorgmehr

Department of Chemistry, Mashhad Branch, Islamic Azad University, Mashhad, Iran &
Research Center for Animal Development Applied Biology, Mashhad Branch,
Islamic Azad University, Mashhad 917568, Iran

Email: almorsali@yahoo.com/morsali@mshdiau.ac.ir

Received 30 June 2016; revised and accepted 29 September 2016

The noncovalent interactions of drug pentoxifylline (PTX) with (5, 5) pristine and COOH functionalized-carbon nanotube and the mechanisms of covalent  functionalization of the drug, lisofylline (LSF) with (5, 5) COOH and COOCl functionalized carbon nanotube have been studied by density functional theory calculations. Quantum molecular descriptors for four configurations of noncovalent interaction are calculated. It is found that binding of PTX with COOH functionalized CNT is thermodynamically favorable. COOH and COCl functionalized CNT can bind to lysofylline via OH (COOH mechanism) and Cl (COCl mechanism) groups, respectively. The barrier energies of two mechanisms have been evaluated and compared with each other. It was found that the COOH mechanism has activation energy higher than the COCl mechanism, and hence the reason for suitability of COCl pathway for covalent functionalization.

Keywords: Theoretical chemistry, Density functional calculations, Pentoxifylline, Lisofylline,
Quantum molecular descriptors, Carbon nanotubes, Reaction mechanisms

 

Indian Journal of Chemistry

Vol. 55A, October 2016, pp. 1209-1215

 

 

Charge transfer interaction of 8-hydroxyquinoline with DDQ: Spectrophotometric, thermodynamic and molecular modeling studies

Baindla Naveen, Lakkadi Arunapriya & Tigulla Parthasarathy*

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

Email: sarathychem@gmail.com

Received 3 August 2015; revised and accepted 27 September 2016

The charge transfer complex of the donor, 8-hydroxyquinoline (8HQ) with the π-acceptor 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) in acetonitrile medium has been studied spectrophotometrically at different temperatures. The 8HQ reacts instantaneously with DDQ to form reddish brown charge transfer complex. Absorption spectra of the complex shows multi-charge transfer bands at 456, 548 and 588 nm. The high values of the formation constant and molecular extinction coefficient, calculated from the Benesi-Hildebrand equation, show the high stability of the CT complex. Enthalpy and entropy of CT complex formation have been estimated by using van’t Hoff equation where the more negative value of ΔH° confirms strong bonding between donor and acceptor. The signs of ΔH°, ΔS° and ΔG° reveal that the CT complex formation process is exothermic and a spontaneous process. The experimental studies are complemented by quantum chemical calculations at DFT (B3LYP/6-31G) level of theory, including bond lengths, bond angles, Mulliken electron charge on atoms and molecular electrostatic potential maps which are helpful in assigning the CT route. In addition, GAMESS interface computations are performed to characterize the highest occupied molecular orbital and lowest unoccupied molecular orbital surfaces of the complex. A good consistency was found between experimental and theoretical results.

Keywords: Charge transfer, Thermodynamic parameters, Molecular modeling, 8-Hydroxyquinoline