Indian Journal of Chemistry

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

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

Total visitors: 2576 since 13-11-2014

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

 

 

 

 

 

VOLUME 53A

NUMBER 11

NOVEMBER 2014

 

CONTENTS

 

 

1359

 

A theoretical investigation on the cooperativity effect, reduced density gradient, stability and aromaticity in the benzonitrile∙∙∙H2O complex with Na+ or Cl–

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Jiang-Bo Xie* & Wen-Jing Shi

 

 

 

The anti-cooperative structures are more stable than the cooperative structures. Most of the ternary complexes with Na+ exhibit
the
cooperativity effects, while most of the Cl– systems show the anti-cooperativities.

 

Fig. 1.tif

 

 

 

 

1371

 

Relative stabilities and spectroscopic characterization of C82O3 based on C82 (C3v)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yifei Teng, Tanzhang Chen, Jingshan Du,
Qiwen Teng & Shi Wu*

 

 

 

The most stable geometry of C82O3 is 1,6,2,3,4,5-C82O3 with annulene-like structure. All the three oxygen atoms are added
to that hexagon which is surrounded by six other hexagons.

 

 

 

 

1377

 

Synthesis of pure and aluminum oxide doped TiO2 nanorods and study of lattice strain and activation energy of crystalline phases

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M Riazian

 

 

 

Syntheses of TiO2 nanorods in anatase, rutile and Ti8O15
phases, as well as TiO2 nanorods fabricated with aluminum
oxide as dopant by using the sol-gel method are reported.
An aggregative structure is observed at high calcination temperatures with the formation of spherical particles.

 

 

 

 

 

1384

 

Multifunctional P and Mn co-doped titania nanoparticles as efficient visible light driven photocatalyst

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Susmitha Thota, Sivarao Tirukkovalluri*,
Sreedhar Bojja & Girija Sankar G

 

 

 

Phosphorous and manganese co-doped titanium dioxide nanopowder exhibits excellent photocatalytic activity with hydroxyl radical as the reactive oxygen species in destruction of E. coli and degradation of azo dye under visible light. Co-doping results in formation of smaller particle size and reduced band gap.

 

 

 

 

 

Notes

 

1391

 

New fluorescent chemodosimeter for Cu2+ based
on Schiff base derived from 1-naphthylamine and
2-chlorobenzaldehyde

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Jutika Kumar & Diganta Kumar Das*

 

 

 

The condensation product of 1-naphthylamine and 2-chloro-benzaldehyde acts as a fluorescent “on” chemodosimeter for Cu2+ due to the ability of the latter to form a tris-chelate complex with Cu2+ and subsequent release of the fluorescent 1-naphthylamine.

 

 

 

1397

 

Reaction of titanium(IV) tetraisopropoxide with salicylidene-2-aminopyridine and spectral studies

 

 

 

 

 

 

 

 

 

 

 

Raj Kumar Dubey* & Avadhesh Pratap Singh

 

 

 

Titanium(IV) complexes in six and seven coordinate states have been synthesized by the isopropanol-ligand reaction.

 

 

 

 

1402

 

Structural effects of cationic surfactants in polyacrylamide-surfactant interaction: Micellisation/ adsorption of polyacrylamide

 

 

 

 

 

 

 

 

 

 

P S Niranjan & S K Upadhyay*

 

 

 

Increasing the polymer content, increasing –CH2 group in the tail of the cationic surfactant or increasing the bulkiness of the hydrophobic head group of the surfactant favour adsorption of the polymer on the surfactant.

 

GA

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

Indian Journal of Chemistry

Vol. 53A, November 2014, pp. 1359-1370

 

 

A theoretical investigation on the cooperativity effect, reduced density gradient, stability and aromaticity in the benzonitrile∙∙∙H2O complex
with Na+ or Cl
–

Jiang-Bo Xiea, * & Wen-Jing Shib

aCollege of Materials Science and Engineering, North University of China, Taiyuan 030051, China

Email: xjb209@126.com

bThe Third Hospital of Shanxi Medical University, Taiyuan 030053, China

Received 26 May 2014; revised and accepted 15 October 2014

The cooperativity effect between the H-bonding and Na+∙∙∙σ/π or Cl–∙∙∙H–O/C interactions, the reduced density gradient (RDG) and the aromaticity evaluated by nucleus-independent chemical shift in Na+/Cl–∙∙∙benzonitrile∙∙∙H2O complex are investigated by using the B3LYP and MP2(full) methods with the 6-311++G(2d,p) basis set. The results show that the influence of the Na+∙∙∙σ/π or Cl–∙∙∙H–O/C interaction on H-bond is more pronounced than that of the latter on the former. Most of the ternary complexes with Na+ exhibit the cooperativity effects while most of the Cl– systems show anti-cooperativities. The cooperativity effect is observed in the complex in which Na+ or Cl– point towards either benzonitrile or H2O, while the anti-cooperativity effect is seen in the system where the ion points simultaneously to benzonitrile and H2O. The anti-cooperative structures are more stable than the cooperative structures. The cooperativity effect has a notable influence on the aromaticity and π→π* conjugative effect. The analyses of RDG and AIM (atoms in molecules) confirm the existence of cooperativity.

Keywords: Theoretical chemistry, Cooperativity effect, Noncovalent interactions, Reduced density gradient, Stability, Aromaticity

 

Indian Journal of Chemistry

Vol. 53A, November 2014, pp. 1371-1376

 

 

Relative stabilities and spectroscopic characterization of
C82O3 based on C82 (C3v)

Yifei Tenga,b, Tanzhang Chena, Jingshan Dua, Qiwen Tenga & Shi Wua, *

aDepartment of Chemistry, Zhejiang University, Hangzhou 310027, PR China

Email: wushi@zju.edu.cn

bDepartment of Chemistry, Jilin University, Changchun 130012, PR China

Received 12 February 2014; revised and accepted 12 September 2014

The relative stabilities of the twenty possible isomers for C82O3 based on C82 (C3v) have been studied using density function theory. The most stable geometry of C82O3 has been found to be 1,6,2,3,4,5-C82O3 with annulene-like structure, where the additive bonds are located on the same hexagon surrounded by other six hexagons. The annulene-like isomers with the low cyclic tension of C82O3 are more stable than the epoxy isomers. Generally, the energy gaps of the C82O3 isomers are wider than that of C82 (C3v). The chemical shifts of the bridged carbon atoms in C82O3 move upfield in contrast to those of the corresponding carbon atoms in C82 (C3v). Different from the anti-aromaticity of C82 (C3v), the epoxy isomers of C82O3 basically show the aromaticity.

Keywords: Theoretical chemistry, Density functional calculations, Stability, Fullerenes, Exohedral fullerenes, Energy gap, NMR spectroscopy, Aromaticity, Chemical shifts

 

Indian Journal of Chemistry

Vol. 53A, November 2014, pp. 1377-1383

 

 

Synthesis of pure and aluminum oxide doped TiO2 nanorods and study of
lattice strain and activation energy of crystalline phases

M Riazian

Department of Engineering, Tonekabon branch, Islamic Azad University, Tonekabon, Iran

Email: m.riazian@toniau.ac.ir

Received 8 May 2014; revised and accepted 20 October 2014

Synthesis of TiO2 nanorods in anatase, rutile and Ti8O15 phases, as well as TiO2 nanorods fabricated with aluminum oxide as dopant by using the sol-gel method is reported. The morphologies and the crystal structures of TiO2 nanorods are characterized by field emission scanning electron microscopy, atomic force microscopy and
X-ray diffractometer techniques. The obtained results illustrate an aggregative structure at high calcined temperatures with the formation of spherical particles. The effects of chemical compositions and calcined temperatures on surface topography and crystallization of phases are studied. In addition, the activation energy of nanoparticles formation in pure and doped state are calculated during thermal treatment.

Keywords: Nanomaterials, Crystalline phases, Nanorods, Titania, Lattice Strain, Activation energy, Alumina, Dopants, Sol-gel method

 

Indian Journal of Chemistry

Vol. 53A, November 2014, pp. 1384-1390

Multifunctional P and Mn co-doped titania nanoparticles as
efficient visible light driven photocatalyst

Susmitha Thotaa, Sivarao Tirukkovalluria, *, Sreedhar Bojjab & Girija Sankar Gc

aDepartment of Inorganic & Analytical Chemistry, School of Chemistry, Andhra University,
Visakhapatnam 530 003, Andhra Pradesh, India

Email: sivaraotvalluri.16@gmail.com

bInorganic & Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology,
Hyderabad 500 007, Andhra Pradesh, India

cPharmaceutical Biotechnology Division, Andhra University College of Pharmaceutical Sciences,
Andhra University, Visakhapatnam 530 003, Andhra Pradesh, India

Received 5 May 2014; revised and accepted 25 September 2014

Phosphorus and manganese co-doped titanium dioxide nanoparticles have been synthesized by sol-gel method and characterized by XRD, UV-visible DRS, XPS, SEM, TEM and BET. XRD data show the anatase phase in all the samples, while XPS analysis shows the dopant phosphorus in the P5+ state and manganese in the Mn4+/Mn3+ states. The co-doped catalysts show a particle size of 7 nm, with strong absorption in the visible region. The photocatalytic activity of the as-prepared catalysts has been tested by degradation of the azodye, acid orange 7 under artificial light as well as under direct sunlight. Photoluminiscence studies with the co-doped catalysts show enhanced generation of hydroxyl radicals, the key oxidative species in photocatalytic reactions. In addition, the antibacterial activity of the nanoparticles against Escherichia coli has also been investigated. The results indicate that the as co-doped TiO2 nanoparticles can be used not only as an efficient photocatalyst for potential applications in the fields of pollution abatement process but also as an excellent antibacterial agent.

Keywords: Photochemistry, Nanoparticles, Dye degradation, Azo dyes, Photocatalysts, Co-doped photocatalysts, Titania, Manganese, Phosphorus, Antibacterial activity

Indian Journal of Chemistry

Vol. 53A, November 2014, pp. 1391-1396

 

 

New fluorescent chemodosimeter for Cu2+ based on Schiff base derived from
1-naphthylamine and 2-chlorobenzaldehyde

Jutika Kumar & Diganta Kumar Das*

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

Email: digantakdas@gmail.com

Received 10 June 2014; re-revised and accepted 10 October 2014

On condensation of 1-naphthylamine with 2-chlorobenzaldehyde, the Schiff base (Z)-N-(2-chlorobenzylidene)naphthalene-1-amine (L) is formed which shows moderate fluorescence. L on interaction with Cu2+ hydrolyses back into fluorescent 1-naphthylamine and hence acts as fluorescent chemodosimeter for Cu2+ by
“off-on” mode with an ca. 18 times enhancement in fluorescent intensity (detection limit is 10-5 M). The other hydrolysed product, 2-chlorobenzaldehyde, forms a tris chelate complex with Cu2+, as shown by UV/visible spectroscopy and cyclic voltammetry. The metal ions, Na+, K+, Ca2+, Mn2+, Fe2+, Co2+, Ni2+, Cd2+, Hg2+, Pb2+ and Ag+, do not interfere while in the case of Zn2+, moderate interference is observed.

Keywords: Fluorescence, Chemodosimeters, Sensors, Copper, Naphthylamine, Chlorobenzaldehyde, Schiff bases

 

Indian Journal of Chemistry

Vol. 53A, November 2014, pp. 1397-1401

 

 

Reaction of titanium(IV) tetraisopropoxide with
salicylidene-2-aminopyridine and spectral studies

Raj Kumar Dubey* & Avadhesh Pratap Singh

Synthetic Inorganic and Metallo-organic Research Laboratory, Department of Chemistry,
University of Allahabad, Allahabad 211 002, India

Email: rajalkoxy@yahoo.com

Received 23 February 2014; re-revised and accepted 21 October 2014

Reaction of Ti(OPri)4 with salicylidene-2-aminopyridine in different molar ratio(s) afforded mononuclear complexes of the type, [(sap)nTi(OPri)4-n] (1-3), (where n = 1-3; sap = salicylidene-2-aminopyridine). The reaction of complex (2) with N-methyl-diethanolamine in equimolar ratio afforded the complex [(sap)2Ti(mdea)] (4). All these complexes have been characterized by elemental (C, H, N and Ti) analyses and spectral (IR, NMR (1H, 13C)) studies. The molecular structure as well as composition of the complexes has been tentatively assigned on the basis of these spectral and mass fragmentation studies.

Keywords: Coordination chemistry, Alkoxides, Metal alkoxides, Schiff bases, Titanium

 

Indian Journal of Chemistry

Vol. 53A, November 2014, pp. 1402-1406

 

Structural effects of cationic surfactants in polyacrylamide-surfactant interaction: Micellisation/adsorption of polyacrylamide

P S Niranjan & S K Upadhyay*

Department of Chemistry, Harcourt Butler Technological Institute, Kanpur 208 002, India

Email:upadhyay_s_k@rediffmail.com

Received 20 June 2014; revised and accepted 22 October 2014

The structural effects of two cationic surfactants, viz., dodecyl trimethyl ammonium bromide and benzalkonium chloride, in polyacrylamide surfactant interactions has been studied. The effect of structural features of the surfactant on the micellization and/or on adsorption has been studied in terms of CMC/C20 ratio. An increase in the polymer content, increasing –CH2 group in the tail of the cationic surfactant or increasing the bulkiness of the hydrophobic head group of the surfactant favors the adsorption of polymer on the surfacant.

Keywords: Cationic surfactants, Adsorption of polymers, Micellisation, Dodecyltrimethyl ammonium bromide, Benzalkonium chloride, Polyacrylamide