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 7

JULY 2016

 

CONTENTS

 

 

769

 

Does HF prefer to be attached to X or M of XHHM
(X = F, Cl, Br; M=Li, Na, K) system? A B3LYP and MP2 theoretical investigation into cooperativity effect

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Hai-bin Wang, Wen-jing Shi*, Fu-de Ren &
Ying-xin Tan

 

 

 

Stronger cooperativity effect in FH∙∙∙XH∙∙∙HM than in
XH∙∙∙HM∙∙∙FH leads to FH preferring to be attached to X.

 

 

 

 

782

 

Theoretical study of hydrogen bonded picolinic acid-water complexes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Mridula Guin*, Ananth N Nayak &
Netkal M Made Gowda

 

 

 

Quantum chemical calculations performed on the hydrogen bonded picolinic acid-water complexes by Hartree-Fock, second-order Moller-Plesset perturbation theory, density functional theory, and density functional theory with dispersion correction using
6-311++G(d,p) basis set have identified three monohydrated complexes, all of which are minima on the potential energy surface at all levels of computations. Among the three hydrated picolinic acid complexes, the structures PA-W1 and PA-W3 retain intramolecular OH∙∙∙N interactions upon hydration. Of these, the complex PA-W1, containing three different types of hydrogen bonding, is the most stable structure.

 

 

 

 

793

 

Physicochemical studies on effect of additives on clouding behavior and thermodynamics of polyoxyethylene (20) sorbitan monooleate

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Md. Anamul Hoque*, Attikunahar Mitu,
Mohammad-Omar-Faruk Patoary &
D M Shafiqul Islam

 

 

 

Cloud point of Tween 80, is determined in aqueous medium and in presence of aqueous solutions of salts, viz., sodium chloride, sodium sulfate, sodium nitrate, and, water soluble polymers, viz., polyvinylpyrrolidone, polyvinyl alcohol, polyethylene glycol. The addition of salts lowers the cloud point of Tween 80 with SO42- the most efficient cloud point depressor as compared to the other monovalent ions, Cl- and NO3-. The values of change in standard free energy, enthalpy and entropy decrease with increase of concentration of Tween-80.

 

 

 

Notes

 

803

 

Solar light induced photodegradation of oxytetracyline using Zr doped TiO2/CaO based nanocomposite

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Pankaj Raizada*, Bhanu Priya, Pankaj Thakur & Pardeep Singh

 

 

 

Zr-TiO2/CaO exhibits significant photocatalytic activity under solar light for OTC degradation. The monohydrate fluoroferrate of bipyridine is built up from Fe4F10N8 tetrahedron connected by eight nitrogen atoms of four 2,2'-bipyridine molecules and separated by H2O molecules. The main feature of this atomic arrangement is the coexistence of two oxidation states of iron cations and hybrid class II with 0-D dimensionality.

 

 

 

 

 

810

 

A new hybrid iron fluoride bipyridine with mixed valence: Fe2F5(2,2'-bipyridine)2H2O

 

 

 

 

 

 

 

 

 

 

Mouna Smida*, Mohamed Damak &
Santiago Garcia-Granda

 

 

 

The new mixed compound Fe2F5(2,2'-bipyridine)2H2O crystallizes in the triclinic system with space group .

 

 

 

 

816

 

Synthesis and characterization of [Ni-Al-Fe]
nanocomposite and its application for the removal of cadmium(II) and zinc(II) ions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Y V S Sai Krishna, R Ravichandra Babu* &
P V Satyam

 

 

 

[Ni-Al-Fe] nanocomposite of 10 nm size has been synthesized via solution combustion route using aqueous solutions containing aluminum nitrate, iron nitrate and nickel nitrate as oxidizers and glycine as fuel. The synthesized composite has been used as a potential adsorbent for the removal of Cd(II) and Zn(II) from aqueous solution. The process reaches equilibrium within 35 min and is highly pH dependant; the removal of Cd(II) is significant at a pH 6.5 while the removal of Zn(II) is significant at pH 9.0.

 

 

 

 

820

 

Investigations on interaction between atazanvir sulphate and bovine serum albumin by fluorescence spectroscopy

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Umesh S Mote* & G B Kolekar

 

 

 

The interaction between bovine serum albumin and atazanvir sulphate has been investigated at the physiological pH 7.4 using fluoresence spectroscopy. Synchronous fluorescence spectra and three dimensional spectra show that the conformation of BSA undergoes a change upon interaction with AS.

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 


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Indian Journal of Chemistry

Vol. 55A, July 2016, pp. 769-781

 

 

Does HF prefer to be attached to X or M of XHHM (X = F, Cl, Br; M = Li, Na, K) system? A B3LYP and MP2 theoretical investigation
into cooperativity effect

Hai-bin Wanga, Wen-jing Shib, * , Fu-de Rena & Ying-xin Tana

aCollege of Chemical Engineering and Environment, North University of China, Taiyuan 030051, China

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

Email: wenjingfd@126.com

Received 10 March 2015; revised and accepted 24 June 2016

The cooperativity effects are investigated in the possible linear dihydrogen-bonded ternary complexes,
F
H∙∙∙XH∙∙∙HM and XH∙∙∙HM∙∙∙FH, and non-dihydrogen-bonded quaternary systems, FH∙∙∙X∙∙∙HH∙∙∙M+ and X∙∙∙HH∙∙∙M+∙∙∙FH (X=F, Cl, Br; M=Li, Na, K) using the DFT-B3LYP/6-311++G(3df,2p) and MP2(full)/6-311++G(3df,2p) methods. The result shows that for the dihydrogen-bonded complex, remarkable cooperativity effect is found and the cooperativity effect of the H∙∙∙H bond on the H∙∙∙X or M∙∙∙F interaction is more pronounced than that of the H∙∙∙X or M∙∙∙F contact on the H∙∙∙H interaction. The complexation energy and cooperativity effect in FH∙∙∙XH∙∙∙HM are larger than those of the corresponding XH∙∙∙HM∙∙∙FH system. Thus, the FH∙∙∙XH∙∙∙HM complex is preferentially formed and FH prefers to be attached to the X end. For the non-dihydrogen-bonded quaternary system, due to the stronger complexation energy and cooperativity effect of Cl∙∙∙HH∙∙∙Li+∙∙∙FH or FH∙∙∙Br∙∙∙HH∙∙∙K+ as compared to those of FH∙∙∙Cl∙∙∙HH∙∙∙Li+ or
Br∙∙∙HH∙∙∙K+∙∙∙
FH, FH prefers to be attached to Li+ or Br. Cooperativity effect is analyzed using the charges on hydrogen in the H∙∙∙H moiety, surface electrostatic potentials and atoms in molecules analysis.

Keywords: Theoretical chemistry, Density functional calculations, Cooperativity effect, Dihydrogen bonds, Hydrogen bonds

 

Indian Journal of Chemistry

Vol. 55A, July 2016, pp. 782-792

 

 

Theoretical study of hydrogen bonded picolinic acid-water complexes

Mridula Guin*, Ananth N Nayak & Netkal M Made Gowda

aPooja Bhagavat Memorial Mahajana PG Centre, University of Mysore, KRS Road, Mysore 570 016, India

Email: mridula.guin@gmail.com

Received 11 March 2016; revised and accepted 20 June 2016

Quantum chemical calculations have been performed on the hydrogen bonded picolinic acid-water complexes by Hartree-Fock, second-order Moller-Plesset perturbation theory, density functional theory, and density functional theory with dispersion correction using 6-311++G(d,p) basis set. For the isolated picolinic acid moiety, four stable stationary points, corresponding to four different conformers are found at all levels of calculation. The structure with intramolecular COO-HN hydrogen bond is found to be the most stable conformer at all levels of theory. Taking the lowest energy conformer as the starting geometry, three different conformers are predicted for the binary complexes of picolinic acid with water. Geometrical parameters, interaction energy, vibrational analysis in detail have been investigated. The intramolecular hydrogen bond is retained in two complexes while structural deformation occurs in one complex due to cleavage of the intramolecular hydrogen bond. The natural bond orbital analysis and atoms in molecules theory have been applied to understand the nature of interaction present in picolinic acid-water complexes.

Keywords: Theoretical chemistry, Density functional calculations, Ab initio calculations, Hydrogen bonding,
Atom-in-molecule analysis, Natural bond orbitals

 

Indian Journal of Chemistry

Vol. 55A, July 2016, pp. 793-802

 

 

Physicochemical studies on effect of additives on clouding behavior and thermodynamics of polyoxyethylene (20) sorbitan monooleate

Md. Anamul Hoque*, Attikunahar Mitu, Mohammad-Omar-Faruk Patoary & D M Shafiqul Islam

Department of Chemistry, Jahangirnagar University, Savar, Dhaka 1342, Bangladesh

Email: ahoque_ju@yahoo.com

Received 31 January 2016; revised and accepted 20 June 2016

Cloud point (CP) of nonionic surfactant, namely polyoxyethylene (20) sorbitan monooleate (Tween-80) in aqueous environment and in the presence of different additives such as salts (sodium chloride, NaCl; sodium sulfate, Na2SO4; sodium nitrate, NaNO3) and polymers (polyvinylpyrrolidone, PVP; polyvinyl alcohol, PVA; polyethylene glycol, PEG) have been studied. The CP values of Tween-80 in aqueous medium are found to decrease with increase of surfactant concentration. The CP values of Tween-80 are lower in magnitude in the presence of sodium salts as compared to those in aqueous medium; the effect of sodium salts (between 0.1 and 10 mmol L-1) in reducing CP values were found to be in the order: Na2SO4 ˃ NaCl ˃ NaNO3. The CP values of Tween-80 solutions also decrease with increasing concentrations of polymers used. The values of ∆G0c are positive in all the cases, indicating the non-spontaneous nature of clouding. ∆H0c and ∆S0c values were found to be almost negative in the presence of salts and polymers, except in the case of the PEG-water system. The negative values of ∆H0c and ∆S0c decrease with increasing concentrations of salts and polymers.

Keywords: Cloud point, Tween-80, Surfactants, Hydrophobic interactions, Thermodynamic parameters

 

Indian Journal of Chemistry

Vol. 55A, July 2016, pp. 803-809

 

 

Solar light induced photodegradation of oxytetracyline using Zr doped TiO2/CaO based nanocomposite

Pankaj Raizadaa, *, Bhanu Priyaa, Pankaj Thakura,b & Pardeep Singha

aSchool of Chemistry, Faculty of Basic Sciences, Shoolini University, Solan (HP) 173 212, India

Email: pankajchem1@gmail.com

bCenter for Advanced Biomaterials for Healthcare, Istituto Italiano Di Tecnologia, Naples 80125, Italy

Received 3 July 2015; re-revised and accepted 27 June 2016

Zr doped TiO2/CaO (Zr-TiO2/CaO) has been synthesized by sol-gel method and its photocatalytic activity tested for the removal of oxytetracycline (OTC) from aqueous solution. Zr-TiO2/CaO has been characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, energy diffraction
X-ray, Fourier transform infrared spectroscopy and UV-visible spectral analysis. SEM results confirm the dispersion of Zr doped TiO2 on calcium oxide support. The Zr-TiO2/CaO nanocomposite exhibits semicrystalline structure with average size of 50 nm. The photocatalytic activity of Zr-TiO2/CaO has been evaluated for the photodegradation of OTC under solar light. The synergetic adsorption and photocatalysis (A+P) is most efficient for oxytetracycline removal. The effect of various reaction parameters such as OTC concentration, pH of reaction solution and catalyst loading has been evaluated for OTC degradation. The photocatalytic degradation of oxytetracycline obeys pseudo-first order kinetics. The nanocomposite exhibits significant recyclability due to easy separation and stability in the reaction solution. The oxidative removal occurrs through hydroxyl radical formation. The nanocomposite displays excellent photocatalytic property for degradation of oxytetracycline and may have potential applications in water treatment.

Keywords: Photocatalysis, Photodegradation, Oxytetracycline degradation, Nanocomposites, Titania,
Doped titania
, Zirconium doped titania, Calcium oxide

Indian Journal of Chemistry

Vol. 55A, July 2016, pp. 810-815

 

 

A new hybrid iron fluoride bipyridine with mixed valence:
Fe2F5(2,2
'-bipyridine)2H2O

Mouna Smidaa, b, *, Mohamed Dammaka, Santiago Garcia-Grandab

aLaboratoire de Chimie Inorganique, Facult des Sciences de Sfax, Dpartement de Chimie,
Universit de Sfax, BP 1171, 3000 Sfax, Tunisie

bDpartement de Chimie et Physique Analytique, Facult de Chimie,
Universit dOviedo-CINN, 33006 Oviedo, Espagne

Email: mouna.smida@yahoo.fr

Received 5 September 2015; revised and accepted 1 June 2016

Hydrothermal synthesis of iron fluoride compound, Fe2F5(2,2'-bipyridine)2H2O, and its characterization by single crystal X-ray diffraction is reported. The compound is found to crystallize in the triclinic space group . The monohydrate fluoroferrate of bipyridine is built up from Fe4F10N8 tetrahedron connected by eight nitrogen atoms of four 2,2'-bipyridine molecules and separated by H2O molecules. The main feature of this atomic arrangement is the coexistence of two oxidation states of iron cations and hybrid class II with 0-D dimensionality. Thermal and IR spectral analysis have been carried out for the title compound to confirm the hematite compound as residual and the presence of organic molecule , respectively. Magnetic characterization does not reveal any ferromagnetic component in the range of magnetic field from -20 kOe to 20 kOe at room temperature.

Keywords: Coordination chemistry, Hydrothermal synthesis, X-ray diffraction, Inorganic-organic hybrid compounds, Crystal structure, Hybrid compounds, Thermal analysis, Iron, Fluoroferrates, Metal organic framwork

 

Indian Journal of Chemistry

Vol. 55A, July 2016, pp. 816-819

 

 

Synthesis and characterization of [Ni-Al-Fe] nanocomposite and its application for the removal of cadmium(II) and zinc(II) ions

Y V S Sai Krishnaa, R Ravichandra Babua, *, P V Satyamb

aDepartment of chemistry, GITAM University, Visakhapatnam, Andhra Pradesh 530 045, India

Email: rrcbabu7@yahoo.in

bDepartment of Atomic Energy, Institute of Physics, Bhubaneswar, Odissa, India

Received 9 January 2016; revised and accepted 29 June 2016

The applicability of [Ni-Al-Fe] trioxide nano composite for the selective removal of toxic metals from wastewater has been investigated. The [Ni-Al-Fe] nanocomposite of 10 nm size has been synthesized via solution combustion route using aqueous solutions containing aluminum nitrate, iron nitrate and nickel nitrate as oxidizers and glycine as fuel. The calcined composite oxide has been characterized by powder x-ray diffraction, scanning electron microscope and transmission electron microscope. The surface area of the nanocomposite is determined to be 91 m2/g using Brunauer-Emmett-Teller method. Batch experiments carried out to determine the adsorption kinetics and the efficiency of removal of trace metals such as zinc and cadmium under different experimental conditions show the process to be highly pH dependant, which makes the nanocomposite selectively adsorb these two metals. The adsorption of the two metals reached equilibrium within 35 min; the adsorption data well fitted with Langmuir and Freundlich isotherms.

Keywords: Nanocomposites, Oxides, Trioxides, Adsorption, Nickel, Aluminium, Iron, Cadmium, Zinc

 

 

 

 

Indian Journal of Chemistry

Vol. 55A, July 2016, pp. 820-823

 

 

Investigations on interaction between atazanvir sulphate and bovine
serum albumin by fluorescence spectroscopy

Umesh S Motea,* & G B Kolekarb

aPG Department of Physical Chemistry, Karmaveer Bhaurao Patil College, Urun-Islampur,
Tal. Walwa, Dist. Sangli 415 409, Maharashtra, India

Email: moteumesh@gmail.com

b Department of Chemistry, Shivaji University, Kolhapur 416 004 Maharashtra, India

Received 29 October 2015; revised and accepted 30 June 2016

The interaction between bovine serum albumin (BSA) and atazanvir sulphate (AS) has been investigated under the physiological pH 7.4 condition using fluoresence spectroscopy. The binding constant, number of binding site, thermodynamic parameters such as ∆G, ∆H, ∆S and nature of binding forces between BSA-AS have been obtained from the steady state fluorescence quenching of BSA by AS. The static quenching is confirmed from Stern-Volmer quenching constant at different temperatures. The effect of AS on the conformation of BSA has been analyzed using synchronous and three-dimensional fluorescence spectroscopy.

Keywords: Fluorescence quenching, Thermodynamic parameters, Synchronous fluorescence, Binding constant