Indian Journal of Chemistry

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

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

Total visitors: 592 since 19-01-2018

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

 

 

 

 

VOLUME 57A

NUMBER 01

JANUARY 2018

 

CONTENTS

 

 

9

 

Calcium oxalate crystallization in SDS solutions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Yan Li, Xifeng Lu, Xiaodeng Yang* & Yulin Wangc

 

 

 

Sodium dodecyl sulfate inhibits CaC2O4 crystallization and growth significantly through electrostatic interaction between DS2- and Ca2+, while hydroxy isopropyl chitosan promotes the growth of CaC2O4 (020) surface due to adsorption of NH2 groups. Both Ca2+ and C2O42- inhibit the growth of (020) surface remarkably when their concentrations are not the same. Ethanol increasingly inhibits the growth of the (101) and (020) surfaces with increasing.(Vethanol/VH2O). Mg2+ ions induce formation of spherical COD when the ratios of Mg2+]/[Ca2+] are 1:4 and 4:1, and cruciate-flowered COD when the ratio is 1:1. The electrostatic interaction between SDS and Ca2+ ions and the formed CDS plays a key role in CaC2O4 crystallization.

 

 

 

 

18

 

Enhanced photocatalytic activity of mesoporous
nano titania decorated with zinc phthalocyanine

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

P V R K Ramacharyulu* & G K Prasad*

 

 

 

Zinc phthalocyanine decorated mesoporous titania (Znpc-TiO2) with a specific surface area of 247 m2 g-1 has been synthesized by a hydrothermal method, This visible light active nanocatalyst degrades sulfur mustard, a highly toxic chemical warfare agent, as well as malchite green dye, photocatalytically to nontoxic intermediates and finally into SO2, CO2 and H2O. Znpc-TiO2 requires an exposure time of as low as 60 min, while with undoped TiO2 almost six times (360 min) longer irradiation time is required.

 

 

 

 

26

 

In situ synthesis and characterization of Prussian blue nanocubes on graphene oxide and its application for H2O2 reduction

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Cheng-xiang Ge, Peng-jun Li, Juan-hua Lai &
Ping Qiu
*

 

 

 

An effective and facile in situ electroless deposition approach has been developed for growing high-quality Prussian blue nanocubes on the surface of graphene oxide (PBNCs/GO) in a controlled manner. The coverage and loading of PB NPs on the surface of GO nanosheets can be tuned by control over the experimental parameters. It exhibits prominent electrocatalytic activity towards reduction of hydrogen peroxide, with a linear calibration in the range of 0.0022.8 mM and a detection limit of 0.48 M. The response is within less than 5 s, while the detection sensitivity is 2502 A mM-1cm-2.

 

 

IJCA-1768_Fig. 1.tif

 

 

 

 

34

 

A highly specific heterostructure composed of N-doped TiO2 anastase nanoparticles and double layer Au for detection of thiophene molecule: A DFT study

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Amirali Abbasi* & Jaber Jahanbin Sardroodi

 

 

 

Adsorption of thiophene molecule on pristine, N-doped and Cu/N codoped TiO2-supported Au overlayers has been studied by DFT calculations, taking into consideration the effects of van der Waals interactions. Thiophene interacts with TiO2 supported Au overlayer by its active sulfur atom, providing a double contact point at the interface region. Thiophene molecule can be adsorbed on both the Au as well as five-fold coordinated titanium sites of TiO2 supported Au overlayers. Adsorption of thiophene molecule on the N-doped TiO2 supported Au overlayers is energetically more favorable than adsorption on the undoped systems.

 

 

 

 

 

44

 

Crystal structure, configurational and DFT study of nickel(II) complexes with N2O-donor type Schiff base ligand

 

 

 

 

 

 

 

 

 

 

 

Yogendra Pratap Singh, Ram N Patel* &
Yogendra Singh

 

 

 

Nickel(II) complexes [Ni(HL)(L)]NO3 (1) and [Ni(L)2]4H2O (2) have been synthesized and characterized via single crystal X-ray structural analysis. Supramolecular architecture in both (1) and (2) is shown by CHπ and ππ interactions. The molecular structures and spectral properties of the complexes have been explained by DFT and TD-DFT calculations.

 

 

 

Notes

 

52

 

 

Early lanthanoid substituted organic-inorganic hybrids of silico- and germane-tungstates: Syntheses, crystal structures and solid properties

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Rakesh Gupta, Swati Parbhakar, Imran Khan, Jogendra Nath Behera & Firasat Hussain*

 

 

 

Alkali salts of organic-inorganic hybrid 3d-4f heterometallic germanotungstates, viz., [{Cu2(1,10-phen)2(-CH3COO)2}Ln(α-MW11O39)2]11‒ [M = SiIV, GeIV, Ln = LaIII), CeIII,
CeIV, LaIII, CeIII, CeIV have been prepared under mild reaction conditions. All the compounds are well characterized with
SC-XRD, FT-IR
spectroscopy, powder-XRD, liquid UV/vis, elemental and thermogravimetric analysis. All the compounds form polymeric chain assistance with copper organic complexes.

 

 

 

 

59

 

Coumarin based azo dyes as anion sensors:
A spectrophotometric study

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Nilanjan Chakraborty, Sutanwi Bhuiya,
Arijit Chakraborty* & Suman Das
*

 

 

 

Two 4-hydroxy coumarin based azo dyes, viz.,
(E)-3-((2-chlorophenyl)-diazenyl)-4-hydroxy-2H-chromen-2-one and (E)-4-hydroxy-3-((4-nitrophenyl)diazenyl)-2H-chromen-2-one have been synthesized and their anion detection ability has been studied for selective detection of fluoride and acetate ions through the naked eye. On addition of 4 equivalents of fluoride or acetate to the CH3CN solution of the receptors, the colour changes from light yellow to light red, while addition of other anions does not show any significant change in colour under identical experimental conditions. In fluorescence studies, both the receptors show quenching in the presence of fluoride and acetate ions.

 

 

 

 

67

 

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, January 2018, pp. 9-17

 

Calcium oxalate crystallization in SDS solutions

Yan Lia, Xifeng Lub, Xiaodeng Yanga,* & Yulin Wangc

aKey Laboratory of Fine Chemicals (Shandong Province), Qilu University of Technology, Jinan 250353, PR China

bLunan Institute of Coal Chemical Engineering, Jining 272000, PR China

cCollege of Jining Polytechnic, Jining 272000, PR China

Email: yangxiaodeng@qlu.edu.cn

Received 1 November 2017; revised and accepted 15 December 2017

Sodium dodecyl sulfate (SDS) and hydroxy isopropyl chitosan (HPCHS) are employed as modulation agents for crystallization of CaC2O4. The effects of concentrations of SDS and HPCHS, [Ca2+]/[C2O42-], [Mg2+]/[Ca2+] and ratio of Vethanol/Vwater and [Mg2+]/[Ca2+] on the crystallization are investigated. The CaC2O4 particles are characterized by scanning electron microscopy, powder X-ray diffraction, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The results show that SDS inhibits the crystallization and growth of CaC2O4 particles due to the interaction between dodecyl sulfate and Ca2+ and also the formation of calcium dodecyl sulfate. Based on an analysis of the CaC2O4 and solution properties of SDS/Ca2+ and HPCHS/SDS/Ca2+, a mechanism for CaC2O4 crystallization in SDS solutions is proposed. This work is of significance in inhibiting abnormal mineralization.

Keywords: Crystallization, Calcium oxalate, Sodium dodecyl sulfate, Hydroxy isopropyl chitosan

 

Indian Journal of Chemistry

Vol. 57A, January 2018, pp. 18-25

 

Enhanced photocatalytic activity of mesoporous
nano titania decoratedwith zinc phthalocyanine

P V R K Ramacharyulua, b, * & G K Prasada,*

aDefence R&D Establishment, Jhansi Road, Gwalior 474 002, MP, India

bNational Dong Hwa University, Hualien 97401, Taiwan, ROC

Email: ramamsc2007@gmail.com/ gkprasad2001@gmail.com

Received 3 August 2017; re-revised and accepted 26 December 2017

Zinc phthalocyanine decorated mesoporous titania (Znpc-TiO2), has been synthesized by a hydrothermal method, This visible light active nanocatalyst with a specific surface area of 247 m2 g-1 degrades one of the highly toxic chemical warfare agents, sulfur mustard and malchite green dye photocatalytically in the sunlight with an exposure time of as low as 60 min.

Keywords: Photocatalysis, Degradation, Dye degradation, Visible light degradation, Detoxification, Nanoparticles, Sulfur mustard, Malchite green, Titania

 

Indian Journal of Chemistry

Vol. 57A, January 2018, pp. 26-33

 

In situ synthesis and characterization of Prussian blue nanocubes
on graphene oxide and its application for H2O2 reduction

Cheng-xiang Gea, Peng-jun Lib, Juan-hua Laic & Ping Qiub, *

aHefei Center for Disease Control and Prevention of Anhui Province, Hefei 230061, China

bDepartment of Chemistry, Nanchang University, Nanchang 330031, China

Email: pingqiu@ncu.edu.cn

cJiangxi Medical Device Testing Center, Nanchang 330047, China

An effective and facile in situ electroless deposition approach has been developed for growing high-quality Prussian blue nanocubes on the surface of graphene oxide (PBNCs/GO) in a controlled manner. The resulting hybrids are characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared, ultraviolet visible, X-ray diffraction and electrochemical techniques. The electrochemical behavior on the modified electrode is discussed in detail. A linear calibration of the biosensor is obtained in the range of 0.0022.8 mM with a detection limit of 0.48 M. The response is within less than 5 s and the detection sensitivity is 2502 A mM-1cm-2. The proposed approach allows simple and controlled preparation of transition metal hexacyanoferrate nanocrystals/graphene oxide and is promising for the study of unique shape-, size-, and structure- dependent properties for optoelectronic, magnetic, and electrocatalytic applications.

Keywords: Nanocubes, Prussian blue nanocubes, Graphene oxide, Reduction, Hydrogen peroxide reduction, Biosensors

 

Indian Journal of Chemistry

Vol. 57A, January 2018, pp. 34-43

 

A highly specific heterostructure composed of N-doped TiO2
anatase nanoparticles and double layer Au for detection of
thiophene molecule: A DFT study

Amirali Abbasi, a, b, c, * & Jaber Jahanbin Sardroodi a, b, c

aMolecular Simulation laboratory (MSL),
bDepartment of Chemistry, Faculty of Basic Sciences,
cComputational Nanomaterials Research Group (CNRG),
Azarbaijan Shahid Madani University, Tabriz, Iran

Email: a_abbasi@azaruniv.edu

The adsorption of thiophene molecule on the pristine, N-doped and Cu/N codoped TiO2-supported Au overlayers has been studied using density functional theory calculations, taking into consideration the effects of van der Waals interaction. Thiophene molecule can be adsorbed on both the Au and five-fold coordinated titanium sites of TiO2 supported Au overlayers. Various adsorption configurations of thiophene over the considered TiO2 supported Au overlayers are discussed. It is found that with Cu/N codoped nanoparticle as an adsorbent, the adsorption configuration is more stable and consequently the adsorption process is more energetically favorable. The adsorption of thiophene molecule on the N-doped TiO2 supported Au overlayers is more energetically favorable than the adsorption on the undoped ones. On the Cu/N codoped nanoparticle, the adsorption process is more strongly favored. Thus, Cu/N-codoped system can interact with thiophene molecule more efficiently. The considerable overlaps between the PDOSs of the sulfur and titanium atoms indicate chemical bond forms between these two atoms. These chemical bonds confirm chemisorption of thiophene on the TiO2 supported Au overlayers. After the adsorption process, the HOMOs are mainly distributed over the adsorbed thiophene molecule. The charge analysis based on Mulliken charges reveals that charge is transferred from the thiophene molecule to the TiO2 supported Au. This study not only suggests a theoretical basis for adsorption behaviors of thiophene on the TiO2-supported Au overlayers, but also provides an efficient strategy to design and improve highly efficient sensor devices for thiophene detection.

Keywords: Density functional theory, Thiophene, Titania, Supported gold overlayers, Gold overlayers, Molecular orbitals

 

Indian Journal of Chemistry

Vol. 57A, January 2018, pp. 44-51

 

Crystal structure, configurational and DFT study of
nickel(II) complexes with N2O-donor type Schiff base ligand

Yogendra Pratap Singh, Ram N Patel* & Yogendra Singh

Department of Chemistry, APS University, Rewa (MP) 486 003, India

Email: rnp64@ymail.com

Received 11 February 2017; revised and accepted 20 December 2017

Nickel(II) complexes containing a Schiff base (L) derived from 2-pyridinecarboxyldehyde and 2-furoic hydrazide [Ni(HL)(L)]NO3 (1) and [Ni(L)2]4H2O (2) where HL = N'-[(E)-pyridin-2-yl-methylidene]furan-2-carbohydrazide, have been synthesized and comprehensively characterized via physico-chemical techniques as well as by single crystal X-ray structural analysis. In both the complexes, the ligand behaves as mono-anionic tridentate and binds to the nickel(II) ion via deprotonated carbonyl-oxygen, pyridine-nitrogen and azomethine-nitrogen. Magnetic moments and electronic studies suggest an octahedral geometry around nickel(II) ion in both the complexes. The supramolecular architecture in both (1) and (2) are shown by C-H...π and ππ interactions. The molecular structures and spectral properties of the complexes have been explained by DFT and TD-DFT calculations. The electronic excitation energies of these complexes, calculated at TD-DFT levels, are in agreement with values deduced from the experimental UV-visible spectra.

Keywords: Coordination chemistry, Supramolecular architecture, X-ray structures, ππ interactions, C-Hπ interactions, UV-visible spectroscopy, TD-DFT calculations, Schiff bases, Nickel

 

Indian Journal of Chemistry

Vol. 57A, January 2018, pp. 52-58

 

Early lanthanoid substituted organic-inorganic hybrids of
silico- and germano-tungstates: Syntheses, crystal structures
and solid-state properties

Rakesh Guptaa, Swati Parbhakara, Imran Khana,
Jogendra Nath Beherab & Firasat Hussaina, *

aDepartment of Chemistry, University of Delhi, North Campus, Delhi 110 007, India

Email: fhussain@chemistry.du.ac.in

bSchool of Chemical Sciences, National Institute of Science Education and Research (NISER),
P.O. Bhimpur, Padanpur, Jatni, Odisha 752050, India

Received 26 August 2017; accepted 15 December 2017

Organic-inorganic hybrid of 3d-4f heterometallic derivatives of lacunary Keggin type silico- and germano-tungstates: [{Cu2(1,10-phen)2(-CH3COO)2}Ln(α-XW11O39)2]11‒/10‒ {Ln = LaIII, CeIII and CeIV, X = SiIV; LaIII, CeIII, CeIV, X = GeIV; 1,10-phen = 1,10-Phenanthroline} have been synthesized by conventional aqueous solution method under mild reaction conditions. Solid crystalline materials isolated from the solution as an alkali salts (Na+/K+) are characterized by single crystal X-ray diffraction, FT-IR spectroscopy, powder-XRD, ICP-AES, liquid UV/vis and thermogravimetric analysis. FT-IR spectra and PXRD suggest that these compounds are isomorphous. Further, single crystal XRD analyses show that all are organic-inorganic hybrids comprising Peacock and Weakley type sandwich-type [Ln(α-XW11O39)2]13−/12‒ (X = SiIV and GeIV) polyanion as the fundamental building block unit. These sandwich type species form polymeric chain assistance with copper organic complexes. These polymeric chains further assemble into 2-D structures by π-π stacking.

Keywords: Polyoxometalates, 3d-4f Heterometallic complexes, Organic-inorganic hybrids, Single crystal XRD

 

Indian Journal of Chemistry

Vol. 57A, January 2018, pp. 59-65

 

Coumarin based azo dyes as anion sensors: A spectrophotometric study

Nilanjan Chakrabortya, Sutanwi Bhuiyab,
Arijit Chakrabortya, c, * & Suman Dasb, *

aDepartment of Chemistry, Maulana Azad College, 8, Rafi Ahmed Kidwai Road,
Kolkata 700 013, West Bengal, India

bDepartment of Chemistry, Jadavpur University,
Kolkata 700 032, West Bengal, India

Email: sumandas10@yahoo.com

cDepartment of Chemistry, Acharya B N Seal College,
Cooch Behar 730 161, West Bengal, India

Received 10 July 2017; revised and accepted 28 December 2017

Two 4-hydroxy coumarin based dyes (1 and 2) have been synthesized and their anion detection ability has been studied, for detection of fluoride and acetate ions selectively through the naked eye. On addition of 4 equivalents of fluoride and acetate to the CH3CN solution of the receptors 1 and 2, colour changes from light yellow to light red while the similar addition of other anions like dihydrogen phosphate, chloride, bromide and iodide does not show any significant change in colour under identical experimental conditions. The corresponding UV-vis data show a blue shift of the band of receptor 1 and a red shift of the band of receptor 2 for both fluoride and acetate ions. In fluorescence studies, both the receptors show quenching in the presence of fluoride and acetate ions. Stoichiometry of anionic interaction has been determined from 1H-NMR titrations and Jobs plot. Theoretical studies using density functional theory and time dependent density functional theory have been explored. Detection of fluoride in aqueous medium by paper strips is also reported.

Keywords: Sensors, Anion sensors, Colorimetric sensors, Fluoride ions, Acetate ions, Azo dyes,
4-Hydroxycoumarins, Coumarins NMR titrations