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 57A

NUMBER 02

FEBRUARY 2018

 

CONTENTS

 

 

143

 

Theoretical study of 11B NMR chemical shifts of prototypical boranes: The case of closo-[B12H12]2-,
nest-B11H15, and arachno-B10H16

 

 

 

 

 

 

 

 

 

 

 

A Morales-Bayuelo, J M Catalán Lavín &
R Ramírez-Tagle
*

 

 

 

Structural and electronic dependence of 11B chemical shifts are studied by DFT calculations for a series of borane structures, viz., closo-[B12H12]2-, nest-[B11H15], and arachno-[B10H16]. Three types of environments are identified for the borane systems, in increasing order of chemical shielding as: B-H < B-H-B < B-B-B. The obtained chemical shifts are in good agreement with the available experimental results and reflect the extent of heterogeneity of the electronic environments in terms of symmetry and the number of boron cores.

 

 

 

 

150

 

Theoretical investigation into the cooperativity effect and thermodynamic property of β-nitroguanidine∙C2F4∙H2O ternary complex

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Bin Li*, Guang-ming Zhao & Xiao-juan Guo

 

 

 

The H-bonding cooperativity effects in β-NQ∙∙∙C2F4∙∙∙H2O ternary complex are investigated by the B3LYP and MP2(full) methods with 6-311++G(2df,2p) basis set. Thermodynamic cooperativity effects are evaluated at 298.15 K. The influence of the N–H∙∙∙O or O–H∙∙∙F H-bonding interaction on the N–H∙∙∙F interaction is more pronounced than that of the latter on the former. Weak cooperativity effect appears in the linear complexes while notable anti-cooperativity effect is seen in the cyclic systems. Enthalpy change is the major factor driving the cooperativity. The complexation energies correlate well with the local minima of surface electrostatic potentials or internal charge separations.

 

 

 

Notes

 

163

 

Binding interaction of a piperazinylquinoline derivative with β-cyclodextrin and Cd2+ ions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

M Sumithra, G Tamil Selvan, S Suganthi,
P Mosae Selvakumar & Israel V M V Enoch
*

 

 

 

Cd2+ ion sensing by 3-methyl-2-(piper-azin-l-yl)quinoline using fluorescence spectroscopy is reported. The host-guest complex formation of the quinoline-piperazine conjugate with
β-cyclodextrin is studied using UV-visible absorption, fluorescence, and 2-dimensional ROESY spectroscopic methods. The 1:1 Cd2+ complexation of the quinoline-piperazine conjugate is achieved on encapsulation by β-cyclodextrin.

 

 

 

 

 

168

 

Ion-pair single-drop microextraction with ATR-FTIR determination of phosphate in water samples

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Swati Chandrawanshi, Santosh Kumar Verma & Manas Kanti Deb*

 

 

 

An ion-pair single-drop microextraction procedure followed by ATR-FTIR has been developed for analysis of phosphate in water samples. This method is based on the extraction of the phosphate-cetyltrimethylammonium bromide ion-pair by single-drop extraction procedure. The calibration plot for phosphate is linear over the range of 1–900 ng mL-1 (r2 = 0.998). The limit of detection, limit
of quantification, standard deviation and relative standard deviation of six replicate measurements are respectively 0.34 ng mL-1,
1.12 ng mL-1, 0.001 and 0.94–3.36%.

 

 

 

 

175

 

Urease immobilized potentiometric biosensor for determination of urea

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Kawan Sihombing, Monica Chrisdayanti Tamba, Winry Sulistiani Marbun & Manihar Situmorang*

 

 

 

Potentiometric urea biosensor is constructed by immobilizing  urease at tungsten electrode using polyvinyl alcohol matrix followed by sealing with plasticised polyvinyl chloride. The sensing device gives fast, linear and sensitive response to
urea over 0.01–50 mM (slope 42.7 mV per decade urea,
r2 = 0.993), with detection limit of 0.01 mM urea
.

 

 

 

 

 

181

 

Functional 1,8-naphthyridine copper(I) complex
as efficient catalyst for n-arylation of imidazoles coupling reactions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Gao-Zhang Gou*, Na Wu, Ju-Cheng Zhang,
Ling Shi, Gui-Yang Liu, Wei Liu, Chao-Yong Mang
& Shao-Ming Chi
*

 

 

 

The functional 1,8-naphthyridine copper(I) complex catalyzes the cross-coupling reaction of aryl halides with imidazoles by C–N bond formation with a low catalyst loading (1%, molar fraction) and cheap base even under aerobic conditions. The procedure tolerates aryl halides with various functional groups (such as methyl, methoxy, acetyl, fluoro, nitrile and nitro groups) and gives the corresponding coupling products in moderate to high yields.

 

 

 

 

186

 

BODIPY-based fluorescent sensors with tunable binding ability to fluoride and hydrogen sulfate anions

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Qian Li*, Yehong Guo & Yuan Chen

 

 

 

The binding and sensing abilities of BODIPY based fluorescent sensors 1 and 2 towards various anions are studied by absorption, emission and 1H NMR titrations spectroscopy. Sensor 1 shows selective response toward fluoride anions through hydrogen bonding interaction, while sensor 2 acts as a highly selective ‘‘Off–On’’ fluorescent sensor for hydrogen sulfate anion in DMSO solvent.

 

 

 

 

193

 

Guide to Authors

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

 

 

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Indian Journal of Chemistry

Vol 57A, February 2018, pp. 143-149

 

Theoretical study of 11B NMR chemical shifts of prototypical boranes:
The case of closo-[B12H12]2-, nest-B11H15, and arachno-B10H16

A Morales-Bayueloa, b, J M Catalán Lavínc & R Ramírez-Taglec, *

aCentro de Investigación de Procesos del Tecnológico Comfenalco. Fundación Universitaria
Tecnológico Comfenalco, Cartagena de Indias, Colombia

bGrupo de investigaciones básicas y clínicas de la universidad del Sinú, Cartagena de Indias, Colombia

cFacultad de Ingenieria Ciencia y Tecnologia, Universidad Bernardo O´Higgins, Santiago, Chile

Email: rramirez@ubo.cl

Received 31 July 2017; re-revised and accepted 31 January 2018

The structural and electronic dependence of the 11B chemical shifts for a series of borane structures, namely, closo-[B12H12]2-, nest-[B11H15], and arachno-[B10H16] are investigated using density functional theory calculations. Three types of environments are identified for the borane systems, in increasing order of chemical shielding as: B-H < B-H-B < B-B-B. The obtained chemical shifts are in good agreement with the available experimental results and reflect the extent of heterogeneity of the electronic environments present in these chemical systems in terms of symmetry and the number of boron cores. In addition, results of molecular quantum similarity studies using similarity descriptors such as overlap and coulomb indices and Euclidean distances are also reported.

Keywords: Theoretical chemistry, Borane clusters, Superatoms, NMR spectroscopy, Quantum similarity

 

Indian Journal of Chemistry

Vol 57A, February 2018, pp. 150-162

 

Theoretical investigation into the cooperativity effect and thermodynamic property of β-nitroguanidine∙C2F4 H2O ternary complex

Bin Li*, Guang-ming Zhao & Xiao-juan Guo

School of Environment and Safety Engineering, North University of China, Taiyuan 030051, China

Email: sxzbhjgc@163.com

The H-bonding cooperativity effects in β-NQ (nitroguanidine)∙∙∙C2F4∙∙∙H2O ternary complex are investigated by the B3LYP and MP2(full) methods with the 6-311++G(2df,2p) basis set. The thermodynamic cooperativity effects are evaluated at 298.15 K. The result shows that C2F4 can be used as a wastewater treatment agent for β-NQ. The influence of the N–H∙∙∙O or O–H∙∙∙F H-bonding interaction on the N–H∙∙∙F interaction is more pronounced than that of the latter on the former. The weak cooperativity effect appears in the linear complex while the notable anti-cooperativity effect is seen in the cyclic system. The enthalpy change is the major factor driving the cooperativity. There is no obvious correlation between the cooperativity effects evaluated by interaction energies and those from thermodynamic data. The complexation energies (Eint.) correlate well with the local minima of surface electrostatic potentials (VS,min) or internal charge separations (Π). AIM (atom in molecule) analysis is used to reveal the nature of cooperativity effect. It can be inferred that the wastewater treatment for explosives can be viewed as a cooperativity process of coexisting intermolecular interactions, and also a thermodynamic cooperativity process.

Keywords: Theoretical chemistry, Cooperativity effect, Thermodynamic cooperativity, Atom-in-molecule analysis,
MP2 method, Surface electrostatic potential

 

Indian Journal of Chemistry

Vol. 57A, February 2018, pp. 163-167

 

Binding interaction of a piperazinylquinoline derivative with
β-cyclodextrin and Cd2+ ions

M Sumithraa, G Tamil Selvana, S Suganthia,
P Mosae Selvakumara & Israel VMV Enocha, b, *

aChemistry Research Lab, Department of Science and Humanities, Karunya University,
Coimbatore 641 114, Tamil Nadu, India

bNanotoxiology Research Lab, Department of Science and Humanities, Karunya University,
Coimbatore 641 114, Tamil Nadu, India

Email: drisraelenoch@gmail.com

Received 14 April 2017; revised and accepted 31 January 2018

Cd2+ ion sensing by 3-methyl-2-(piper-azin-l-yl)quinoline using fluorescence spectroscopy is reported. The host-guest complex formation of the compound with β-cyclodextrin is studied using UV-visible absorption, fluorescence, and 2-dimensional ROESY spectroscopic methods. The stoichiometry and the mode of binding of the compound with the host molecule are reported. The 1:1 Cd2+ complexation of the compound is effected on encapsulation by β-cyclodextrin.

Keywords: Analytical chemistry, Host-guest complexation, Chemosensors, Encapsulation, Fluorescence spectroscopy, Cadmium, Piperazinylquinolines, β-Cyclodextrin

 

Indian Journal of Chemistry

Vol 57A, February 2018, pp. 168-174

 

Ion-pair single-drop microextraction with ATR-FTIR
determination ofphosphate in water samples

Swati Chandrawanshia, Santosh Kumar Vermab & Manas Kanti Deba, *

aSchool of Studies in Chemistry, Pt. Ravishankar Shukla University, Raipur, 492010, Chhattisgarh, India

Email: debmanas@yahoo.com

bState Forensic Science Laboratory, Home (Police) Department, Government of Chhattisgarh,
Raipur, 492001, India

Received 13 November 2017; revised and accepted 30 January 2018

A simple, rapid and green ion-pair single-drop microextraction procedure followed by attenuated total reflectance-Fourier transform infrared technique has been developed for the analysis of phosphate in water samples. This method is based on the extraction of the phosphate-cetyltrimethylammonium bromide ion-pair by the single-drop extraction procedure. The linear range for calibration plot of phosphate is 1-900 ng mL-1, with good correlation coefficient (r2 = 0.998). The limit of detection, limit of quantification, standard deviation and relative standard deviation of six replicate measurements are respectively 0.34 ng mL-1, 1.12 ng mL-1, 0.001 and 0.94-3.36%. The significant parameters such as selection of solvent, their volume, ion-pair reagent and their concentration, extraction time, stirring rate, sample pH, extraction temperature and effect of salt concentration are studied and optimized. The present method is successfully applied for the quantification of phosphate in water samples with minimal solvent consumption and sensitivity as compared with the conventional methods.

Keywords: Analytical chemistry, Phosphate, Ion-pair complex, Ion-pair, Single drop microextraction, Attenuated total reflectance spectroscopy, Fourier transform infrared spectroscopy, Water analysis

 

Indian Journal of Chemistry

Vol. 57A, February 2018, pp. 175-180

 

Urease immobilized potentiometric biosensor for determination of urea

Kawan Sihombing, Monica Chrisdayanti Tamba, Winry Sulistiani Marbun & Manihar Situmorang*

Department of Chemistry, Faculty of Mathematics and Natural Science, Universitas Negeri Medan,
Jl. Willem Iskandar Psr V Medan, North Sumatera, 20221, Indonesia

Email: msitumorang@unimed.ac.id

 

A simple potentiometric biosensor for the determination of urea is reported in this work. The biosensor has been constructed by immobilization of urease at tungsten electrode using polyvinyl alcohol matrix followed by the sealing process with plasticised polyvinyl chloride. The sensing device gives fast and sensitive response to urea. A linear calibration curve in the concentration range of 0.01–50 mM urea is obtained with slope 42.7 mV per decade urea concentration (r2 = 0.993), and detection a limit of 0.01 mM urea.

Keywords: Electroanalytical chemistry, Biosensors, Potentiometric biosensors, Enzyme electrode, Tungsten electrode, Immobilized enzyme, urea

 

Indian Journal of Chemistry

Vol. 57A, February 2018, pp. 181-185

 

Functional 1,8-naphthyridine copper(I) complex as efficient catalyst for
n-arylation of imidazoles coupling reactions

Gao-Zhang Goua, *, Na Wua, Ju-Cheng Zhanga, Ling Shia, Gui-Yang Liua, Wei Liua,
Chao-Yong Mangb & Shao-Ming Chic, *

aSchool of Science, Honghe University, Mengzi, Yunnan 661199, PR China

Email: hhxylxyhxx@126.com (GZG)

bCollege of Pharmaceutical Science and Chemistry, Dali University,
Dali, Yunnan 671000, PR China

cCollege of Chemistry and Chemical Engineering, Yunnan Normal University,
Kunming 650092, PR China

Email: chishaoming@gmail.com (SMC)

Received 21 September 2017; revised and accepted 29 January 2018

The functional 1,8-naphthyridine copper(I) complex, synthesized through a non-catalyst C(sp3)–H methylenation, catalyzes the cross-coupling reaction of aryl halides with imidazoles, by C―N bond formation. The Cu(I) complex catalyzes the reaction with a low catalyst loading (1%, molar fraction) and cheap base even under aerobic conditions. The procedure tolerates aryl halides with various functional groups (such as methyl, methoxy, acetyl, fluoro, nitrile and nitro groups) and gives the corresponding coupling products in moderate to high yields.

Keywords: Catalysts, Cross-coupling reactions, N-Arylation, Copper(I) complex, Imidazoles,

 

Indian Journal of Chemistry

Vol. 57A, February 2018, pp. 186-191

 

BODIPY-based fluorescent sensors with tunable binding ability
to fluoride and hydrogen sulfate anions

Qian Li*, Yehong Guo & Yuan Chen

College of Agronomy, Department of Cultivation and Identification of Chinese Herbal Medicine/ Institute
of Chinese Medicinal Materials, Gansu Agricultural University, Lanzhou, 730070, PR China

Email: liqian1984@gsau.edu.cn

 

The binding and sensing abilities of BODIPY based fluorescent sensors 1 and 2 towards various anions have been studied by absorption, emission and 1H NMR titrations spectroscopy. Sensor 1 shows selective response toward fluoride anions through hydrogen bonding interaction, while sensor 2 acts as a highly selective ‘‘Off–On’’ fluorescent sensor for hydrogen sulfate anion in DMSO solvent. The fluorescence response of sensor 2 towards HSO4- may be due to the suppressed PET (photo-induced electron transfer) process induced by the multiple hydrogen bonding interactions between sensor 2 and HSO4-.

Keywords: Fluorescent sensors, Off-On sensors, BODIPY derivatives, Hydrogen sulfate, Fluoride