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 54A

NUMBER 12

DECEMBER 2015

 

CONTENTS

 

 

1423

 

Hydrogen sorption in phosphorous substituted
carbon material

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Arjunan Ariharan, Balasubramanian Viswanathan*
& Vaiyapuri Nandhakumar

 

 

 

Phosphorus substituted carbon materials calcined at 600 °C and
800 °C show hydrogen storage capacity of
2.6 wt% and 2 wt% respectively at 298 K and 100 bar pressure. The hydrogen storage capacity decreases with increase in carbonization temperature.

 

 

IJCA-564 GA.tif

 

 

 

1434

 

Synthesis of ZrO2 and ZrO2/SiO2 particles and photocatalytic degradation of methylene blue

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ali İmran Vaizoğullar*, Ahmet Balci &
Mehmet Uğurlu

 

 

 

SiO2 particles (0.6 µm dia.) have been synthesized from tetraethyl orthosilicate and then decorated with ZrO2 synthesized from zirconium tetrabutoxide. The composite shows Si-O-Zr bridges between SiO2-ZrO2 particles and ZrO2 deposited on the SiO2 surface. The UV/O3/SiO2/ZrO2 system shows the highest rate for photodegradation of methylene blue as a sample pollutant. ZrO2/SiO2 spherical nanocomposite particles are more active than ZrO2 because of lattice deformation due to stabilization of t-ZrO2 phase by SiO2. Ozone contributes to the photoactivity by creating superoxide and hydroxide radicals.

 

 

 

 

1440

 

Synthesis of zinc sulfide nanoparticles stabilized by sodium dodecylsulfate micelles and evaluation of photocatalytic activity

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Longjam Meerabai Devi† & Devendra P S Negi*

 

 

 

The photocatalytic degradation of methyl orange by SDS stabilized ZnS nanoparticles is found to be highly efficient. Nearly 98% of the dye is degraded during 10 min of irradiation.

 

 

 

 

 

 

 

1446

 

Pyrene-appended Schiff base as a turn-on fluorescence sensor for Al3+ detection and interaction with DNA

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Uttam Panda, Kuheli Das, Paramita Dutta & Chittaranjan Sinha*

 

 

 

Pyrene appended Schiff base, 1,3-bis-((E)-pyrene-1-yl-methyleneamino)propan-2-ol (HL) fluoresces at 419 nm and
508 nm in DMF solution upon excitation at 344 nm. The addition of Al3+ results in a significant 100 fold increase in its fluorescent intensity with the emission maximum red shifted from 421 nm to 508 nm with intense green emission due to the formation of a 1:2 stoichiometric [Al2Cl5(L)] complex.
The limit of detection is found to be 7.42´10-8 M. The complexation inhibits the photo-induced electron transfer process and the CHEF mechanism is responsible for the turn-on fluorescence sensitivity.

 

 

 

Fig-2.tif

 

 

Notes

 

1451

 

Synthesis, characterization and DFT calculations of N,O Schiff base complex of copper(II)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sudipto Dey, Koushik Ghosh, Shibashis Halder, Corrado Rizzoli & Partha Roy*

 

 

 

A mononuclear complex of Cu(II) with an N,O donor Schiff
base ligand, 2-methoxy-6-(3-morpholinopropyliminomethyl)phenol, has been synthesized and characterized. The structure of the complex, confirmed by single crystal X-ray analysis, shows that both the ligands attached to one metal center are zwitterions, where nitrogen atom of the morpholine ring is protonated. Fluorescence spectral study shows that the ligand displays an emission band at 535 nm on excitation at 418 nm. The presence of Cu2+ ion in the complex quenches its emission intensity.

 

FIG1

 

 

1459

 

Synthesis, molecular structure and TD-DFT studies on N'-(pyridine-2-ylmethylene)acetohydrazide nickel(II) complexes

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Ram N Patel*, Yogendra Pratap Singh,
Yogendra Singh & Raymond J Butcher

 

 

 

Synthesis and characterization of two new mononuclear nickel(II) complexes, viz., [Ni(L)2].(NO3)2.H2O and [Ni(HL)(L)].ClO4.(H2O)2 are reported. All the complexes are structurally characterized by single crystal X-ray analysis. Magnetic moment values and spectroscopic data of both complexes show a paramagnetic nickel(II) center  with a tridentate N2O donor Schiff base.

 

  

[Ni(L)2].(NO3)2.H2O              [Ni(HL)(L)].ClO4.(H2O)2

 

 

Authors for correspondence are indicated by (*)

 

 

 

 

 

 

 

 

 

 

 

New
 

 

 

 

 

 

 

 


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Indian Journal of Chemistry

Vol. 54A, December 2015, pp. 1423-1433

 

 

Hydrogen sorption in phosphorous substituted carbon material

Arjunan Ariharana,b, Balasubramanian Viswanathana, * & Vaiyapuri Nandhakumarb

aNational Centre for Catalysis Research, Indian Institute of Technology Madras, Chennai, India
Email: bvnathan@iitm.ac.in

bPG & Research Department of Chemistry, AVVM Sri Pushpam College Poondi, Bharathidasan University,
Trichirapalli 620 001, Tamilnadu, India

Received 6 October 2015; revised and accepted 20 November 2015

The hydrogen storage capacity of phosphorous substituted carbon material with spherical morphology is reported. The phosphorous substituted carbons are synthesized by pyrolyzing a resorcinol formaldehyde resin, chemically bonded with phosphorous. The synthesis is a polycondensation reaction by phosphoric acid with sodium hydroxide as catalyst. Herein resorcinol-formaldehyde resin and phosphoric acid act as carbon and phosphorous sources respectively. The hydrogen adsorption capacity has been studied by high pressure volumetric analyser and shows high sorption capacity of 2.6 and 2 wt% at 298 K and 100 bar pressure for the phosphorous substituted carbon materials prepared by calcining at 600 and 800 °C respectively. This value is higher than the hydrogen sorption capacity of pure carbon under comparable preparation conditions 0.18 and 0.16 wt% at 298 K and 100 bar pressure, calcined at 600 and 800 °C respectively.

Keywords: Hydrogen storage, Carbon materials, Heteroatom substituted carbon, Phosphorus substituted carbon, Carbonization, Hydrogen adsorption capacity.

 

Indian Journal of Chemistry

Vol. 54A, December 2015, pp. 1434-1439

 

 

Synthesis of ZrO2 and ZrO2/SiO2 particles and photocatalytic
degradation of methylene blue

Ali İmran Vaizoğullara, *, Ahmet Balcib & Mehmet Uğurlub

aVocat Sch Helth Care, Med Lab Programme, Muğla Sıtkı Koçman University, Muğla, Turkey
Email: vaizogullar@yahoo.com

bDepartment of Chemistry, Faculty of Science, Muğla Sıtkı Koçman University, 48000 Muğla, Turkey

Received 28 May 2015; revised and accepted 24 November 2015

SiO2 particles (0.6 µm dia.) have been synthesized from tetraethyl orthosilicate and then decorated with ZrO2 synthesized from zirconium tetrabutoxide. X-ray diffraction, infrared spectra, scanning electron microscopy, energy dispersive X-ray spectroscopy and transmission electron microscopy have been used to characterize the ZrO2 and ZrO2/SiO2 catalysts. The results reveal that there are Si-O-Zr bridges between SiO2 and ZrO2 particles and ZrO2 deposited on the SiO2 surface. FT-IR analysis shows Si-O-Zr bonding at
1073 cm-1. XRD analysis shows that amorphous SiO2 and tetragonal ZrO2 particles are formed at 500 °C. SEM and TEM analyses show that SiO2 and ZrO2/SiO2 nanocomposite particles have a spherical morphology with diameter of 700-750 nm and a uniform particle size.  Photoactivity of ZrO2 and ZrO2/SiO2 particles has been investigated in the presence of ozone under UV light with methylene blue as a sample pollutant. Pseudo-first order kinetic model gives R2 values to be 0.69-0.97 and 0.79-0.93 for ZrO2 and ZrO2/SiO2 respectively. This study proves that ozone assisted ZrO2/SiO2 catalyst is an effective and fast-reacting system for photocatalytic removal of organic pollutants present in wastewater.

Keywords: Photocatalytic degradation, Dye degradation, Composites, Nanocomposites, Zirconia, Silica, Methylene blue

 

 

 

 

Indian Journal of Chemistry

Vol. 54A, December 2015, pp. 1440-1445

 

 

Synthesis of zinc sulfide nanoparticles stabilized by sodium dodecylsulfate micelles and evaluation of photocatalytic activity

Longjam Meerabai Devi† & Devendra P S Negi*

Department of Chemistry, North-Eastern Hill University, Permanent Campus, Shillong 793 022, India

Email: dpsnegi@nehu.ac.in; devnegi@yahoo.com

Received 13 March 2015; revised and accepted 27 October 2015

Zinc sulfide nanoparticles have been synthesized using sodium dodecylsulfate micelles as a stabilizing agent. The as-prepared nanoparticles are characterized by ultraviolet-visible spectroscopy, energy dispersive
X-ray spectroscopy, X-ray diffraction and transmission electron microscopy. The photocatalytic activity of the ZnS nanoparticles has been evaluated by monitoring the degradation of methyl orange with a UV-visible spectrophotometer. The effect of ZnS concentration on the photocatalytic degradation of the dye has been investigated. Under optimum experimental conditions, 98% of the dye is degraded in the presence of the photocatalyst during 10 min of irradiation with ultraviolet light. The turnover frequency for methyl orange degradation per mg of ZnS is calculated to be 6×1013 molecules s-1. The effect of SDS concentration on the photocatalytic degradation of the dye has also been investigated. The results suggest that SDS micelles do not catalyze the degradation of the dye. The mechanism of the photocatalytic degradation of methyl orange has been discussed.

Keywords: Photocatalysis, Nanoparticles, Zinc sulphide, Micelles, Degradation, Photocatalytic degradation,
Dye degradation

 

Indian Journal of Chemistry

Vol. 54A, December 2015, pp. 1446-1450

 

 

Pyrene-appended Schiff base as a turn-on fluorescence sensor for Al3+
detection and interaction with DNA

Uttam Panda, Kuheli Das, Paramita Dutta & Chittaranjan Sinha*

Department of Chemistry, Jadavpur University, Kolkata 700 032, India

Email: c_r_sinha@yahoo.com

Received 16 September 2015; accepted 23 November 2015

Pyrene appended Schiff base, 1,3-bis-((E)-pyrene-1-ylmethyleneamino)propan-2-ol (HL) fluoresces at
419 nm and 508 nm in DMF solution upon excitation at 344 nm. The addition of Al3+ results in a significant 100 fold increase of its fluorescent intensity with the emission maximum red shifted from 421 nm to 508 nm with intense green emission. This phenomenon may be attributed to the formation of a 1:2 stoichiometric [Al2Cl5(L)] complex, which has been supported by Jobs, NMR titration and mass spectral data. The complexation inhibits the photo-induced electron transfer process and the cheletropic enhancement of fluorescence mechanism is responsible for the turn-on fluorescence sensitivity. The limit of detection of Al3+ (7.42
´10-8 M) is the second lowest in the series of pyrene functionalized chemosensor. Both HL and its Al3+ complex, [Al2Cl5(L)], show DNA stacking interaction (binding constant Kb 9.8´104 M-1 (of HL) and
3.8
´104 M-1(of [Al2Cl5(L)]).

Keywords: Coordination chemistry, Schiff bases, Cheletropic enhancement, Sensors, Fluorescent sensors, Aluminium, Pyrene fluorophore

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 54A, December 2015, pp. 1451-1458

 

 

Synthesis, characterization and DFT calculations of N,O Schiff
base complex of copper(II)

Sudipto Deya, Koushik Ghosha, Shibashis Haldera, Corrado Rizzolib & Partha Roya, *

aDepartment of Chemistry, Jadavpur University, Jadavpur, Kolkata 700 032, India

Email: proy@chemistry.jdvu.ac.in

bUniversita' degli Studi di Parma, Dipartimento di Chimica, “Parco Area delle Scienze
17/A, I-43124 Parma, Italy

Received 20 June 2015; revised and accepted 23 November 2015

Mononuclear copper(II) complex of the Schiff base, 2-methoxy-6-(3-morpholinopropyl-iminomethyl) phenol, [Cu(HL)2](ClO4)2].H2O (1) has been synthesized and characterized by elemental analysis and different spectroscopic techniques. The structure of (1) is confirmed by single crystal X-ray diffraction analysis. The complex (1) crystallizes in the monoclinic space group P21/n. The crystal structure of the mononuclear complex exhibits two Schiff base ligands bound to the copper atom and two perchlorate ions as
non-coordinating species. Both the ligands in (1) are zwitterions where nitrogen atom of the morpholine ring is protonated. Fluorescence spectral study shows that HL displays an emission band at 535 nm on excitation at 418 nm. The presence of Cu2+ ion in complex (1) quenches its emission intensity. DFT and TDDFT calculations have been carried out to investigate the spectral transitions.

Keywords: Coordination chemistry, Schiff bases, Density functional calculations, NO ligands, Fluorescence, Crystal structure, Copper

 

Indian Journal of Chemistry

Vol. 54A, December 2015, pp. 1459-1465

 

 

Synthesis, molecular structure and TD-DFT studies on N'-(pyridine-2-ylmethylene)acetohydrazide nickel(II) complexes

Ram N Patela, *, Yogendra Pratap Singha, Yogendra Singha & Raymond J Butcherb

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

Email: rnp64@ymail.com

bDepartment of Inorganic & Structural Chemistry, Howard University, Washington DC, 22031 USA

Received 10 October 2015; revised and accepted 26 November 2015

Nickel(II) complexes of a Schiff base derived from 2-pyridinecarboxyldehyde and acetylhydrazide, viz., [Ni(L)2].(NO3)2.H2O (1) and [Ni(HL)(L)].ClO4.(H2O)2 (2) (where L = N'-(pyridine-2-ylmethylene)acetohydrazide), have been synthesized and characterized by physicochemical techniques as well as by single crystal X-ray structural analysis. The supramolecular architecture in both complexes (1) and (2) are totally guided by complicated H-bondings. The molecular structures and spectral properties of the ligand and 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, Schiff bases, Density functional calculations, Nickel