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 03

MARCH 2018

 

CONTENTS

 

 

409

 

Oxovanadium(IV) complexes of polypyridyl bases as photocytotoxic and DNA crosslinking agents

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Arun Kumar, Akanksha Dixit, Samya Banerjee, Sanjoy Mukherjee, Somarupa Sahoo,
Anjali A Karande* & Akhil R Chakravarty
*

 

 

 

Dichlorooxovanadium(IV) complexes of N,N,N-donor polypyridyl bases with a trans-{VCl2} moiety show DNA crosslinking property. The complex with a dipyridophenazine moiety as a photosensitizer displays photocytotoxicity in cancer cells under visible light (400-700 nm) by hydroxyl radical-mediated apoptosis with low dark toxicity and significantly less activity in
normal cells.

 

 

 

 

418

 

Arylazoimidazole complexes of lead(II)-halide and their photochromism

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Debashis Mallick, Bharati Chowdhury,
Chandana Sen, Kamal Krishna Sarkar,
Srikanta Jana, Sudipa Mondal & Chittaranjan Sinha
*

 

 

 

The arylazoimidazoles complexes, [Pb(Raai-CnH2n+1)X2] in DMF solution exhibit E-to-Z isomerisation about the N=N group of the coordinated Raai-CnH2n+1 upon irradiation with UV light. The rate and quantum yields of the photoisomerisation of the complexes follows the sequence: [Pb(Raai-CnH2n+1)Cl2] < [Pb(Raai-CnH2n+1)Br2] < [Pb(Raai-CnH2n+1)I2] < Raai-CnH2n+1.
The activation energy of reverse isomerisation (Z-to-E) of [Pb(Raai-CnH2n+1)X2] is lower than that of the free ligand, while the entropy of activation is a large negative in the complexes.

 

 

 

 

427

 

Catalytic liquid phase oxidation of cyclohexane with tert-butylhydroperoxide over transition metal exchanged α-zirconium phosphate

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Savita Khare*, Priti Shrivastava, Rajendra Chokhare, Jagat Singh Kirar & Swati Parashar

 

 

 

The catalytic system, α-ZrP.M/dry TBHP, shows 50% selectivity each for cyclohexanone and cyclohexanol with 6.12% conversion in oxidation of cyclohexane after 5 h of reaction. The order of reactivity of a-ZrP.M for the oxidation of cyclohexane to cyclohexanone and cyclohexanol is: a-ZrP.Mn(II) > a-ZrP.Cu(II) > a-ZrP.Fe(III). The catalyst can be reused for three cycles.

 

 

 

 

435

 

Synthesis, characterization, luminescence and photocatalytic studies of layered pervoskites NaMMgWO6 (M = La, Pr, Sm)

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Sreenu K, Gundeboina Ravi, CH Sudhakar Reddy, Ravinder Guje & M Vithal*

 

 

 

The synthesis, characterization, and, optical and photocatalytic studies of AA'BB'X6 type perovskites, (NaMMgWO6, M = La, Pr, Sm), prepared by ethylene glycol assisted gel-burning method, are reported. Photocatalytic studies in the presence of NLMW, NPMW and NSMW show methyl violet degradation to be about 91%, 80% and 78% after 180 min visible light illumination respectively. In the case of methyl blue, degradation to the extent of 94%, 88% and 86% respectively (including photolysis of MB) is observed in the presence of NLMW, NPMW and NSMW.

 

 

 

 

Notes

 

444

 

Methacryloyloxycalix[4]arene based ion imprinted polymer as Ag(I) potentiometric sensor

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

İzzet Şener, Şeyma Avcı, Deniz Uğurağ &
Ebru Birlik zktk
*

 

 

 

A potentiometric sensor for determination of Ag(I) ions has been prepared via suspension polymerization using ethylene glycol dimethacrylic acid as cross-linker, 2, 2-azobisisobutyronitrile as
initiator and methacryloyloxycalix[4]arene as the monomer. The sensor responds to Ag(I) in the pH range of 2.08.0 with a linear working range of 1.010-3 1.010-7 M and detection limit of 1.5310-8 M.

 

 

 

 

449

 

Sonochemical synthesis of ZnO, NiO and α-Fe2O3 nanoparticles and their catalytic activity for thermal decomposition of ammonium perchlorate

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

 

Seyed Ghorban Hosseini* & Zahra Khodadadipoor

 

 

 

NiO, ZnO and α-Fe2O3 nanoparticles are successfully prepared by ultrasonic method and investigated for their catalytic activity in the thermal decomposition of ammonium perchlorate. In the presence of ZnO and NiO nanoparticles, the high temperature decomposition peak of ammonium perchlorate decreases by about 120 C and 105 C, respectively. In the presence of α-Fe2O3 nanoparticles, the high temperature decomposition peak of ammonium perchlorate decreases by 67 C, while the low temperature decomposition peak disappears.

 

 

 

 

 

 

Guide to Authors

 

 

 

 

 

 

Authors for correspondence are indicated by (*)

 

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Indian Journal of Chemistry

Vol. 57A, March 2018, pp. 409-417

 

Oxovanadium(IV) complexes of polypyridyl bases as
photocytotoxic and DNA crosslinking agents

Arun Kumara, Akanksha Dixitb, Samya Banerjeea, Sanjoy Mukherjeea, Somarupa Sahooa,
Anjali A Karandeb, * & Akhil R Chakravartya, *

aDepartment of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560 012, India

Email: arc@iisc.ac.in

bDepartment of Biochemistry, Indian Institute of Science, Bangalore 560 012, India

Email: anjali@iisc.ac.in

Received 29 December 2017; revised and accepted 26 February 2018

Dichlorooxovanadium(IV) complexes of polypyridyl bases (B), viz., [VO(B)Cl2] (1 and 2) of N,N,N-donor ligands 2-(2-pyridyl)-1,10-phenanthroline (pyphen in 1) and 3-(pyridin-2-yl)dipyrido[3,2-a:2',3'-c]phenazine (pydppz in 2) have been prepared, and their anticancer activity studied. The complexes show good solubility in most polar solvent and are non-electrolytes. They show 1:1 electrolytic property in 20% aqueous DMF, and 1:2 electrolytic character in 20% aqueous DMF upon photo-irradiation with visible light (400700 nm). Complex 1 shows DNA crosslinking property on dissociation of the V-Cl bond(s) as ascertained from its DNA melting profile and ethidium bromide displacement assay. The complexes 1 and 2 are photocytotoxic towards HeLa (IC50: 16.9 mM and 0.87 mM respectively) and MCF-7 (IC50: 19.5 mM and 1.4 mM respectively) cancer cells, but exhibit less toxicity in normal embryonic fibroblast 3T3 cells with IC50 values of ~40 and ~25 M in visible light (400-700 nm) for complexes 1 and 2 respectively. Complex 2 also displays light induced plasmid DNA cleavage activity. The light-induced cellular damage leads to generation of reactive oxygen species followed by apoptotic cell death.

Keywords: Bioinorganic chemistry, Photocytotoxicity, Cytotoxicity, DNA crosslinks, DNA cleavage, Vanadium, Polypyridyl bases

 

Indian Journal of Chemistry

Vol. 57A, March 2018, pp. 418-426

 

Arylazoimidazole complexes of lead(II)-halide and their photochromism

Debashis Mallicka, Bharati Chowdhuryb, Chandana Senb, Kamal Krishna Sarkarc,
Srikanta Janab, Sudipa Mondalb & Chittaranjan Sinhab,*

aDepartment of Chemistry, Mrinalini Datta Mahavidyapith, Birati, Kolkata 700 051, India

bDepartment of Chemistry, Inorganic Chemistry Section, Jadavpur University, Kolkata 700 032, India

cDepartment of Chemistry, Mahadevananda Mahavidyalaya, SN Banerjee Rd, Monirampore, Kolkata,
West Bengal 700120, India

Email: crsjuchem@gmail.com

Received 6 November 2017; revised and accepted 27 February 2018

Lead(II) complexes of 1-alkyl-2-(arylazo)imidazole (Raai-CnH2n+1), [Pb(Raai-CnH2n+1)X2] (X = Cl, Br, I; and Raai-CnH2n+1, R = H, Me and n = 4, 6, 8) have been characterized by UV-vis, IR and 1H-NMR spectroscopy. The coordinated Raai-CnH2n+1 in the complexes undergoes E-to-Z (trans-to-cis) isomerisation about the N=N group upon being irradiated with UV light in DMF solution. The rate and quantum yields of E-to-Z photoisomerisation (fEZ) of the complexes are poorer than the respective free ligand response and are also affected by the nature of halide present (Cl-, Br- and I-). Variation in physicochemical parameters may be correlated with the effective mass of the photochrome. The rate of isomerisation follows the sequence: [Pb(Raai-CnH2n+1)Cl2] < [Pb(Raai-CnH2n+1)Br2] < [Pb(Raai-CnH2n+1)I2]. The Z-to-E isomerisation has been carried out at varying temperatures (298308 K) to determine the activation energy of Z-to-E (cis-to-trans) isomerisation (Ea: 47.0963.42 kJ mol-1) and the entropy of activation (DS: 166.52 to 109.0 J mol-1 K-1) which is a large negative in the complexes. Theoretical calculation supports cleavage of Pb(II)-N(azo) bond followed by the N=N rotation in a three-coordinated symmetry rather than the four-coordinated symmetry.

Keywords: Photochromism, Density functional calculations, Arylazoimidazoles, Lead halide complexes

 

Indian Journal of Chemistry

Vol. 57A, March 2018, pp. 427-434

 

Catalytic liquid phase oxidation of cyclohexane with
tert-butylhydroperoxide over transition metal
exchanged α-zirconium phosphate

Savita Khare*, Priti Shrivastava, Rajendra Chokhare, Jagat Singh Kirar & Swati Parashar

School of Chemical Sciences, Devi Ahilya Vishwavidyalaya, Takshashila Campus,
Khandwa Road, Indore, 452 001 (MP), India

Email: savitakhare20@gmail.com

Received 22 August 2017; re-revised and accepted 23 February 2018

Transition metal exchanged a-zirconium phosphate, a-ZrP.M (where, M = Mn(II), Cu(II) and Fe(III)) has been prepared by ion exchange method and characterized by X-ray diffraction, scanning electron micrographs, energy dispersive X-ray analysis, Fourier transform infrared and atomic absorption spectroscopy. The catalytic activity of a-ZrP.M is tested for the oxidation of the cyclohexane in liquid phase with tert-butylhydroperoxide as an oxidant. In the oxidation reaction, cyclohexane is oxidized to cyclohexanol and cyclohexanone. The order of reactivity of a-ZrP.M for the oxidation of cyclohexane to cyclohexanone and cyclohexanol is: a-ZrP.Mn(II) > a-ZrP.Cu(II) > a-ZrP.Fe(III). A maximum of 6.12% conversion and 100% selectivity for KA oil (cyclohexanone (K) + cyclohexanol (A)) for oxidation of cyclohexane is observed with the
a-ZrP.Mn(II)/TBHP system after 5 h of reaction. Influence of various reaction parameters, viz. concentrations of oxidant and catalyst, reaction temperature, etc., has been studied. The catalyst, a-ZrP.Mn(II), can be recycled three times under similar reaction conditions.

Keywords: Catalysts, Heterogeneous catalysts, Oxidation, Liquid phase oxidation, Cyclohexane,
tert-Butylhydroperoxide, Transition metals,
a-Zirconium phosphate

 

Indian Journal of Chemistry

Vol. 57A, March 2018, pp. 435-443

 

Synthesis, characterization, luminescence and photocatalytic studies of layered perovskites NaMMgWO6 (M = La, Pr, Sm)

Sreenu K, Gundeboina Ravi, CH Sudhakar Reddy, Ravinder Guje & M Vithal*

Department of Chemistry, Osmania University, Hyderabad 500 007, Telangana, India

Email: muga_vithal@osmania.ac.in

The synthesis, characterization, optical and photocatalytic studies of AA'BB'X6 type perovskites, NaMMgWO6 (M = La, Pr, Sm), which have an ordering of both the cation sub-lattices, is reported. The obtained NaMMgWO6 materials have been prepared using ethylene glycol assisted gel-burning method and characterized by X-ray diffraction patterns, UV-vis diffused reflectance spectra, scanning electron microscopy, Fourier transformation infrared spectra, energy dispersive spectra and fluorescence spectra. The photocatalytic dye degradation performance of the as-synthesized perovskites has been evaluated with methylene blue and methyl violet as model water pollutants using radical quenchers.

Keywords: Perovskites, Layered perovskites, Photocatalytic activity, Photoluminescence, Chromaticity, X-ray diffraction, Band gap energy, Gel burning method

 

 

 

 

 

 

 

 

Indian Journal of Chemistry

Vol. 57A, March 2018, pp. 444-448

 

Methacryloyloxycalix[4]arene based ion imprinted
polymer as Ag(I) potentiometric sensor

İzzet Şenera, Şeyma Avcıb, Deniz Uğurağb & Ebru Birlik zktkb

aDepartment of Food Engineering, Kastamonu University Kastamonu, Turkey

bDepartment of Chemistry, Eskişehir Osmangazi University, Eskişehir, Turkey

Email: ebirlik@ogu.edu.tr

Received 6 November 2017; revised and accepted 27 February 2018

A new potentiometric sensor for the rapid, easy and cheap determination of Ag(I) ions is proposed. This sensor has been prepared via suspension polymerization using ethylene glycol dimethacrylic acid (EDMA) as cross-linker,
2, 2-azobisisobutyronitrile (AIBN) as initiator and methacryloyloxycalix[4]arene as the monomer. The ion imprinted polymer-based Ag(I) memory sensor has been prepared by dispersing Ag(I) imprinted polymer throughout the DBP plasticizer and embedding in PVC. The sensor responds to Ag(I) in the pH range of 2.08.0 with a working range of 1.
010-3 1.010-7 M and detection limit of 1.5310-8 M.

Keywords: Sensors, Potentiometric sensors, Ion-selective electrodes, Ion imprinted polymers, Silver imprinted polymers

 

Indian Journal of Chemistry

Vol. 57A, March 2018, pp. 449-453

 

Sonochemical synthesis of ZnO, NiO and α-Fe2O3 nanoparticles and their catalytic activity for thermal decomposition of ammonium perchlorate

Seyed Ghorban Hosseini* & Zahra Khodadadipoor

Department of Chemistry, Malek Ashtar University of Technology, P.O. Box 16765-3454, Tehran, Iran

Email: hoseinitol@yahoo.com

ZnO, NiO and α-Fe2O3 nanoparticles are synthesized by a simple and facile sonochemical calcination of zinc acetate, nickel acetate, and iron chloride as precursors. The as-prepared products are characterized by powder X-ray diffraction, and field emission scanning electron microscopy. The catalytic efficiency of these as-prepared oxides for thermal decomposition of ammonium perchlorate has been investigated by thermal gravimetric analysis and differential scanning calorimetry. The results show that addition of 2% as-prepared samples leads to merging of the two exothermic peaks of ammonium perchlorate into one peak. In the presence of ZnO and NiO nanoparticles, the high temperature decomposition peak of ammonium perchlorate decreases by about 120 C and 105 C, respectively. In the presence of α-Fe2O3 nanoparticles, the high temperature decomposition peak of ammonium perchlorate decreases by 67 C, while the peak of the low temperature decomposition disappears.

Keywords: Thermal decomposition, Ammonium perchlorate, Oxides, Metal oxides, Nanoparticles, Sonochemical synthesis