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Indian Journal of Chemistry

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

 

 

49

VOLUME 44A

NUMBER 2

FEBRUARY 2005

 

 

 

CONTENTS

 

  Papers

 221

A quantum chemical investigation of electrophilic addition reaction of bromine to bicyclo[3.2.2]nona-6,8-diene

 

  

Rıza Abbasoğlu*, S Savaşkan Yılmaz &  Yaşar Gök

 

 

 Full geometric optimization of bicyclo[3.2.2]nona-6,8-diene (BND) has been done by semiempirical and ab initio methods The molecular complexes of BND with bromine have been investigated by AM1 method and their stable configurations determined. Because of electronic factors, BND...Br2 (endo1) complex is more stable than BND…Br2 (endo 2).

 227

Aqueous solubility of freons in presence of nitrogen, oxygen and carbon dioxide

 

 

 

  

 

 

Sunita Mahata, B Guha Niyogi* & A Guha

 

 

 The solubilities of freons in water in terms of Henry’s constant in presence of N2, O2 and CO2 have been studied at 298.15 K and at 1 atm. pressure using the Scaled Particle Theory. KH increases with increase in the mole fraction of N2, O2 and CO2 except for CF4 in all cases and for CCl2F2 and CClF3 in presence of CO2. For a particular composition, the solubility follows the order: CO2 > O2 > N2.

232

Kinetic studies on the reactions of various 9-chloroacridines with some arylsulphonyl hydrazides and antiinflammatory and kinase inhibition activitiy of the products

 

 

 

 

 

 

 

 

Sham M Sondhi, Gurudas Bhattacharjee*, Rafid K Jameel, Ashok Kumar & Kiran Bajaj

 

 

 

241

Uncatalysed and catalysed reaction of acidic chlorite with acridine orange

 

 Brijesh Pare*, Rajani Vijay, S B Jonnalagadda & VW Bhagwat

 

 

 

245

Kinetics of oxidative degradation and deamination of atenolol by aqueous alkaline permanganate

 

G C Hiremath, R M Kulkarni & S T Nandibewoor*

 

 

The kinetics of the oxidative degradation of atenolol (ATN) by permanganate in aqueous alkaline medium at constant ionic strength of 0.30 mol dm-3 has been studied spectrophotometrically using a rapid kinetic accessory. The reaction is first order in [permanganate ion] and is less than unit order each in [ATN] and [alkali].

 251

Destructive adsorption of methyl parathion over nanocrystalline MgO

 

 

Vanga S Reddy, A Radheshyam, R Dwivedi, R K Gupta, V R Chumbale & R Prasad*

 

 

Destructive adsorption of methyl parathion has been investigated over some transition metal oxides and alkali earth metal oxides. Performance of alkaline earth oxides has been found to be better than that of transition metal oxides and best performance has been shown by aerogel method prepared nanocrystalline AP- MgO.

256

Precursors for mixed metal oxide nanoparticles: Synthesis and characterization of m-oxoalkoxides of some bivalent metals and their b-diketonates

  

Malti Sharma, Ajay K Bhagi, Harish K Sharma, Priti, Ritu Kansal,  Ram Kumar, Pramesh N Kapoor*

 

 

 

261

Synthesis and structural characterization of a novel homo-binuclear complex [Cu(dinemac)-(H2O)2][Cu(dipic)2].3H2O: Assembly of discrete cationic and anionic components in a 1D chain through H bonding

 

 

 

  

 

 

 

Ambarish Ray, Dipankar Maiti, Mahammad Ali*, William S Sheldrick & Heike Mayer-Figge

 

 

 

265

Synthesis and mesomorphic characterization of Cu(II), Ni(II) and Pd(II) complexes with azomethine and chalcone as bridging group

 

 

 

 

 

 

 

B T Thaker*, P K Tandel, A S Patel, C J Vyas, M S Jesani & D M Patel

 

 

 

 

n= 8,10,12,14,16,18 and M= Cu(II),Ni(II) and Pd(II)

271

Characterization of charge-transfer complex formation between 3,6-diamino-9H-carbazole and 3,6-dinitro-9H-carbazole

 

 

 

 

 

Subhas Chandra Maity, Dipakranjan Mal & Mrinal M Maiti*

 

 

Electron donor-acceptor (EDA) interaction between 3,6-diamino-9H-carbazole (DAC) as the donor, and 3,6-dinitro-9H-carbazole (DNC) as the acceptor, has been characterized. Benesi-Hildebrand plots of the DAC-DNC system in acetonitrile at 300 K in the wavelength range of 620-660 nm indicate a strong EDA interaction with both the thermodynamic formation constant K, and the molar absorptivity el of the order of two. IR spectral, DSC, and XRD data also clearly indicate a strong EDA interaction even in their 1:1 molar mixture in solid state.

277

Synthesis and characterization of transition metal encapsulated derivatives of 16 and 18 membered [N4] macrocycles modified with four carbonyl functions bearing cyclic tetrapeptide features

 

Zafar Ahmad Siddiqi*, V J Mathew & Shah Mohammad Shadab

 

 

Encapsulation of transition metal ions in [N4] macrocycles modified with endocyclic carbonyl functions, a mimic to cyclic tetrapeptide, is reported. It involves chelation via protonated aza biting sites of the peptide functions.

Notes

 

286

 

Probabilistic cellular automata model for reaction diffusion systems

 

 

 

 

K A Khan* & R A Khan

 

 

 

 

291

 

Quantum-chemical studies on the interactions of b-cyclodextrin and 4-methylpyridine

 

 

 

 

 

 

 

 

 

 

En-cui Yang, Xiao-jun Zhao* & Hua Fang

 

 

 

Semi-empirical PM3 calculations have been performed on the inclusion complexation of b-cyclodextrin with
4-methylpyridine for methyl group up and down inclusion orientations, respectively.

295

Spectrofluorometric studies on the intermolecular interaction in some aqueous surfactant-polymer solutions

 

 

 

 

 

 

 

O P Yadav*, Payal Jamwal & D V S Jain

 

 

Using anthracene as a fluorescence probe, the intermolecular interaction in sodium dodecyl sulphate (SDS)+poly(N-vinyl-2-pyrrolidone) (PVP) and bis(2-ethylhexyl sulphosuccinate sodium salt) (AOT)+polyvinyl alcohol (PVA) in aqueous solutions have been investigated. Fluorescence data show that binding of premicellar aggregates of anionic surfactant, SDS, with PVP takes place over the surfactant concentration 3-15 mmol dm-3 prior to usual micelle formation. However, in the case of AOT+PVA, instead of binding of surfactant with the polymer, formation of mixed micelles having CMC value lower than that for pure AOT has been observed.

299

Molecular ribbons: Hydrothermal synthesis and structural characterization of [{Cu(dipic)-(H2O)}2(μ-4,4¢-bipy)].2H2O (dipic=pyridine-2,6-dicarboxylato; 4,4¢-bipy=4,4¢-bipyridyl)

 

 

 

 

 

 

Sudalaiandi Kumaresan* & Palani Ramadevi

 

 

Hydrothermal reaction of Cu(OAc)2.H2O with pyridine-2,6-dicarboxylic acid (dipicH2) and 4,4¢-bipyridine (4,4¢-bipy) affords an inorganic–organic hybrid material with an empirical formula, C24H18O10N4Cu2.2H2O. Single crystal X-ray study shows that the complex crystallizes in the triclinic space group P-1. The unit cell contains one and a half molecules of [{Cu(C7H3NO4)(H2O)}2(C10H8N2)]. 2H2O. The crystal structure displays ribbons in which the 4,4¢-bipy ligands are all nearly parallel.

303

Synthesis and characterization of some ruthenium(II) complexes containing triphenyl-phosphine or triphenylarsine with imidazoles

 

 

 

 

Ashish Malhotra, Prashant Sarkhel, Mohua Das & Raj K Poddar*

 

 

Reactions of [RuX2(PPh3)3] (X = Cl or Br) and [RuCl3(PPh3)3] with L (Im, BzIm or 2-MeIm) have been carried out in benzene and compounds of the type [RuX2(PPh3)(L)3] are obtained. Reactions of [RuCl3(AsPh3)2(MeOH)] and [RuBr3(AsPh3)3] with L (L = Im and BzIm) in benzene at room temperature or refluxing conditions lead to the formation of [RuX2(AsPh3)(Im)3] and [RuX2(BzIm)4], respectively.

307

K-NEXAFS investigations on some copper (II) complexes

 

 

 

 

 

 

 

Pooja Sharma* & Ashutosh Mishra

 

 

Near edge X-ray absorption fine structure (NEXAFS) covering energy range up to about 50 eV of some copper(II) complexes with 3-arylazo-7-hydroxy-4-methylcoumarin as ligand has been studied. The observed X-ray parameters e.g. chemical shift, shift of principal absorption maximum, edge-width, fractional oxidation number and percentage covalency have been used to explain the structure of the complexes and these parameters have also been correlated with earlier studies.

312

Square-wave voltammetric method for the determination of trace levels of manganese(II) and its application to the analysis of low alloy steel

 

 

 

 

Aditi A Dalvi, M M Palrecha & R Sundaresan*

 

 

A highly sensitive, rapid and simple square-wave voltammetric procedure for the determination of Mn(II) has been developed. Mn(II) in 0.1 M triethanolamine and 0.15 M KOH gives a well-defined, reversible peak at -0.456V vs. Ag/AgCl. The calibration curve is linear in the concentration range of 0-100 mg/ml. The minimum concentration that can be determined is found to be 40 ng/ml (s.d. = 4.2%). Effect of various ions, which commonly occur with Mn(II), has also been studed.

 Authors for correspondence are indicated by (*)

 

 

Indian Journal of Chemistry

Vol. 44A, February 2005, pp. 221-226

 

A quantum chemical investigation of electrophilic addition reaction of bromine to bicyclo[3.2.2]nona-6,8-diene

Rıza Abbasoğlu*, S Savaşkan Yılmaz & Yaşar Gök

 

Full geometric optimization of  bicyclo[3.2.2]nona-6,8-diene (BND)  has been done  by semiempirical and ab initio methods and the structure of the molecule has also been investigated. The double bond (I)  situated in  the opposite direction of  methylene group in  BND  molecule is more exo pyramidalized than the other double bond (II). The electron density (qi,HOMO) of the double bond(I) in HOMO of the molecule is more than that of the (II) double bond. Exo and endo faces of exo pyramidalized double bonds of the molecule are not equal and electron density is higher in endo faces. The molecular complexes of BND with bromine have been investigated by AM1 method and their stable configurations determined. The reason for  endo molecular complexes being  more stable than exo  is that the stability is caused by electronic and steric factors. Because of electronic factors, BND...Br2(endo1) complex is more stable than BND…Br2 (endo 2). The endo-bridged bromonium cation(I) is relatively more stable than the endo-bridged cation(IV). Endo-facial stereoselectivity and regioselectivity should be observed in the addition of  bromine to  BND molecule. Endo-facial stereoselectivity is caused  by electronic and  steric effects, regioselectivity by electronic effects. The  rearranged  bromocarbonium cation(V) is the most  stable  among the cationic intermediates and the ionic addition reaction occurs via this cation.

 

 

 

Indian Journal of Chemistry

Vol. 43A, January 2005, pp. 227-231

 

Aqueous solubility of freons in presence of nitrogen, oxygen and carbon dioxide

Sunita Mahata, B. Guha Niyogi* & A. Guha

 

The solubilities of freons in water in terms of Henry’s constant (KH) in presence of N2, O2 and CO2 have been studied at 298.15 K and at 1 atmospheric pressure using the Scaled Particle Theory (SPT). The values of KH have been found to increase with increase in the mole fraction of N2, O2 and CO2 except for CF4 in all cases and for CCl2F2 and CClF3 in presence of CO2. For a particular composition the solubilites follow the order CO2 > O2 > N2.

 

 

 

Indian Journal of Chemistry

Vol. 44A, February 2005, pp. 232-240

 

Kinetic studies on the reactions of various 9-chloroacridines with some arylsulphonyl hydrazides and antiinflammatory and kinase inhibition activitiy of the products

Sham M Sondhi, Gurudas Bhattacharjee*, Rafid K Jameel, Ashok Kumar & Kiran Bajaj

 

9-Chloro-2,4(un)substituted acridines (1a-e) have been condensed with benzenesulphonyl hydrazide (2a), p-toluenesulphonyl hydrazide (2b), and 4-methoxybenzenesulphonyl-hydrazides (2c) to obtain the corresponding condensed products 3a-o. The structures of all the compounds synthesized have been confirmed by spectroscopic methods. Antiinflammatory and kinase inhibition activities of all the compounds (3a–o) have been investigated. Compounds 3e,h,i,n exhibit good and 3a-d,f,g,j-m,o exhibit moderate anti-inflammatory activity. Kinetic studies on the concerned aromatic nucleophilic substitution (SNAr) have been carried out in methanol (MeOH). Another three reactions of 1a with suphonyl hydrazide 2a-c have been studied in DMSO under the same conditions for comparison. The base catalysed mechanism (modified heteroconjugate BH+SB, BH+B) has been proposed for the reaction in MeOH. The effect of substituents on the benzene ring of the sulphonyl hydrazide is in the order: MeO>Me>H, reflecting the importance of electron-donating behaviour of the substituent in enhancing the nucleophilcity of hydrazide group and also in stabilizing the zwitterionic complex T±.

 

IPC Code: Int.Cl.7 B01J

 

 

 

Indian Journal of Chemistry

Vol. 44A, February 2005, pp. 241-244

 

Uncatalysed and catalysed reaction of acidic chlorite with acridine orange

Brijesh Pare*, Rajani Vijay, SB Jonnalagadda & VW Bhagwat

 

The kinetics and mechanism of uncatalysed and Ru(III) catalyzed oxidative degradation of acridine orange {3,6-bis(dimethylamino)acridine zinc chloride double salt}(AO+) by sodium chlorite in acidic medium has been investigated. With excess concentration of other reactants, both uncatalysed and catalyzed reactions follow pseudo-first order kinetics with respect to [AO+]. The uncatalysed reaction follows fractional order kinetics in oxidant and first order kinetics in catalyst [Ru(III)]. Role of acid has been found to be complex. The rate coefficient of the uncatalysed reaction is 4.45´10-4s-1 while the catalytic constant for the catalyzed reaction is 8.00´10-4s-1. Increase in ionic strength by the addition of neutral salt (Na2SO4) resulted in decrease in rate constant value suggesting that oppositely charged species are involved in rate determining step. The effect of change in pH has also been reported. The overall stoichiometry of the reaction has been found to be 2AO+ + 3ClO2- + 3H+ + 6H2O = 2P + 2(CH3)2N+OH + 2CH3CH2OH + 3HCl, where P is 7-aminoquinoline-2,3-dicarboxylic acid. The catalytic range for Ru(III) is found to be 1.0´10-8 mol dm-3. Ru(III) has been found to be complexed with chlorite. A mechanism consistent with the experimental results has been proposed.

 

IPC Code: Int.Cl.7 B01J 23/46; C07B 33/00

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp. 245-250

 

Kinetics of oxidative degradation and deamination of atenolol by aqueous alkaline permanganate

G C Hiremath, R M Kulkarni & S T Nandibewoor*

 

The kinetics of the oxidative degradation of atenolol (ATN) by permanganate in aqueous alkaline medium at constant ionic strength of 0.30 mol dm-3 has been studied spectrophotometrically using a rapid kinetic accessory. The reaction is first order in [permanganate ion] and has less than unit order each in [ATN] and [alkali]. Initial addition of products and change in ionic strength have no significant effect on the reaction rate. However, decrease in dielectric constant of the medium increases the rate. The oxidation in alkaline medium has been shown to proceed via permanganate-atenolol complex, which decomposes slowly in a rate determining step followed by a fast reaction between a free radical of atenolol and another molecule of permanganate species to give the products. The main products have been identified by IR, NMR, fluorimetric and mass spectral studies. The reaction constants involved in the mechanism are evaluated and a good agreement between observed rate constants and the calculated rate constants is obtained. The activation parameters are computed with respect to slow step of the proposed mechanism.

 

IPC Code: Int.Cl.7 C07B 33/00

 

 

 

Indian Journal of Chemistry

Vol. 44A, February 2005, pp. 251-255

 

Destructive adsorption of methyl parathion over nanocrystalline MgO

Vanga S Reddy, A Radheshyam, R Dwivedi, R K Gupta, V R Chumbalec & R Prasad*

 

Destructive adsorption of methyl parathion (MP) has been investigated over few transition metal oxides and alkali earth metal oxides. Performance of alkaline earth oxides have been found to be better than transition metal oxides and best performance has been shown by aerogel method prepared nanocrystalline AP-MgO. The AP-MgO powder has been characterized by XRD, AFM and BET surface area measurements. Destructive adsorption of MP over AP-MgO has been compared with that of activated carbon. Both are found to adsorb methyl parathion effectively. An IR investigation of the surface of treated AP-MgO and activated carbon reveals that activated carbon adsorbs methyl parathion as such in the molecular form and AP-MgO adsorbs it destructively.

 

IPC Code: Int. Cl.7 B01D 15/00; H05G

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp. 256-260

 

Precursors for mixed metal oxide nanoparticles: Synthesis and characterization of m-oxoalkoxides of some bivalent metals and their b-diketonates

Malti Sharma, Ajay K Bhagi, Harish K Sharma, Priti, Ritu Kansal, Ram Kumar & Pramesh N Kapoor*

 

New heterobimetallic derivatives of the type M{OAl(OPri)2}2 (M = Sn, Pb, Cd) have been prepared by the reactions of M(OAc)2 with Al(OPri)3 in 1:2 molar ratio in hydrocarbon solvent (xylene/toluene) with the continuous liberation of isopropyl acetate. Furthermore, reactions of M{OAl(OPri)2}2 (M = Ca, Pb, Cd) with b-diketones (acetylacetone, benzoyl acetone) have also been carried out to obtain modified derivatives. These new derivatives have been characterized by elemental analyses and spectroscopic [IR, NMR (1H, 13C, 27Al and 119Sn)] studies.

 

IPC Code: Int.Cl.7 C07F 3/08; C07F 7/22; C07F 7/24; C07F 5/00

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp. 261-264

 

Synthesis and structural characterization of a novel homo-binuclear complex [Cu(dinemac)(H2O)2][Cu(dipic)2].3H2O: Assembly of discrete cationic and anionic components in a 1D chain through H bonding

Ambarish Ray, Dipankar Maiti, Mahammad Ali*, William S Sheldrick & Heike Mayer-Figge

 

This work describes the synthesis and structural characterization of a novel homo-binuclear copper(II) complex [Cu(dinemac)(H2O)2][Cu(dipic)2].3H2O (1), in which the macrocylic cationic modules are assembled with the anionic components through H bonding. The X-ray structural analysis indicates that the central atoms Cu(1) and Cu(2) of the two independent cations lie on crystallographic centers of symmetry and that the independent anion with its central atom Cu¢ is sited at a general position. The asymmetric unit of 1 consists of two halves of [Cu(dinemac)(H2O)2]2+ cations, a [Cu(dipic)2]2- anion and three water molecules. The room temperature solid state EPR spectrum of the polycrystalline sample is typical for a non-distorted or exchange averaged mononuclear Cu(II) complex with gav=2.146±0.005 and DHpp=9.5 mT.

 

IPC Code: Int Cl.7 C07F 1/08

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp. 265-270

 

Synthesis and mesomorphic characterization of Cu(II), Ni(II) and Pd(II) complexes with azomethine and chalcone as bridging group

B T Thaker*, P K Tandel, A S Patel, C J Vyas, M S Jesani & D M Patel

 

The synthesis and mesomorphic properties of a homologous series of 4-(4¢-n-alkoxy propionyl) imine-2²-hydroxy benzaldehyde (where n = 8, 10, 12, 14, 16, 18 n-alkyl) and their Cu(II), Ni(II) and Pd(II) complexes are reported here. All the compounds have been characterized by physical methods such as complexometric titration, elemental analysis, IR, 1H NMR, UV/Visible, ESR (RT and LNT) and TGA studies. Liquid crystalline properties of the ligands and complexes have been studied by DSC analysis and polarized optical microscopy.

 

IPC Code: Int.Cl.7 C07F 1/08; C07F 15/04; C07F 15/00

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp. 271-276

 

Characterization of charge-transfer complex formation between 3,6-diamino-9H-carbazole and 3,6-dinitro-9H-carbazole

Subhas Chandra Maity, Dipakranjan Mal & Mrinal M Maiti*

 

Electron donor-acceptor (EDA) interaction between 3,6-diamino-9H-carbazole (DAC) as the donor, and 3,6-dinitro-9H-carbazole (DNC) as the acceptor, has been characterized from IR spectral, differential scanning calorimetric (DSC), and X-ray diffraction analyses, in addition to UV-vis spectral studies. Benesi-Hildebrand plots of the DAC-DNC system in acetonitrile at 300 K in the wavelength range of 620-660 nm indicate a strong EDA interaction with both the thermodynamic formation constant K, and the molar absorptivity el of the order of two. IR spectral, DSC, and XRD data also clearly indicate a strong EDA interaction even in their 1:1 molar mixture in solid state.

 

IPC Code: Int. Cl.7 G01N 21/00; C07D 209/82

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp 277-285

 

Synthesis and characterization of transition metal encapsulated derivatives of 16- and 18- membered [N4] macrocycles modified with four carbonyl functions bearing cyclic tetrapeptide features

Zafar Ahmad Siddiqi*, V J Mathew & Shah Mohammad Shadab

 

Condensation reactions of 1,2-diaminoethane or 1,3-diaminopropane with cyclic dicarboxylic acid anhydrides (succinic anhydride or phthalic anhydride) as well as their corresponding acids in 1:1 mole ratio in dioxane have afforded 16- or 18-membered macrocycles (L1-L4). Physico-chemical and spectroscopic data reveal the presence of cyclic tetraamide/tetrapeptide functions. The macrocycles behave as strong chelating agents forming stable solid complexes with the stoichiometries [MLX2] (L = L1 - L4; M = Fe, Co or Cu; X = Cl or ClO4) and [MLX2]X (M = Fe or Cr). Spectral data indicate coordination through amide/peptide nitrogen without its deprotonation and suggest that metal ions lie in the basal plane of the macrocyclic cavity. The coordination geometry has been ascertained from magnetic moment measurements, ligand field spectra and EPR studies. The anisotropic EPR signals observed for Cu (II) complexes with g> g > 2.0 confirm tetragonality in the geometry. However, the corresponding orbital reduction parameter k>k and the magnitude of G<4.0 suggest a significant contribution of the exchange coupling in the distortion of the Oh geometry of Cu (II) complex.

 

 

 

Indian Journal of Chemistry

Vol. 44A, February 2005, pp. 286-290

 

Probabilistic cellular automata model for reaction diffusion systems

K A Khan* & R A Khan

 

Class of cellular automata (CA) for modeling reaction diffusion systems has been presented. The construction of the CA is general enough to be applicable to large class of reaction diffusion equations. The automata are based on running average procedure and on probabilistic table look up to implement diffusion reactions. The evolution of probabilistic CA simulates a spatially distributed process, given by a partial differential equation (PDE). The solutions are very isotropic despite the discreteness and the anisotropic nature of the CA. The adverse effects of discretization are overcome by the use of probabilistic rules. In order to obtain the assurance of the proposed method, the probabilistic CA approach for evolution of reaction diffusion process usually given by PDE is proposed.

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp. 291-294

 

Quantum-chemical studies on the interactions of b-cyclodextrin and 4-methylpyridine

En-cui Yang, Xiao-jun Zhao* & Hua Fang

 

Semi-empirical PM3 calculations have been performed on the inclusion complexation of b-cyclodextrin (b-CD) with 4-methylpyridine for methyl group up and down inclusion orientations, respectively. The single point energy of the resultant complexes are further computed at the level of B3LYP/3-21G* in vacuo and in water solution. The results obtained show that the complexation orientation in which the methyl group is located near the primary hydroxyl rim of the CD cavity is found to be more favourable energetically arising from the effective hydrophobic interactions. The statistical thermodynamics calculations at 1 atm and 298.15K suggest that the inclusion complexation processes of two different orientations are enthalpy-driven in origin.

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp 295-298

 

Spectrofluorometric studies on the intermolecular interaction in some aqueous surfactant-polymer solutions

O P Yadav*, Payal Jamwal & D V S Jain

 

Using anthracene as a fluorescence probe, the intermolecular interaction in sodium dodecyl sulphate (SDS)+poly(N-vinyl-2-pyrrolidone) (PVP) and bis(2-ethylhexyl sulphosuccinate sodium salt) (AOT)+polyvinyl alcohol (PVA) in aqueous solutions have been investigated. From the observed vibronic band intensity ratio, I1/I3, (at lem = 340 nm and l em = 404 nm), in the fluorescence spectra of 10-6 mol dm-3 anthracene as a function of surfactant concentration, the order of polarity of microenvironment around the probe in aqueous surfactant+polymer solutions has been assessed. Fluorescence data show that binding of premicellar aggregates of anionic surfactant, SDS, with PVP takes place, over the surfactant concentration of 3-15 mmol dm-3 prior to usual micelle formation. However, in the case of AOT+PVA, instead of binding of surfactant with the polymer, formation of mixed micelles having CMC value lower than that for pure AOT has been observed.

 

IPC Code: Int. Cl7. G01N 21/64

 

 

 

Indian Journal of Chemistry

Vol. 44A, February 2005, pp. 299-302

 

Molecular ribbons: Hydrothermal synthesis and structural characterization of [{Cu(dipic)(H2O)}2(μ-4,4¢-bipy)].2H2O (dipic=pyridine-2,6-dicarboxylato; 4,4¢-bipy=4,4¢-bipyridyl)

Sudalaiandi Kumaresan* & Palani Ramadevi

 

Hydrothermal reaction of Cu(OAc)2.H2O with pyridine-2,6-dicarboxylic acid (dipicH2) and 4,4¢-bipyridine (4,4¢-bipy) afforded  an inorganic–organic hybrid material with an empirical formula, C24H18O10N4Cu2.2H2O (1). Single crystal X-ray structure determination shows that complex (1) crystallized in the triclinic space group P-1. The unit cell contains one and a half molecules of [{Cu(C7H3NO4)(H2O)}2(C10H8N2)].2H2O (1). The crystal structure displays ribbons of (1) in which the 4,4¢-bipy ligands are all nearly parallel. The binuclear molecules associate through hydrogen bonding and weak Cu××××O interactions.

 

IPC Code: Int. Cl.7 C07F 1/08

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp. 303-306

 

Synthesis and characterization of some ruthenium(II) complexes containing triphenylphosphine or triphenylarsine with imidazoles

Ashish Malhotra, Prashant Sarkhel, Mohua Das & Raj K Poddar*

 

Reactions of [RuX2(PPh3)3] (X = Cl or Br) and [RuCl3(PPh3)3] with L (Im, BzIm or 2-MeIm) have been carried out in benzene and compounds of the type [RuX2(PPh3)(L)3] are obtained. Reactions of [RuCl3(AsPh3)2(MeOH)] and [RuBr3(AsPh3)3] with L (L = Im and BzIm) in benzene at room temperature or refluxing conditions lead to the formation of [RuX2(AsPh3)(Im)3] and [RuX2(BzIm)4], respectively. All the compounds have been characterized by analytical data, conductivity measurements, IR, NMR, UV-visible and cyclic voltametric studies.

 

IPC Code: Int. Cl.7 C07F 15/00

 

 

 

Indian Journal of Chemistry

 Vol. 44A, February 2005, pp. 307-311

 

K-NEXAFS investigations on some copper (II) complexes

Pooja Sharma* & Ashutosh Mishra

 

Near edge X-ray absorption fine structure (NEXAFS) covering energy range up to about 50 eV have been studied. The present studies include some copper (II) complexes of biological interest with 3-arylazo-7-hydroxy-4-methylcoumarin as ligand. Studies have been carried out on Seifert X-ray generator and Cauchois type bent crystal X-ray spectrograph of 0.4-m radius. The observed X-ray parameters e.g. chemical shift, shift of principal absorption maximum, edge-width, fractional oxidation number and percentage covalency have been used to explain the structure of the complexes and these parameters have also been correlated with earlier chemical studies.

 

IPC Code: Int Cl7. C07F 1/08, H05G

 

 

 

Indian Journal of Chemistry

Vol. 44A, February 2005, pp. 312-314

 

Square-wave voltammetric method for the determination of trace levels of manganese(II) and its application to the analysis of low alloy steel

Aditi A Dalvi, M M Palrecha & R Sundaresan*

 

A highly sensitive, rapid and simple square-wave voltammetric procedure for the determination of Mn(II) has been developed. Mn(II) in triethanolamine (0.1 M) and KOH (0.15 M) gives a well-defined, reversible peak at -0.456V vs. Ag/AgCl. The calibration curve is linear in the concentration range of 0-100 mg/ml. The minimum concentration that can be determined is found to be 40 ng/ml (s.d. = 4.2%). Effect of various ions, which commonly occur with Mn(II), has also been studied. The procedure has been applied for the determination of Mn(II) in low alloy steel samples.

 

IPC Code: Int.Cl.7 G01N 27/00