Sankaralingam Arunachalam

Bharathidasan University, Tiruchchināppalli, Tamil Nādu, India

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Publications (39)79.34 Total impact

  • [Show abstract] [Hide abstract]
    ABSTRACT: The novel surfactant copper(II) complexes, [Cu(ip)2DA](ClO4)21, [Cu(dpqc)2DA](ClO4)22, [Cu(dppn)2DA](ClO4)23, where ip=imidazo[4,5-f][1,10]phenanthroline, dpqc=dipyrido[3,2-a:2',4'-c](6,7,8,9-tetrahydro)phenazine, dppn=benzo[1]dipyrido[3,2-a':2',3'-c]phenazine and DA-dodecylamine, were synthesized and characterized by physico-chemical and spectroscopic methods. In these complexes 1-3, the geometry of copper metal ions was described as square pyramidal. The critical micelle concentration (CMC) value of these surfactant copper(II) complexes in aqueous solution was found out from conductance measurements. Specific conductivity data at different temperatures served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔGm°, ΔHm° and ΔSm°). The binding interaction of these complexes with DNA (calf thymus DNA) in Tris buffer was studied by physico-chemical techniques. In the presence of the DNA UV-vis spectrum of complexes showed red shift of the absorption band along with significant hypochromicity indicating intercalation of our complexes with nucleic acids. Competitive binding study with ethidium bromide (EB) shows that the complexes exhibit the ability to displace the nucleic acid-bound EB indicating that the complexes bind to nucleic acids in strong competition with EB for the intercalative binding site. Observed changes in the circular dichoric spectra of DNA in the presence of surfactant complexes support the strong binding of complexes with DNA. CV results also confirm this mode of binding. Some significant thermodynamic parameters of the binding of the titled complexes to DNA have also been determined. The results reveal that the extent of DNA binding of 3 was greater than that of 1 and 2. The antibacterial and antifungal screening tests of these complexes have shown good results compared to its precursor chloride complexes.
    Colloids and surfaces B: Biointerfaces 06/2014; 122C:151-157. · 3.55 Impact Factor
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    ABSTRACT: A series of surfactant-copper(II) Schiff base complexes (1-6) of the general formula, [Cu(sal-R2)2] and [Cu(5-OMe-sal-R2)2], {where, sal = salicylaldehyde, 5-OMe-sal = 5-methoxy- salicylaldehyde, and R2 = dodecylamine (DA), tetradecylamine (TA), or cetylamine (CA)} have been synthesized and characterized by spectroscopic, ESI-MS, and elemental analysis methods. For a special reason, the structure of one of the complexes (2) was resolved by single crystal X-ray diffraction analysis and it indicates the presence of a distorted square-planar geometry in the complex. Analysis of the binding of these complexes with DNA has been carried out adapting UV-visible-, fluorescence-, as well as circular dichroism spectroscopic methods and viscosity experiments. The results indicate that the complexes bind via minor groove mode involving the hydrophobic surfactant chain. Increase in the length of the aliphatic chain of the ligands facilitates the binding. Further, molecular docking calculations have been performed to understand the nature as well as order of binding of these complexes with DNA. This docking analysis also suggested that the complexes interact with DNA through the alkyl chain present in the Schiff base ligands via the minor groove. In addition, the cytotoxic property of the surfactant-copper(II) Schiff base complexes have been studied against a breast cancer cell line. All six complexes reduced the visibility of the cells but complexes 2, 3, 5, and 6 brought about this effect at fairly low concentrations. Analyzed further, but a small percentage of cells succumbed to necrosis. Of these complexes (6) proved to be the most efficient aptotoxic agent.
    Journal of biomolecular structure & dynamics 05/2014; · 4.99 Impact Factor
  • Karuppiah Nagaraj, Subramanian Ambika, Sankaralingam Arunachalam
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    ABSTRACT: A surfactant-copper(II) complex, [Cu(dpq)2DA](ClO4)2 (dpq = dipyrido[3,2-d:2'-3'-f]quinoxaline; DA-dodecylamine), was synthesized and characterized on the basis of elemental analyses, UV-vis, IR, and EPR spectra. The critical micelle concentration (CMC) value of this surfactant-copper(II) complex in aqueous solution was found out from conductance measurements. Specific conductivity data at different temperature served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization ([Formula: see text], [Formula: see text], and [Formula: see text]). In addition, the complex has been examined by its ability to bind to nucleic acids (DNA and RNA) in tris-HCl buffer by UV-vis absorption, emission spectroscopy techniques, and viscosity measurements. The complex has been found to bind strongly to nucleic acids with apparent binding constants at DNA and RNA is 4.3 × 10(5), 9.0 × 10(5) M(-1), respectively. UV-vis studies of the interaction of the complex with DNA/RNA have revealed that the complex can bind to both DNA and RNA by the intercalative binding mode via ligand dpq into the base pairs of DNA and RNA which has been verified by viscosity measurements. The presence of long aliphatic chain in the surfactant complex increases this hydrophobic interaction. The binding constants have been calculated. The cytotoxic activity of this complex on human liver carcinoma cancer cells was determined by adopting 3-(4, 5-dimethylthiazol-2-yl)-2, 5- diphenyl tetrazolium bromide assay and specific staining techniques. The antimicrobial and antifungal screening tests of this complex have shown good results.
    Journal of biomolecular structure & dynamics 01/2014; · 4.99 Impact Factor
  • Journal of Luminescence 01/2014; · 2.14 Impact Factor
  • Karuppiah Nagaraj, Sankaralingam Arunachalam
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    ABSTRACT: The kinetics of reduction of the surfactant complex ions cis-[Co(phen)2(C12H25NH2)2]3+ and cis-[Co(bpy)2(C12H25NH2)2]3+ (phen = 1,10-phenanthroline, bpy = 2,2′-bipyridine, C12H25NH2 = dodecylamine) in solutions of unilamellar vesicles of dipalmitoylphosphatidylcholine (DPPC) were studied at different temperatures by a spectrophotometric method under pseudo-first-order conditions using an excess of the reductant. Experimentally the reaction was found to be second order and the electron transfer postulated as outer sphere. Below the phase temperature of DPPC the second-order rate constant for this electron-transfer reaction of both the complexes was found to decrease with increasing concentration of the liposome. Above the phase transition temperature the reaction rate was found to increase with increasing concentration of DPPC. Below the phase transfer temperature the results have been explained on the basis of electrostatic double layer repulsion which prevents the vesicles from accumulation of surfactant–cobalt(III) complexes in the interior of the vesicle membrane. Above the phase transfer temperature the release of the surfactant–cobalt(III) complex molecules from the interior core to the exterior surface of the vesicle through the strong hydrophobic effect increases the reaction rate. The main driving force for this phenomenon is considered to be the intervesicular hydrophobic interaction between the surfactant complexes and vesicles surface. We could observe isokinetic relationships for both the complexes of the present study at the phase transfer temperature of DPPC.
    Monatshefte fuer Chemie/Chemical Monthly 01/2014; 145(3). · 1.63 Impact Factor
  • Karuppiah Nagaraj, Subramanian Sakthinathan, Sankaralingam Arunachalam
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    ABSTRACT: A new water-soluble surfactant copper(II) complex [Cu(sal-ala)(phen)(DA)] (sal-ala = salicylalanine, phen = 1,10-phenanthroline, DA = dodecylamine), has been synthesized and characterized by physico-chemical and spectroscopic methods. The critical micelle concentration (CMC) values of this surfactant-copper(II) complex in aqueous solution were obtained from conductance measurements. Specific conductivity data (at 303, 308, 313. 318 and 323 K) served for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔG(0)m, ΔH(0)m and ΔS(0)m). The interaction of this complex with nucleic acids (DNA and RNA) has been explored by using electronic absorption spectral titration, competitive binding experiment, cyclic voltammetry, circular dichroism (CD) spectra, and viscosity measurements. Electronic absorption studies have revealed that the complex can bind to nucleic acids by the intercalative binding mode which has been verified by viscosity measurements. The DNA binding constants have also been calculated (Kb = 1.2 × 10(5) M(-1) for DNA and Kb = 1.6 × 10(5) M(-1) for RNA). Competitive binding study with ethidium bromide (EB) showed that the complex exhibits the ability to displace the DNA-bound-EB indicating that the complex binds to DNA in strong competition with EB for the intercalative binding site. The presence of hydrophobic ligands, alanine Schiff-base, phenanthroline and long aliphatic chain amine in the complex were responsible for this strong intercalative binding. The surfactant-copper (II) complex was screened for its antibacterial and antifungal activities against various microorganisms. The results were compared with the standard drugs, amikacin(antibacterial) and ketokonazole(antifungal).
    Journal of Fluorescence 12/2013; · 1.79 Impact Factor
  • Selvan Nehru, Sankaralingam Arunachalam, Renganathan Arun, Kumpati Premkumar
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    ABSTRACT: A new series of pendant-type polymer-cobalt(III) complexes, [Co(LL)2(BPEI)Cl](2+), (where BPEI = branched polyethyleneimine, LL = dipyrido[3,2-a:2',3'-c](6,7,8,9-tetrahydro)phenazine (dpqc), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq) and imidazo[4,5-f]1,10-phenanthroline (ip)) each with three different degrees of coordination have been synthesized and characterized. Studies to know the mode and strength of interaction between these polymer-metal complexes and calf thymus DNA have been performed by UV-Visible absorption and emission techniques. Among these series, each polymer metal complex having higher binding strength with DNA has been selected to test against human cancer/normal cell lines. On the basis of these spectral studies, it is proposed that our polymer-metal complexes bind with DNA mainly through intercalation along with some electrostatic binding. The order of binding strength for the complexes with ligand, dpqc > dpq > ip. The analysis of the results suggests that polymer-cobalt(III) complexes with higher degree of coordination effectively binds with DNA due to the presence of large number of positively charged cobalt(III) chelates in the polymer chain which cooperatively act to increase the overall binding strength. These polymer-cobalt(III) complexes with hydrophobic ligands around the cobalt(III) metal centre favour the base stacking interactions via intercalation. All the complexes show very good anticancer activities and increasing of binding strength results in higher inhibition value. The polymer-cobalt(III) complex with dpqc ligand possess two fold increased anticancer activity when compared to complexes with other ligands against MCF-7 cells. Besides, the complexes were insensitive towards the growth of normal cells (HEK-293) at the IC50 concentration.
    Journal of biomolecular structure & dynamics 09/2013; · 4.99 Impact Factor
  • Karuppiah Nagaraj, Sankaralingam Arunachalam
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    ABSTRACT: The interaction of cis-[Co(phen)2(HA)2](ClO4)3, a cationic surfactant complex (phen=1,10- phenanthroline, HA= hexadecylamine), with calf thymus DNA has been studied by UV-Visible absorption, fluorescence spectroscopy, cyclic voltammetry, circular dichroism, and viscosity measurements. The spectroscopic studies together with cyclic voltammetry and viscosity experiments support that the surfactant-cobalt(III) complex binds to calf thymus DNA (CT DNA) by intercalation through the aliphatic chain present in the complex into the base pairs of DNA. The presence of phenanthroline ligand with larger π-frame work may also enhance intercalation. Besides the effect of binding of surfactant cobalt(III) complex to DNA in presence of β-cyclodextrin has also studied. In presence of β-cyclodextrin the binding occurs through surface and (or) groove binding. The complex was investigated as one of the potential selective anticancer prodrugs. The complex was tested also in vitro on human monolayer tumour cell lines: HepG2 (Human hepatocellular liver carcinoma).
    International journal of biological macromolecules 09/2013; · 2.37 Impact Factor
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    ABSTRACT: The comparative binding effect of single and double aliphatic chain containing surfactant-cobalt(III) complexes cis-[Co(bpy)2(DA)2](ClO4)3⋅2H2O (1), cis-[Co(bpy)2(DA)Cl](ClO4)2⋅2H2O (2), cis-[Co(phen)2(CA)2](ClO4)3⋅2H2O (3), and cis-[Co(phen)2(CA)Cl](ClO4)2⋅2H2O (4) with bovine serum albumin (BSA) under physiological condition was analyzed by steady state, time resolved fluorescence, synchronous, three-dimensional fluorescence, UV-Visible absorption and circular dichroism spectroscopic techniques. The results show that these complexes cause the fluorescence quenching of BSA through a static mechanism. The binding constants (Kb) and the number of binding sites were calculated and binding constant values are found in the range of 10(4)-10(5)M(-1). The results indicate that compared to single chain complex, double chain surfactant-cobalt(III) complex interacts strongly with BSA. Also the sign of thermodynamic parameters (ΔG°, ΔH°, and ΔS°) indicate that all the complexes interact with BSA through hydrophobic force. The binding distance (r) between complexes and BSA was calculated using Förster non-radiation energy transfer theory and found to be less than 7nm. The results of synchronous, three dimensional fluorescence and circular dichroism spectroscopic methods indicate that the double chain surfactant-cobalt(III) complexes changed the conformation of the protein considerably than the respective single chain surfactant-cobalt(III) complexes. Antimicrobial studies of the complexes showed good activities against pathogenic microorganisms.
    Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 05/2013; 113C:415-422. · 1.98 Impact Factor
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    ABSTRACT: Water soluble polymer-copper(II) complexes with various degrees of coordination in the polymer chain were synthesized and characterized by elemental analysis, IR, UV-visible and EPR spectra. The DNA/RNA binding behavior of these polymer-copper(II) complexes was examined by UV-visible absorption, emission and circular dichroism spectroscopic methods, and cyclic voltammetry techniques. The binding of the polymer-copper(II) complexes with DNA/RNA was mainly through intercalation but some amount of electrostatic interaction was also observed. This binding capacity increased with the degree of coordination of the complexes. The polymer-copper(II) complex having the highest degree of coordination was subjected to analysis of cytotoxic and antimicrobial properties. The cytotoxicity study indicated that the polymer-copper(II) complexes affected the viability of MCF-7 mammary carcinoma cells, and the cells responded to the treatment with mostly through apoptosis although a few cells succumbed to necrosis. The antimicrobial screening showed activity against some human pathogens.
    Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 02/2013; 109C:23-31. · 1.98 Impact Factor
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    ABSTRACT: The interaction of two water soluble branched polyethyleneimine-copper(II) complexes containing bipyridine/phenanthroline with bovine serum albumin (BSA) was studied by, UV-Visible absorption, fluorescence, lifetime measurements and circular dichroism spectroscopic techniques. The polymer-copper(II) complexes strongly quench the intrinsic fluorescence of BSA is the static quenching mechanism through hydrogen bonds and van der Waal's attraction. The distance r, between the BSA and the complexes seems to be less than 2nm indicating that the energy transfer between the donor and acceptor occurs with high probability. Synchronous fluorescence studies indicate the binding of polymer-copper(II) complexes with BSA mostly changes the polarity around tryptophan residues rather than tyrosine residues. The circular dichroism studies indicate that the binding has induced considerable amount of conformational changes in the protein. The complexes also show some antibacterial and antifungal properties.
    Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy 05/2012; 96:108-16. · 1.98 Impact Factor
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    ABSTRACT: The characteristics of the binding reaction of surfactant-cobalt(III) complex, cis-[Co(phen)₂(C₁₄H₂₉NH₂)]Cl₂·3H₂O (phen=1,10-phenanthroline, C₁₄H₂₉NH₂=tetradecylamine) with human serum albumin (HSA) were studied by fluorescence and UV-vis absorption spectroscopy. In addition, the effect of the surfactant-cobalt(III) complex on the conformation of HSA was analysed using synchronous fluorescence spectroscopy. The experimental results showed that surfactant-cobalt(III) complex caused the fluorescence quenching of HSA through a combination of static and dynamic quenching. The number of binding sites (n) and apparent binding constant (K(a)) of surfactant-cobalt(III) complex (above and below the critical micelle concentration (cmc) were determined at various temperatures. According to the thermodynamic parameters, it is likely that hydrophobic interactions are involved in the binding process. The cancer chemotherapeutic potential of surfactant-cobalt(III) complex on ME-180 cervical cancer cell was determined using MTT assay and specific staining techniques. The complex affected the viability of the cells significantly and the cells succumbed through an apoptosis process as seen in the nuclear morphology and cytoplasmic features. In addition, single-cell electrophoresis indicated DNA damage.
    Colloids and surfaces B: Biointerfaces 08/2011; 86(1):35-44. · 3.55 Impact Factor
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    ABSTRACT: The polymer-copper(II) complex samples, [Cu(phen)(l-Val) BPEI]Cl·H(2)O, with varying degrees of coordination in the polymer chain, were prepared and characterized by elemental analysis and spectroscopic methods. The binding of these complex samples with both DNA and RNA has been investigated. The experimental results indicate that the polyethyleneimine-copper(II) complex samples bind with DNA and RNA mostly through surface binding; but hydrogen bonding and van der Waals interactions are also present. Evaluation of cytotoxic activity of a sample of polymer-copper(II) complex with higher degree of coordination against different cancer cell lines proved that the complex exhibited cytotoxic specificity and significant cancer cell inhibition rate.
    European journal of medicinal chemistry 07/2011; 46(7):3013-21. · 3.27 Impact Factor
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    ABSTRACT: The cancer chemotherapeutic potential of surfactant-cobalt(III) complexes, cis-[Co(bpy)(2)(C(14)H(29)NH(2))Cl](ClO(4))(2)·3 H(2)O (1) and cis-[Co(phen)(2)(C(14)H(29)NH(2))Cl](ClO(4))(2)·3 H(2)O (2) (bpy = 2,2'-bipyridine, phen = 1,10-phenanthroline) on MCF-7 breast cancer cell was determined adopting MTT assay and specific staining techniques. The complexes affected the viability of the cells significantly and the cells succumbed to apoptosis as seen in the changes in the nuclear morphology and cytoplasmic features. Since the complex 2 appeared to be more potent, further assays were carried out on the complex 2. Single-cell electrophoresis indicated DNA damage. The translocation of phosphatidyl serine and loss of mitochondrial potential was revealed by annexin V-Cy3 staining and JC-1 staining respectively. Western blot analysis revealed up-regulation of pro-apoptotic p53 and down-regulation of anti-apoptotic Bcl-2 protein. Taken together, the surfactant-cobalt(III) complex 2 would be a potential candidate for further investigation for application as a chemotherapeutic for cancers in general and estrogen receptor-positive breast cancer in particular.
    Archiv der Pharmazie 05/2011; 344(7):422-30. · 1.54 Impact Factor
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    ABSTRACT: The cytotoxic activity of the polymer–copper(II) complex, [Cu(bpy)2(BPEI)]Cl2·4H2O (bpy=2,2′-bipyridine, BPEI=branched polyethyleneimine) on NCI-H460 human lung cancer cells was determined adopting MTT assay and specific staining techniques. Many of the cultured NCI-H460 cancer cells treated with this complex suffered loss of viability and death mostly through apoptosis and/or necrosis as evidenced by the changes in the nuclear morphology and cytoplasmic features. KeywordsPolymer–metal complex–Copper complex–Cytotoxicity–Apoptosis–Necrosis
    Medicinal Chemistry Research 01/2011; 20(6):726-731. · 1.61 Impact Factor
  • K. Sasikala, S. Arunachalam
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    ABSTRACT: The electron transfer kinetics of the reaction between the surfactant-cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2]3+, cis-α-[Co(trien)(C12H25NH2)2]3+(en:ethylenediamine, trien:triethylenetetramine, C12H25NH2 : dodecylamine) by iron(II) in aqueous solution was studied at 298, 303, 308 K by spectrophotometry method under pseudo-first-order conditions using an excess of the reductant in self-micelles formed by the oxidant, cobalt(III) complex molecules, themselves. The rate constant of the electron transfer reaction depends on the initial concentration of the surfactant cobalt(III) complexes. ΔS# also varies with initial concentration of the surfactant cobalt(III) complexes. By assuming outer-sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of the self-micelles formed by the surfactant cobalt(III) complexes in the reaction medium. The rate constant of each complex increases with initial concentration of one of the reactants surfactant-cobalt(III) complex, which shows that self micelles formed by surfactant-cobalt(III) complex itself has much influence on these reactions. The electron transfer reaction of the surfactant-cobalt(III) complexes was also carried out in a medium of various concentrations of β-cyclodextrin. β-cyclodextrin retarded the rate of the reaction.
    Journal of Dispersion Science and Technology 12/2010; 31(12):1618-1623. · 0.60 Impact Factor
  • K. Sasikala, S. Arunachalam
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    ABSTRACT: AbstractThe surfactant complex ion cis-[Co(tmd)2(C12H25NH2)2]3+ (tmd=1,3-propanediamine, C12H25NH2=dodecylamine) has been synthesized and characterized by elemental analysis and spectral data. In addition we have determined the critical micelle concentration of the surfactant–cobalt(III) complex and studied the kinetics and mechanism of the complex with ferrocyanide anion. The reaction is found to be second order, and the second-order rate constant increases with increasing initial concentration of the surfactant–cobalt(III) complex due to the presence of self-micelles formed by the complex itself. The thermodynamic parameters were determined. The results have been analyzed. Graphical abstract KeywordsSurfactant–cobalt(III) complex-Self-micelles-Critical micelle concentration-Electron transfer
    Monatshefte fuer Chemie/Chemical Monthly 01/2010; 141(3):309-316. · 1.63 Impact Factor
  • K. Sasikala, S. Arunachalam
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    ABSTRACT: The kinetics and mechanism of reduction of the surfactant-cobalt(III) complex ions, cis-[Co(bpy)2(C12H25NH2)2]3+ and cis-[Co(phen)2(C12H25NH2)2]3+ (bpy = bipyridyl, phen = 1,10-phenan-throline, C12H25NH2 = dodecylamine) by Fe(CN6)4− in self-micelles were studied at different temperatures. Experimentally the reaction was found to be second order and the electron transfer postulated as outersphere. The rate constant for the electron transfer reaction for both the complexes was found to increase with increase in the initial concentration of the surfactant-cobalt(III) complex. This peculiar behaviour of dependence of second-order rate constant on the initial concentration of one of the reactants has been attributed to the presence of various concentration of micelles under different initial concentration of the surfactantcobalt(III) complexes in the reaction medium. The effect of inclusion of the long aliphatic chain of the surfactant complex ions into β-cyclodextrin on these reactions has also been studied.
    Colloid Journal 01/2010; 72(4):530-537. · 0.63 Impact Factor
  • Jagadeesan Lakshmipraba, Sankaralingam Arunachalam
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    ABSTRACT: The binding interactions between tRNA and polyethyleneimine-anchored copper(II) complexes with 1,10-phenanthroline and 2,2′-bipyridine ligands and varying degrees of coordination have been studied using physico-chemical techniques. In both sets of polyethyleneimine-anchored complexes, the complexes with higher degree of coordination bind more strongly to tRNA than those with lower degree of coordination. Binding to tRNA appears to be mainly electrostatic in nature.
    Transition Metal Chemistry 01/2010; 35(4):477-482. · 1.18 Impact Factor
  • Kathan Sasikala, Sankaralingam Arunachalam
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    ABSTRACT: The kinetics and mechanism of iron(II) reduction of the surfactant–cobalt(III) complex ions, cis-[Co(bpy)2(C12H25NH2)2]3+, cis-[Co(phen)2(C12H25NH2)2]3+ (bpy=2,2′ bipyridine, phen=1,10 phenanthroline, C12H25NH2=dodecylamine) in self-micelles were studied at different temperatures. Experimentally the reaction was found to be second order and the electron transfer postulated as outer-sphere. The second order rate constant for this electron transfer reaction for both the complex ions was found to increase with increase in the initial concentration of these surfactant–cobalt(III) complex ions. The effect of inclusion of the long aliphatic chain of the surfactant complex ions into β-cyclodextrin on these reactions has also been studied.
    Colloids and Surfaces A-physicochemical and Engineering Aspects - COLLOID SURFACE A. 01/2009; 335(1):98-102.