Synthesis, characterization, molecular modeling, binding energies of ß-cyclodextrin-inclusion complexes of quercetin: Modification of photo physical behavior upon ß-CD complexation.

We prepared a naturally occurring flavanoid namely quercetin from tea leaves and analyzed by Absorption, Emission, FT-IR, 1H, 13C nmr spectra and ESI-MS analysis. The inclusion behavior of quercetin in cyclodextrins like α-, ß-, γ-, per-6-ABCD and mono-6-ABCD cavities were supported such as UV-vis., Emission, FT-IR and ICD spectra and energy minimization studies. From the absorption and emission results, the type of complexes formed were found to depend on stoichiometry of Host:Guest. FT-IR data of CD complexes of quercetin supported inclusion complex formation of the substrate with α-, ß- and γ-CDs. The inclusion of host-guest complexation of quercetin with α-, ß-, γ-CDs, per-6-ABCD and mono-6-ABCDs provides very valuable information about the CD:quercetin complexes, the study also shows that ß-CD complexation improves water solubility, chemical stability and bioavailability of quercetin. Besides, phase solubility studies also supported the formation of 1:1 drug-CD soluble complexes. All these spectral results provide insight into the binding behavior of substrate into CD cavity in the order per-6-ABCD > Mono-6-ABCD > γ-CD > ß-CD > α-CD. The proposed model also finds strong support from the fact with excess CD this exciton coupling disappears indicates the formation of only 1:1 complex.

Effect of hydrophobicity and size of the ligands on the intercalative binding interactions of some metallo-surfactants containing π-conjugated systems with yeast tRNA.

The intercalative yeast t-RNA binding behavior of some metallo-surfactant complexes, Co(ip)2(TA)2](ClO4)3 (1) and [Co(dpq)2(TA)2](ClO4)3 (2) where TA = Tetradecylamine (Myristylamine), ip = imidazo[4,5-f][1,10]phenanthroline and dpq = dipyrido[3,2-d:2'-3'-f]quinoxaline containing π-conjugated systems (both below and above critical micelle concentration) have been investigated by means of absorption spectral titration, competitive binding, circular dichroism, cyclic voltammetry, and viscometry measurements. Absorption spectral titration results implicate yeast tRNA has significant effects on the binding behaviors of two surfactant complexes via intercalative mode showed a significant absorption band of hypochromicity with red shift. The intrinsic binding constant values below and above CMC were determined as Kb = 6.12 × 105 M-1, 2.31 × 106 M-1, for complex (1) and 7.23 × 105 M-1, 3.57 × 106 M-1, for complex (2). In both sets of complexes (1) and (2), the complexes bind more strongly to yeast tRNA in the above critical micelle concentration can be hydrophobic and confirm intercalation. Competitive displacement studies confirmed that complexes bind to yeast tRNA via intercalative mode. Cyclic voltammetry studies suggest the increasing amounts of yeast tRNA, the cathodic potential Epc for the two complexes shows a positive shift in peak potential indicated the process of binding via intercalation. These observations were further validated by CD, and hydrodynamic measurements. All these studies suggesting that a surfactant complex binds to yeast tRNA appear to be mainly intercalative because of hydrophobicity due to extending aromaticity of the π system of the ligand and planarity of the complex has a significant effect on tRNA binding affinity increasing in the order of complexes containing ligands ip < dpq.Communicated by Ramaswamy H. Sarma.

Metallo-Surfactant assisted silver nanoparticles: A new approach for the colorimetric detection of amino acids.

In this study, we report a new class of metallo-surfactant assisted silver nanoparticle produced by reduction process via AgNO3 solution and extract of Turnera Subulata (TS) in aqueous which act as reducing and metallo-surfactant [Co(ip)2(C12H25NH2)2](ClO4)3 (ip = imidazo[4,5-f][1,10]phenanthroline) act as stabilizing agent. In this study the silver nanoparticles produced using Turnera Subulata extract has showed yellowish brown color formation and an absorption peak at 421 nm signaling the biosynthesis of silver nanoparticles. The presence of functional groups in the plant extracts were identified by FTIR analysis. In addition, the effects of ratio, changing the concentration of the metallo surfactant, TS plant leave extract, metal precursors, and pH of the medium have been investigated on the scale of the Ag nanoparticles. Spherical shaped, crystalline in nature and ∼50 nm sized particles were recorded using TEM and DLS analysis. Furthermore, the mechanistic insights into cysteine and dopa detection by silver nanoparticles were investigated using HR-TEM analysis. This induces aggregation in stable silver nanoparticles owing to selective and strong interaction of -SH group of cysteine with silver nanoparticle surface. The biogenic Ag NPs are found to be highly sensitive to amino acids of dopa and cysteine with the diagnosis maximum for both amino acids as low as 0.9 µM (dopa) and 1 µM (cysteine) under optimized conditions.

'On and Off' intercalative binding behaviour of double chain surfactant cobalt(III) complex containing 2, 2'-bipyridyl ligand in ß-Cyclodextrin: A detail approach on Host-guest inclusion of surfactant cobalt(III) complex and CT-DNA binding in micro-heterogeneous medium.

The binding interaction of surfactant cobalt(III) complex, cis-[Co(bpy)2(HA)2](ClO4)3, in which bpy is 2,2-bipyridine and HA is hexadecylamine or cetylamnine with DNA was through intercalative mode via the long aliphatic chains present in the ligands. The binding was investigated by various techniques, electronic absorption, fluorescence spectroscopy, circular dichroism (CD), cyclic voltametry (CV) and viscosimetry measurements. The spectroscopic studies together with cyclic voltammetry and viscosity experiments support that the surfactant cobalt(III) complex binds to calf thymus DNA by intercalation through the aliphatic chain present in the complex into the base pairs of DNA. The presence of bipyridine ligand with larger π-frame work may also enhance intercalation. UV-vis., spectrum showed 4 nm bathochromic shift of the absorption band at 352 nm along with significant hypochromicity for the absorption band of the complex. The intrinsic binding constants(at below and above CMC are Kb = 2.41 × 105M-1, Kb = 3.12 × 106M-1 respectively) is more in keeping with intercalators and suggests this binding mode. The viscosity measurements showed that the surfactant cobalt(III) complex-DNA interaction can be hydrophobic and confirm intercalation. Moreover, the complex induced detectable changes in the CD spectrum of CT-DNA. Competitive binding study with ethidium bromide (EB) shows that the surfactant 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. Also, CV results confirm this mode because, with increasing the CT-DNA concentration, shift to higher potential was observed. Besides the effect of binding of surfactant cobalt(III) complex to DNA in presence of ß-cyclodextrin has also studied. This binding of the surfactant cobalt(III) complex in presence of ß-cyclodextrin medium has been prevented (at below and above CMC are Kb = 5.45 × 104M-1, Kb = 6.92 × 105M-1 respectively) due to the incorporation of the aliphatic chains into the cavity of ß-cyclodextrin. In presence of ß-cyclodextrin the binding occur through surface and (or) groove binding can be attributed to the inclusion of the long aliphatic chain that is present in one of the ligands into cyclodextrin.

States of Aggregation and Phase Transformation Behavior of Metallosurfactant Complexes by Hexacyanoferrate(II): Thermodynamic and Kinetic Investigation of ETR in Ionic Liquids and Liposome Vesicles.

Electronic absorption spectroscopy was used to study the ETR of surfactant-cobalt(III) complexes containing imidazo[4,5-f][1,10]phenanthroline, dipyrido[3,2-d:2'-3'-f]quinoxaline and dipyrido[3,2-a:2',4'-c](6,7,8,9-tetrahydro)phenazine ligands by using ferrocyanide ions in unilamellar vesicles of dipalmitoylphosphotidylcholine (DPPC) and 1-butyl-3-methylimidazolium bromide ((BMIM)Br), at different temperatures under pseudo-first-order conditions using an excess of the reductant. The reactions were found to be second-order and the electron transfer is postulated as occurring in the outer sphere. The rate constant for the electron transfer reactions was found to increase with increasing concentrations of ionic liquids. Besides these, the effects of surfactant complex ions on liposome vesicles in these same reactions have also been studied on the basis of hydrophobicity. We observed that, below the phase transition temperature, there is an increasing amount of surfactant-cobalt(III) complexes expelled from the interior of the vesicle membrane through hydrophobic effects, while above the phase transition temperature, the surfactant-cobalt(III) complexes are expelled from the interior to the exterior surface of the vesicle. Kinetic data and activation parameters are interpreted in respect of an outer-sphere electron transfer mechanism. By assuming the existence of an outer-sphere mechanism, the results have been clarified based on the presence of hydrophobicity, and the size of the ligand increases from an ip to dpqc ligand and the reactants become oppositely charged. In all these media, the ΔS# values are recognized as negative in their direction in all the concentrations of complexes employed, indicative of a more ordered structure of the transition state. This is compatible with a model in which these complexes and [Fe(CN)6]4- ions bind to the DPPC in the transition state. Thus, the results have been interpreted based on the self-aggregation, hydrophobicity, charge densities of the co-ligand and the reactants with opposite charges.

Modification of Electrospun CeO2 Nanofibers with CuCrO2 Particles Applied to Hydrogen Harvest from Steam Reforming of Methanol.

Hydrogen is the alternative renewable energy source for addressing the energy crisis, global warming, and climate change. Hydrogen is mostly obtained in the industrial process by steam reforming of natural gas. In the present work, CuCrO2 particles were attached to the surfaces of electrospun CeO2 nanofibers to form CeO2-CuCrO2 nanofibers. However, the CuCrO2 particles did not readily adhere to the surfaces of the CeO2 nanofibers, so a trace amount of SiO2 was added to the surfaces to make them hydrophilic. After the SiO2 modification, the CeO2 nanofibers were immersed in Cu-Cr-O precursor and annealed in a vacuum atmosphere to form CeO2-CuCrO2 nanofibers. The CuCrO2, CeO2, and CeO2-CuCrO2 nanofibers were examined by X-ray diffraction analysis, transmission electron microscopy, field emission scanning electron microscopy, scanning transmission electron microscope, thermogravimetric analysis, and Brunauer-Emmett-Teller studies (BET). The BET surface area of the CeO2-CuCrO2 nanofibers was 15.06 m2/g. The CeO2-CuCrO2 nanofibers exhibited hydrogen generation rates of up to 1335.16 mL min-1 g-cat-1 at 773 K. Furthermore, the CeO2-CuCrO2 nanofibers produced more hydrogen at lower temperatures. The hydrogen generation performance of these CeO2-CuCrO2 nanofibers could be of great importance in industry and have an economic impact.

Fabrication of CuYO2 Nanofibers by Electrospinning and Applied to Hydrogen Harvest.

Hydrogen can be employed as an alternative renewable energy source in response to climate change, global warming, and the energy problem. Methanol gas steam reforming (SRM) is the major method used in industry to produce hydrogen. In the SRM process, the catalyst nature offers benefits such as low cost, simplicity, and quickness. In this work, delafossite copper yttrium oxide (CuYO2) nanofibers were successfully prepared by electrospinning. The prepared CuYO2 nanofibers have different physical and chemical properties including thermoelectric behavior. The electrospinning method was used to produce as-spun fibers and annealed in an air atmosphere to form Cu2Y2O5 fibers; then, Cu2Y2O5 fibers were annealed in a nitrogen atmosphere to form CuYO2 nanofibers. X-ray diffraction studies and thermogravimetric and transmission electron microscope analysis confirmed the formation of CuYO2 nanofibers. The CuYO2 nanofibers were applied to methanol steam reforming for hydrogen production to confirm their catalytic ability. The CuYO2 nanofibers exhibited high catalytic activity and the best hydrogen production rate of 1967.89 mL min-1 g-cat-1 at 500 °C. The highly specific surface area of CuYO2 nanofibers used in steam reforming reactions could have significant economic and industrial implications. The performance of these CuYO2 nanofibers in hydrogen generation could be very important in industries with a global economic impact. Furthermore, the H2 production performance increases at higher reaction temperatures.

Biophysical insights into the intercalative interaction of surfactant cobalt(III) complexes of certain diimine ligands bound to yeast tRNA: Effects of hydrophobicity.

The interaction of two surfactant cobalt(III) complexes, cis-[Co(ip)2(DA)2](ClO4)3 1 and cis-[Co(dpq)2(DA)2](ClO4)3 2 where ip=imidazo[4,5-f][1,10]phenanthroline and dpq=dipyrido[3,2-d:2'-3'-f]quinoxaline with yeast tRNA have been explored by using electronic absorption, competitive binding, electrochemical studies and viscosity measurements. The results suggest that these complexes can bind to tRNA by intercalation. The presence of hydrophobic diimine ligand and the long aliphatic double chains of these complexes facilitate its intercalative interaction with the hydrophobic interior of the tRNA. The extent of tRNA binding of complex 2 has greater affinity than that of complex containing imidazo[4,5-f][1,10]phenanthroline ligands.

Electron-transfer reactions of cobalt(III) complexes. 1. The kinetic investigation of the reduction of various surfactant cobalt(III) complexes by iron(II) in surface active ionic liquids.

The kinetics of outer sphere electron transfer reaction of surfactant cobalt(III) complex ions, cis-[Co(en)2(C12H25NH2)2](3+) (1), cis-[Co(dp)2(C12H25NH2)2](3+) (2), cis-[Co(trien)(C12H25NH2)2](3+) (3), cis-[Co(bpy)2(C12H25NH2)2](3+) (4) and cis-[Co(phen)2(C12H25NH2)2](3+) (5) (en: ethylenediamine, dp: diaminopropane, trien : triethylenetetramine, bpy: 2,2'-bipyridyl, phen: 1,10-phenanthroline and C12H25NH2 : dodecylamine) have been interrogated by Fe(2+) ion in ionic liquid (1-butyl-3-methylimidazoliumbromide) medium at different temperatures (298, 303, 308, 313, 318 and 323K) by the spectrophotometry method under pseudo first order conditions using an excess of the reductant. Experimentally the reactions were found to be of second order and the electron transfer as outer sphere. The second order rate constant for the electron transfer reaction in ionic liquids was found to increase with increase in the concentration of all these surfactant cobalt(III) complexes. Among these complexes (from en to phen ligand), complex containing the phenanthroline ligand rate is higher compared to other complexes. By assuming the outer sphere mechanism, the results have been explained based on the presence of aggregated structures containing cobalt(III) complexes at the surface of ionic liquids formed by the surfactant cobalt(III) complexes in the reaction medium. The activation parameters (enthalpy of activation ΔH(‡) and entropy of activation ΔS(‡)) of the reaction have been calculated which substantiate the kinetics of the reaction.

Synthesis, CMC determination, and intercalative binding interaction with nucleic acid of a surfactant-copper(II) complex with modified phenanthroline ligand (dpq).

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 (ΔG°(m), ΔH°(m) and ΔS°(m)). 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.

Influence of self-assembly on intercalative DNA binding interaction of double-chain surfactant Co(III) complexes containing imidazo[4,5-f][1,10]phenanthroline and dipyrido[3,2-d:2'-3'-f]quinoxaline ligands: experimental and theoretical study.

A new class of surfactant Co(III) complexes, cis-[Co(ip)2(C12H25NH2)2](ClO4)3 (1) and cis-[Co(dpq)2(C12H25NH2)2](ClO4)3 (2) (ip = imidazo[4,5-f][1,10]phenanthroline, dpq = dipyrido[3,2-d:2'-3'-f]quinoxaline), have been synthesized and characterized by various spectroscopic and physico-chemical techniques. The critical micelle concentration (CMC) values of these complexes in aqueous solution were obtained from conductance measurements. The 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 trend in DNA-binding affinities and the spectral properties of a series of complexes, cis-[Co(ip)2(C12H25NH2)2](ClO4)3 (1) and cis-[Co(dpq)2(C12H25NH2)2](ClO4)3 (2), have been experimentally and theoretically investigated. The experimental results indicate that the size and shape of the intercalated ligand and hydrophobicity of the complexes have a marked effect on the binding affinity of the complexes to CT DNA in intercalation mode, and the order of their intrinsic DNA-binding constants Kb is Kb(1) < Kb(2). In addition, the influence of the extended aromatic ring and optical properties of the complexes can be reasonably explained by applying the DFT calculations. The energy gap between HOMO and LUMO indicates that these complexes are prone to interact with CT DNA. Further, molecular docking calculations have also been performed to understand the nature of binding of the complexes and the result confirms that the complexes interact with CT DNA through the alkyl chain. The cytotoxic activity of these complexes on human liver carcinoma cancer cells were determined adopting MTT assay and specific staining techniques, which revealed that the viability of the cells thus treated was significantly decreased and the cells succumbed to apoptosis as seen in the changes in the nuclear morphology and cytoplasmic features.

Synthesis, micellization behaviour, DNA/RNA binding and biological studies of a surfactant cobalt(III) complex with dipyrido[3,2-a:2',4'-c](6,7,8,9-tetrahydro)phenazine.

A new surfactant cobalt(III) complex, cis-[Co(dpqc)2(DA)2](ClO4)3, where dpqc = dipyrido[3,2-a:2',4'-c](6,7,8,9-tetrahydro)phenazine and DA = dodecylamine, has been synthesized and characterized by elemental analysis, UV-Visible, IR and NMR spectra. The critical micelle concentration (CMC) value of this surfactant cobalt(III) complex in aqueous solution was obtained from conductance measurements. The conductivity data (at 303, 308, 313, 318 and 323 K) were used for the evaluation of the temperature-dependent CMC and the thermodynamics of micellization (ΔG(0) m, ΔH(0) m and ΔS(0) m). Absorption, fluorescence, cyclic voltammetry, circular dichroism and viscosity experiments have been carried out to study the interaction of the surfactant cobalt(III) complex with DNA and RNA. The results suggest that the complex can bind to nucleic acids by intercalation via both the dpqc ligand and the long aliphatic chain of the complex into the base pairs of DNA/RNA. In vitro cytotoxicity experiments show that the surfactant cobalt(III) complex exhibits cytotoxic activity against the HepG2 (human hepatocellular liver carcinoma) tumor cell lines and found to be active.

Synthesis, micellization behavior, antimicrobial and intercalative DNA binding of some novel surfactant copper(II) complexes containing modified phenanthroline ligands.

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.

Synthesis, CMC Determination, Antimicrobial Activity and Nucleic Acid Binding of A Surfactant Copper(II) Complex Containing Phenanthroline and Alanine Schiff-Base.

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).

Binding of a double-chain surfactant-cobalt(III) complex to CT DNA: effect of ß-cyclodextrin in the medium.

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-vis 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 ß-cyclodextrin has also studied. In presence of ß-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 tumor cell lines: HepG2 (human hepatocellular liver carcinoma).