Synthesis,crystal structure,DNA binding properties and antioxidant activities of transition metal complexes with 3-carbaldehyde-chromone semicarbazone

3-Carbaldehyde-chromone semicarbazone (L) and its Cu(II), Zn(II), Ni(II) complexes were synthesized and characterized on the basis of crystal structure and other structural characterization methods. The metal ions and Schiff base ligand can form mononuclear five-coordination complexes with 1:1 metal-to-ligand stoichiometry at the metal ions as centres. The transition metal complexes may be used as potential anticancer drugs, because they bind to calf thymus DNA via an intercalation binding mode with the binding constants at the order of magnitude 10⁵–10⁶ M^? 1, and the metal complexes present stronger DNA binding affinities than the free ligand alone. In addition, the antioxidant activities of the ligand and its metal complexes were investigated through scavenging effects for superoxide anion and hydroxyl radical in vitro, indicating that the compounds show stronger antioxidant activities than some standard antioxidants, such as mannitol and vitamin C.     

Stepwise Formation of Some Bivalent Metal Chelates with Sodium Alizarin Sulphonate

The stepwise protonation constants of the ligand and the stability constants of Alizarin Red S with some bivalent metal ions, Pb²⁺, Cu²⁺, Zn²⁺, and Hg²⁺ have been determined at 30° and at various ionic strengths viz. 0.02, 0.05, 0.15 and 0.20, maintained by sodium perchlorate solution. The formation of the chelate is evident from the shift between the (i) ligand and (ii) ligand and metal titration curves. From the values of the stepwise protonation constants and metal ligand stability constants at various ionic strengths, thermodynamic formation constants were evaluated by extrapolation to zero ionic strength. The order of stability constants was found to be: Cu > Pb > Zn > Hg     

Synthesis,metal ion complexation and antibacterial activities of some thiapodands with lipophilic amide and ester end groups

A series of acyclic analogues of thiacrown ethers (podands) 7–12 with lipophilic amide and ester end groups were synthesized in high yield and in a simple way. Their transition metal ions complexation was studied using a conductometric method in acetonitrile at 25°C. Podands 7 and 11 showed a continuous decrease in the molar conductances in their complexation with Ag⁺, Cu²⁺, Cd²⁺, Hg²⁺, Zn²⁺ and Pb²⁺ which begins to level off at a mole ratio of 1:1 podand to metal indicating the formation of a stable 1:1 complexes. On the other hand, podand 9 also showed the formation of 1:1 complexes with above metal cations except with Hg²⁺ ion, which formed a 1:2 podand-to-metal ratio complex. An influence of end groups on metal ion selectivity is evident. Podands having ethoxy end groups (podands 8, 10 and 12 exhibit pronounced metal ion selectivity over podands having amino end groups (podands 7, 9 and 11). Compounds 10 and 12 with dithiaethylene units and ethoxy end groups provide the best selectivity for Hg²⁺ and Ag⁺ ions. These results suggest that podands 10 and 12 could be useful for the selective removal of Hg²⁺ and Ag⁺ ions from industrial waste that may contain a variety of toxic heavy and transition metal ions. The in vitro antibacterial activity of the investigated compounds was tested against several microorganisms such as Bacillus subtilis (ATCC 6633), Micrococcus luteus (ATCC 10240), Staphylococcus aureus (ATCC 43300), Escherichia coli (ATCC 25922) and Enterobacter aerogenes (ATCC 13048). The antibacterial activity of podand 10 is significant for M. luteus and B. subtilis compared with other podands under investigation.     

Heavy Metal Complexation of Thiol-Containing Peptides from Soy Glycinin Hydrolysates

Many thiol-containing molecules show heavy metal complexation ability and are used as antidotes. In this study, the potential function associated with thiol-containing peptides (TCPs) from soy protein hydrolysates as natural detoxicants for heavy metals is reported. TCPs enriched by Thiopropyl-Sepharose 6B covalent chromatography had different molecular weight distributions as well as different numbers of proton dissociable groups, depending on the proteases and degree of hydrolysis. The major contribution of sulfhydryl groups was confirmed by the largest pH decrease between 8.0 and 8.5 of the pH titration curves. The complexation of TCPs with heavy metalswas evaluated by stability constants (β_n) of TCP-metal complexes whose stoichiometry was found to be 1:1 (ML) and 1:2 (ML₂). TCPs from degree of hydrolysis of 25% hydrolysates gave high affinities towards Hg²⁺, Cd²⁺, and Pb²⁺ (giving similar or even bigger lgβ values than that of glutathione). A significantly positive correlation was found between the logarithm of stability constants for ML₂ (lgβ₂) and the sulfhydryl group content. Molecular weight distribution of TCPs affected the complexation with Pb²⁺ notably more than Hg²⁺ and Cd²⁺. These results suggest that soy TCPs have the potential to be used in the formulation of functional foods to counteract heavy metal accumulation in humans.     

Interaction of poly(maleic anhydride‐alt‐acrylic acid) with transition metal cations,Ni2+, Cu2+, and Cd2+: A study by UV–Vis spectroscopy and viscosimetry

Interactions between poly(maleic anhydride‐alt‐acrylic acid), [poly(MA‐alt‐AA)] and Cu²⁺, Ni²⁺, and Cd²⁺ ions were studied by UV–vis spectroscopy and viscosimetry. Effects of nature and the concentrations of the metal ions on the complex formation were investigated and the formation constants of each complex were determined by the mole‐ratio method. UV–vis studies showed that the complex formation tendency increased in the followed order: Cd(II) < Ni(II) < Cu(II). This order was confirmed by the Irving–William series and the Pearson's classification. The influence of metal ions on the reduced viscosity of poly(MA‐alt‐AA) increased in the following order: Cu(II) < Ni(II) < Cd(II), and this result was explained by the concentration effect. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 2698–2705, 2004     

Structural,morphological and magnetic characterization of metal-chitosan/poly (vinyl amine) complexes

Cu²⁺ and Ni²⁺ complexes of chitosan/poly(vinyl amine) (CS/PVAm) composites were prepared. The metal-CS/PVAm complexes were characterized by FT-IR spectroscopy, SEM-EDX, X-ray diffraction (XRD), and magnetic moment determination. FT-IR spectra of the metal-CS/PVAm complexes showed the characteristic bands of anhidroglucose unit were affected by the metal complexation, and new bands assigned to Me–N and Me-O bonds were observed. SEM images of the surface of metal-composite complexes show the influence of metal ion on the morphology of the complexes, the strong binding of Cu²⁺ and Ni²⁺, involving most of the amino groups, leading to a dense surface structure. The chemical composition on the surface of metal-CS/PVAm complexes was determined from EDX measurements. XRD provided information about the amorphous or crystalline nature of the composite and metal-composite complexes. Using magnetic susceptibility method, the oxidation degree of metal ions from the polymer phase, the homogeneous distribution of the ligand groups from the volume of the CS/PVAm beads, and the existence of the antiferromagnetic interactions between the metal ions were determined.     

Synthesis,complexation and biological effects studies of new thiacrown ethers derived quinoline: part I

A series of new thiacrown ethers derived quinoline 7–9 were synthesized in good yield and in a simple way. Their transition metal ions complexation was studied using a conductometric method in acetonitrile at 25°C. Crowns 7 and 8 showed a continuous decrease in the molar conductances in their complexation with Ag⁺, Cu²⁺, Hg²⁺ and Zn²⁺ which begins to level off at a molar ratio of 1:1 crown to metal, indicating the formation of 1 stable 1:1 complex. On the other hand, crown 9 showed the formation of 1:1 complexes only with Ag⁺, Cu²⁺, Hg²⁺. The in vitro, a preliminary antimicrobial, antioxidant and cytotoxic effects on breast tumor cells were also reported. Five bacterial test strains were included in the present study. Antioxidant activity was measured in terms of the radical scavenging ability and decolorization of 1,1-Diphenyl-2-picrylhydrazyl (DPPH) radicals. Cytotoxic effect of thiacrown was evaluated using MDA MB-231 cell line (human breast adenocarcinoma, ATCC HTB-26).     

New antimicrobial polyurea: Synthesis,characterization, and antibacterial activities of polyurea‐containing thiosemicarbazide–metal complexes

A novel class of polymer–metal complexes was prepared by the condensation of a polymeric ligand with transition‐metal ions. The polymeric ligand was prepared by the addition polymerization of thiosemicarbazides with toluene 2,4‐diisocyanate in a 1 : 1 molar ratio. The polymeric ligand and its polymer–metal complexes were characterized by elemental analysis, thermogravimetric analysis, Fourier transform infrared spectroscopy, and ¹³C‐NMR and ¹H‐NMR spectroscopy. The geometries of the central metal ions were determined by electronic spectra (UV–visible) and magnetic moment measurement. The antibacterial activities of all of the synthesized polymers were investigated against Bacillus subtilis and Staphylococcus aureus (Gram positive) and Escherichia coli and Salmonella typhi (Gram negative). These compounds showed excellent antibacterial activities against these bacteria with the spread plate method on agar plates, and the number of viable bacteria were counted after 24 h of incubation period at 37°C. The antibacterial activity results revealed that the Cu(II) chelated polyurea showed a higher antibacterial activity than the other metal‐chelated polyureas. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Effect of phase modifiers TBP and iso-decanol on the extraction and complexation of Eu3+ with CMPO

The effect of tri-n-butyl phosphate (TBP) and iso-decanol as phase modifiers on the complexation of Eu³⁺ with octyl-phenyl N,N-diisobutyl carbamoyl methyl phosphine oxide (CMPO) was studied. On an increase of iso-decanol the extraction efficiency of Eu³⁺ decreases. The metal–ligand stoichiometry was found to be 1:3. The Eu complex of CMPO–TBP was more symmetric compared to CMPO–iso-decanol. The Eu³⁺ complex exhibited D_3h and C_3h symmetry for 30% and 5% iso-decanol, while that for TBP was C_6v. The radiative, non-radiative life time, electric and magnetic dipole transition probabilities, branching ratio, quantum efficiency etc. were evaluated. The covalency between Eu³⁺ and CMPO is as follows: CMPO–TBP < CMPO-5% iso-decanol < CMPO-30% iso-decanol.     

Removal of Heavy Metal Ions from Water by Cross-Linked Potato Di-Starch Phosphate Polymer

Potato di-starch phosphate polymer was synthesized by cross-linking potato starch with phosphorus oxy-chloride in basic medium and was then dispersed (0.2-1%) in aqueous solutions of divalent heavy metal ions (Cu²⁺, Ni²⁺, Zn²⁺, and Pb²⁺), to investigate their removal efficiency by the starch and was found to increase with increase in the polymeric starch content and increase in the heavy metal ion concentration. The removal order was found to be Pb²⁺ (78.1%) > Cu²⁺ (58.5%) > Zn²⁺ (20.5%) > Ni²⁺ (17.3%) against the constant polymeric starch content. UV-Visible, Fluorescence, FT-IR, SEM, and CHN techniques were used for characterization of different complexes formed.     

Equilibrium studies of ternary systems containing some selected transition metal ions, triazoles and aromatic carboxylic acids

Solution equilibria of the binary and ternary complex systems of the divalent transition metal ions Cu²⁺, Ni²⁺, Zn²⁺, and Co²⁺ with 1,2,4-triazole (TRZ), 3-mercapto-1,2,4-triazole (TRZSH), and 3-amino-1,2,4-triazole (TRZAM) and aromatic carboxylic acids (phthalic, anthranilic, salicylic, and 5-sulfosalicylic acid) have been studied pH-metrically at (25.0±0.1) °C, and a constant ionic strength I=1×10^?1 mol L^?1 NaNO₃ in an aqueous medium. The potentiometric titration curves show that binary and ternary complexes of these ligands are formed in solution. The stability constants of the different binary and ternary complexes formed were calculated on the basis of computer analysis of the titration data. The relative stability of the different ternary complex species is expressed in terms of Δ log K values, log X and R. S.% parameters. The effect of temperature of the medium on both the proton-ligand equilibria for TRZAM and phthalic acid and their metal-ligand equilibria with Cu²⁺, Ni²⁺, and Co²⁺ has been studied along with the corresponding thermodynamic parameters. The complexation behavior of ternary complexes is ascertained using conductivity measurements. In addition, the formation of ternary complexes in solution has been confirmed by using UV-visible spectrophotometry.     

Physicochemical study of the complexation of poly(acrylic acid) with Cu2+ ions in water

The complexation of poly(acrylic acid) (PAA) with Cu²⁺ ions in a dilute aqueous solution has been investigated as a function of the mixing molar ratio of the two species and the neutralization degree (i) of PAA by means of turbidimetry, viscometry, potentiometry, and ultraviolet–visible (UV–vis) spectrophotometry. Turbidimetry reveals that, for i > 0.1, phase separation takes place when the mixing ratio approaches the critical value of two carboxylate ions per Cu²⁺ ion, which is indicative of the formation of a 2 : 1 polymer/metal complex. This complex is very compact, as evidenced by the very low reduced viscosity values obtained just before phase separation. The variation of the fraction of complexed carboxylate anions and complexed Cu²⁺ ions can be followed as a function of the mixing ratio and i from the analysis of the potentiometric results for i < 0.5. Finally, the combination of the potentiometric and UV–vis spectrophotometric results supports the idea that both mononuclear and binuclear PAA/Cu²⁺ complexes are formed in an aqueous solution, depending on the mixing ratio and i. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

HEAVY METAL EXTRACTION WITH THIOCARBAMIC-O-ALKYLESTERS

ABSTRACT

Two types of thiocarbamic-O-alkylesters, four bidentate ligands HL and one bis-bidentate ligand H₂L, were used as extractants for heavy metal ions from aqueous solutions. Silver(I) was extracted as neutral complexes in a yield > 99 %. The underlying stoichiometry and the extraction constants are discussed. The extraction of silver&I) by the bis-bidentate ligand is significantly more effective than the extraction by the analogous bidentate compound. In a dioxane/water mixture neutral, cationic and anionic silver complexes were found by means of pAg and pH potentiometric titrations. The extraction behavior is discussed with regard to the calculated stability constants.     

Extraction of metal ions with non-fluorous bipyridine derivatives as chelating ligands in supercritical carbon dioxide

Three new non-fluorous bipyridine derivatives, bis(2-(2-butoxyethoxy)ethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 1), bis(2-(2-ethoxyethoxy)ethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 2), and bis(2-butoxyethyl)-2,2′-bipyridine-4,4′-dicarboxylate (ligand 3), were synthesized as chelating ligands to remove metal ions from solid matrix into supercritical CO₂ (scCO₂). These produced compounds 1-3 showed considerable solubilities in scCO₂ (8.0 g/l, 4.8 g/l, 7.8 g/l for ligands 1-3 at 313 K, respectively) and the tested solubility data were then calculated and correlated with semiempirical model at different pressures and temperatures, which showed satisfactory agreement with each other and the average absolute relative deviation were in the range of 0.1-28.3%. The effects of pressure, temperature, time, and ligand to metal ratio (5:1 to 75:1) on the extraction efficiency of metal ions were also systematically investigated. The extraction efficiency was 100% for Ni²⁺ and 95.9% for Cu²⁺ in scCO₂ with the system of ligand 1, ultrapure water, and perfluoro-1-octanesulfonic acid tetraethylammonium salt (PFOAT) under the optimized conditions (25 MPa, 313 K, 90 min, and ligand to metal ratio of 10). Although all ligands exhibited good efficiency for Ni²⁺ (>85%) and Cu²⁺ (>70%) extraction, the extraction of mixed metal ions indicated that the bipyridine derivatives had low selectivity. Finally, the detailed calculation results exhibited that the extraction constants (K_ex) of the metal ions increased with the increase of the extraction efficiency in the same extraction system for each same metal ion.     

A ratiometric fluorescent sensor for zinc(II) with high selectivity

Spectroscopic studies revealed that the compound [N,N′-di(quinoline-2-methylene) -1,2-phenylenediimine] (1) exhibited a rather high selectivity toward Zn²⁺ over other metal ions, even Cd²⁺. In acetonitrile, the red shift of fluorescent emission from 396 nm to 426 nm upon zinc binding is due to the formation of a 1:1 metal/ligand complex.     

Conductometric and viscometric investigation of poly(N‐vinylimidazole)‐metal ion complex formation

The complexation of copper (Cu²⁺), cobalt (Co²⁺), and cadmium (Cd²⁺) ions with poly(N‐vinylimidazole) (PVIm) and its protonated form in aqueous solution was studied conductometrically and viscometrically. From the conductometric and viscometric curves, it was found that four imidazole units were coordinated with one metal ion in the complex systems. Both studies showed that the complex formation tendency decreased in the following order: Cu²⁺ > Co²⁺ > Cd²⁺. Complex properties of metal ions with imidazole group were explained by referring to Pearson's treatment, as hard and soft acids and bases. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 376–384, 2002     

Synthesis,characterization, and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid)–metal complexes

The metal‐ion complexation behavior and catalytic activity of 4 mol % N,N′‐methylene bisacrylamide crosslinked poly(acrylic acid) were investigated. The polymeric ligand was prepared by solution polymerization. The metal‐ion complexation was studied with Cr(III), Mn(II), Fe(III), Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal uptake followed the order: Cu(II) > Cr(III) > Mn(II) > Co(II) > Fe(III) > Zn(II) > Ni(II). The polymeric ligand and the metal complexes were characterized by various spectral methods. The catalytic activity of the metal complexes were investigated toward the hydrolysis of p‐nitrophenyl acetate (NPA). The Co(II) complexes exhibited high catalytic activity. The kinetics of catalysis was first order. The hydrolysis was controlled by pH, time, amount of catalyst, and temperature. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 272–279, 2004     

Adsorption of heavy metal ions in ternary systems onto Fe(OH)3

The adsorption behavior of amorphous Fe(OH)₃ has been studied in multicomponent metal system. The metal ions uptake in the ternary system is lower than in the single system, suggesting that certain sites on the surface of the solid are blocked due to competition. The selectivity trend in the ternary system is observed to be Ni²⁺>Zn²⁺>Cd²⁺ which is, however, lost with increase in the temperature of the aqueous solution. Further, the observed selectivity trend is neither related to electronegativity of the metal ions nor to the pH of the hydrolysis, but has been found dependent on charge to radius ratio. The metal ions adsorption is found to increase with pH, while the converse is true with the rise in temperature. The uptake of metal ions data has been interpreted in terms of stoichiometry, binding constants and adsorption capacities. The negative values of ΔG show that uptake of metal ions is favored at lower temperatures, indicating that the adsorption mechanism essentially remains ion exchange in nature.     

Synthesis,characterization, electrochemical behavior,thermal study and antibacterial/antifungal properties of some new zinc(II) coordination compounds

A novel symmetrical Schiff base ligand was prepared by condensation reaction of 2,2-dimethyl-1.3-diaminopropane and (E)3-(2nitrophenyl)acrylaldehyde. The ligand and its Zn(II) coordination compounds were well characterized by the elemental analysis, FTIR, ¹H, ¹³C NMR, UV–vis spectra and molar conductance. Thermal behaviors of all compounds were investigated from the room temperature to 600 °C with a heating rate of 10 °C/min. Furthermore some decomposition thermo-kinetic parameters were evaluated by Coats–Redfern equation at each decomposition step. Electrochemical properties of ligand and its complexes were studied by cyclic voltammetry technique. Also antibacterial/antifungal activities of the ligand and its complexes were tested against three Gram-negative bacteria Escherichia coli (ATCC 25922), Salmonella spp. and Pseudomonas aeruginosa (ATCC 9027) and two Gram-positive bacteria Staphylococcus aureus (ATCC 6538) and Corynebacterium renale and also three fungi (Aspergillus niger, Penicillium chrysogenum and Candida albicans). The results exhibited suitable antibacterial/antifungal properties for ligand and Zn(II) complexes. The study has shown that the complexation of ligand to zinc center lead to enhancement of antibacterial/antifungal activity.     

SOLVENT EXTRACTION OF URANIUM(VI) AND THORIUM(IV) WITH A TETRA-CARBOXYLATED CALIX[4]ARENE AND EFFECT OF ALKALI IONS (Na+, K+)

ABSTRACT

The solvent extraction of uranium(VI) and thorium(IV) with a tetra-carboxylated calix[4]arene (LH₄) in chloroform has been studied in the presence or absence of alkali ions (M⁺=Na⁺, K⁺). When studied alone, UO₂ ²⁺ and Th⁴⁺ were extracted into chloroform as 2:2 and 1:1 metal:ligand complexes, respectively. The efficiency of extraction increases in the presence of alkali ions, due to the formation of heteronuclear complexes. For uranium(VI), the extracted species are found to be both 2:2:2 and 1:1:1 (uoi₂ ²⁺:M⁺:LH₄,) mixed complexes. For Th(IV) in the presence of Na⁺, the formation of a mixed complex in 1:1:1 (Th(IV):Na⁺:LH₄,) proportions has been evidenced. However, the exact nature of this species could not be determined. In practical grounds, LH. may be useful as a selective extracting agent for Th(IV) with respect to U(VI) since separation factor Th(IV)/U(VI) close to 1000 have been measured in competitive extraction, in the presence or absence of alkali ions.