Complexation Of Copper Ions Research Articles

Microscopic Study of a Ligand Induced Electroless Plating Process onto Polymers

The ligand induced electroless plating (LIEP) process was recently developed and thoroughly demonstrated with one of the most used polymers for plating processes: acrylonitrile-butadiene-styrene (ABS). This generic process is based, thanks to the use of diazonium salts as precursors, on the covalent grafting of a thin layer of poly(acrylic acid) (PAA) acting as ligand for metallic salts onto pristine polymer surfaces. This strategy takes advantage of the PAA ion exchange properties. Indeed, carboxylate groups contained in PAA allow one to complex copper ions which are eventually reduced and used as catalysts of the metallic deposition. Essentially based on ABS, ABS-PC (ABS-polycarbonate) and PA (polyamide) substrates, the present paper focuses on the role of the polymer substrate and the relationships between the macroscopic properties and microscopic characterizations such as infrared (IR), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and scanning electron microscopy (SEM). The adhesion strength of the metallic layer deposited via that LIEP process with the bulk polymer substrates was successfully compared with the adhesion of similar copper films deposited by the usual process based on chromic acid etching and palladium-based seed layer, by measuring the T-peel adhesion strength, and by carrying out the common industrial scotch tape test. Lastly, the electrical properties of the deposited layer were studied thanks to a four-point probe and scanning tunneling microscopy (STM) measurements.

Assessment of copper, cadmium and zinc remobilization in Mediterranean marine coastal sediments

The remobilization of copper, cadmium and zinc in sediments of three selected coastal microenvironments of the Aegean Sea (Eastern Mediterranean) is assessed. Various analytical methods and techniques were employed providing concentrations, profiles and forms of metals and organic matter in sediments and pore waters. At Loutropyrgos, a non-industrial site located, however, within an intensively industrialized enclosed gulf, an intense resupply of zinc in pore water from sediment was recorded, correlating with the highest value of weakly bound fraction of zinc determined at this area. The comparatively high zinc concentrations measured in the pore waters (394 nM), exceed considerably those in the overlying seawater (12.5 nM determined by DGT; 13.5 nM total), resulting in the formation of a strong concentration gradient at the sediment–water interface. Potential zinc flux at the sediment–water interface at Loutropyrgos (based on 0.4 mm DGT profile) was calculated equal to 0.8 mmol.m −2.d −1. The half lives of trace metals at Loutropyrgos site, based on the aforementioned DGT profiles, amount to 0.1 y (Zn), 2.8 y (Cd), 4.5 y (Cu), 2.2 y (Mn) and 0.4 y (Fe) pointing out to the reactivity of these metals at the sediment–water interface. The concentration of dissolved organic carbon (DOC) in pore waters of the three selected sites (2.7–5.2 mg/L) was up to four times higher compared to that of the corresponding overlying seawater. Similarly, the concentrations of carbohydrates in pore waters (0.20–0.91 mg/L monosaccharides; 0.71–1.6 mg/L polysaccharides) are an order of magnitude higher than those of seawater, forming a concentration gradient at the sediment–water interface. Total carbohydrates contribute between 34 and 48% of the organic carbon of the pore waters, being significantly higher than those of seawater from the corresponding areas, which were in the range of 15–21%. The complexing capacity as for copper ions (CCu) determined in pore water ranges widely, from 0.03 μM at Kalamos to 3.76 μM at Molos, whereas the corresponding values for cadmium ions (CCd) were non detectable, except for Kalamos site, where the value for CCd was equal to 0.03 μM. A significant increase in the values of CCu, normalized as for DOC, was observed in pore waters in relation to those of overlying seawater. This indicates an ‘enrichment’ of pore waters in dissolved organic ligands for copper ions per unit of DOC. Up to 72% of DOC could be present as ligands capable to complex copper ions.

Copper and Iron Determination with [N,N′‐Bis(salicylidene)‐2,2′‐dimethyl‐1,3‐propanediaminato] in Edible Oils Without Digestion

AbstractA new method for the determination of copper(II) and iron(III) in liquid edible oils which does not require a digestion step was developed. The suggested method involves extraction of metals with [N,N′‐bis(salicylidene)‐2,2′‐dimethyl‐1,3‐propanediaminato] (LDM) followed by flame atomic absorption spectrometry measurement. As a first step, metal complexes of copper(II) and iron(III) ions with LDM were investigated spectrophotometrically. After the analytical properties and experimental conditions of the complexation had been determined, these findings were used to determine the extraction period as a second step. Experimental conditions were optimized using a central composite design. Optimum conditions for Cu(II) and Fe(III) extractions from oil were found: the ratios of the volume of Schiff base solution used to the mass of oil (VLDM/moil; mL g−1) were 0.76 and 1.19 mL g−1, the stirring times were 73 and 67 min, and the temperatures were 31 and 28 °C, respectively. The developed extraction and determination method was tested on certified reference materials; the recovery percentages were found to be 99.4 ± 2.8 and 100.2 ± 5.6 for Cu(II) and Fe(III), respectively. The suggested method was performed on real samples such as olive oil, sunflower oil, corn oil, canola oil and recovery values between 97.2–102.1 for Cu(II) and 94.5–98.6 for Fe(III) were determined. It was concluded that the developed method has some advantages over the common traditional method including rapidity, sensitivity, accuracy, reduced risk and cost.

Redox behaviors of the neurotoxic portion in human prion protein, HuPrP(106–126)

A peptide fragment of human prion protein, HuPrP(106–126), has been reported to mimic the pathological features underlying prion diseases. Although the actual neurotoxic mechanism of HuPrP(106–126) has not been elucidated, several hypotheses has been proposed based on the role for copper. In this study, to understand the toxic function of HuPrP(106–126) from a viewpoint of electrochemical competence, we investigated redox properties of copper ion complexes with four different binding motifs of a model of HuPrP(106–126) based on density functional theory calculations. We found that the HuPrP(106–126)-derived models exhibited diverse redox activities that depended on copper-binding conformations.

Electrochemical characterization of copper chemical mechanical polishing in l-glutamic acid–hydrogen peroxide-based slurries

The effect of l-glutamic acid as complexing agent in the presence of hydrogen peroxide as oxidizer in copper chemical mechanical polishing (CMP) slurry is investigated. In the CMP process, the work surface is moved against a pad, with slurry flowing between the surface and the pad. The polish rate was found to be stable over a wide range of hydrogen peroxide concentration. High concentration of either l-glutamic acid or hydrogen peroxide leads to a reduction in polish rate, but a high concentration of both chemicals does not reduce the polish rate. In the absence of hydrogen peroxide, the Cu polish rate was 0 for all the l-glutamic acid concentrations investigated. However, potentiodynamic polarization curves do not show any sign of passivation when l-glutamic acid was present in the solution. In situ open circuit potential measurements show that copper redox reactions as well as hydrogen peroxide redox reactions contribute in determining the electrochemical behavior. We propose that l-glutamic acid inhibits the copper dissolution by adsorption onto the metallic copper, but enhances copper dissolution by complexing copper ions. The results show that it is possible to conduct controllable copper CMP in mildly acidic slurries with hydrogen peroxide as oxidizer and l-glutamic acid as complexing agent.

The effect of ligand molecular weight on copper salt catalyzed oxidative coupling polymerization of 2,6‐dimethylphenol

AbstractPolyphenylene oxide (PPO) was prepared via oxidative coupling polymerization of 2,6‐dimethylphenol (DMP) catalyzed by copper salt. The ligand was a novel series of random copolymers (PSVP) of styrene and 4‐vinylpyridine prepared by reversible addition‐fragmentation chain transfer (RAFT) copolymerization. The copolymers with well‐controlled molecular weight (MW) were used to study the effects of ligand molecular weight on the catalytic activity and selectivity. It was found that the catalytic activity increased with the molecular weight but there existed an upper MW limit above which no further increase in activity could be achieved. With PSVP of FvPy = 0.39, the critical MW was about 5000 g/mol. The mechanism involved in the successive complexation of copper ions and PSVP was elucidated and the equilibrium constants were estimated by pH titration. It was found that the macromolecular ligand was in favor of bridging CuII ions that formed catalytically active dinuclear copper‐amine complexes. However, the catalytic selectivity was almost independent of the ligand MW. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010

Hydrolysis of Pesticides in Wastewater Catalyzed by Cu(II) Complexes of Silyl Based Cationic Micelles

The effect of cationic surfactant micelles, namely hexadecyl trimethyl silane ammonium chloride (A), dodecyl trimethyl silane ammonium chloride, (B) and their copper (II) ion complexes on the hydrolysis of the pesticides: diazinon, cypermethrin, and carbaryl was studied. The rate of the pesticides decay in water was significantly accelerated in presence of these cationic micellar solutions. Furthermore, the copper (II) ion complexes of these micellar were found to be much more effective in hydrolysis of these pesticides. The results indicate that the complexes with a 1:1 ratio of both ligands to the metal ions are the active species in catalytic hydrolysis of carbaryl pesticide. Kinetic study is explained.

Synthesis, crystal structure and magnetic properties of three unprecedented tri-nuclear and one very rare tetra-nuclear copper(ii) Schiff-base complexes supported by mixed azido/phenoxo/nitrato or acetato bridges

Three novel mixed bridged trinuclear and one tetranuclear copper(II) complexes of tridentate NNO donor Schiff base ligands [Cu(3)(L(1))(2)(mu(1,1)-N(3))(2)(CH(3)OH)(2)(BF(4))(2)] (1), [Cu(3)(L(1))(2)(mu(1,1)-N(3))(2)(mu-NO(3)-1kappaO:2kappaO')(2)] (2), [Cu(3)(L(2))(2)(mu(1,1)-N(3))(2)(mu-NO(3)-1kappaO:2kappaO')(2)] (3) and [Cu(4)(L(3))(2)(mu(1,1)-N(3))(4)(mu-CH(3)COO-1kappaO:2kappaO')(2)] (4) have been synthesized by reaction of the respective tridentate ligands (L(1) = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol, L(2) = 2-[1-(2-diethylamino-ethylimino)-ethyl]-phenol, L(3) = 2-[1-(2-dimethylamino-ethylimino)-methyl]-phenol) with the corresponding copper(ii) salts in the presence of NaN(3). The complexes are characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. Complex 1 is composed of two terminal [Cu(L(1))(mu(1,1)-N(3))] units connected by a central [Cu(BF(4))(2)] unit through nitrogen atoms of end-on azido ligands and a phenoxo oxygen atom of the tridentate ligand. The structures of 2 and 3 are very similar; the only difference is that the central unit is [Cu(NO(3))(2)] and the nitrate group forms an additional mu-NO(3)-1kappaO:2kappaO' bridge between the terminal and central copper atoms. In complex 4, the central unit is a di-mu(1,1)-N(3) bridged dicopper entity, [Cu(2)(mu(1,1)-N(3))(2)(CH(3)COO)(2)] that connects two terminal [Cu(L(3))(mu(1,1)-N(3))] units through end-on azido, phenoxo oxygen and mu-CH(3)COO-1kappaO:2kappaO' triple bridges to result in a tetranuclear unit. Analyses of variable-temperature magnetic susceptibility data indicates that there is a global weak antiferromagnetic interaction between the copper(II) ions in complexes 1-3, with the exchange parameter J of -9.86, -11.6 and -19.98 cm(-1) for 1-3, respectively. In complex 4 theoretical calculations show the presence of an antiferromagnetic coupling in the triple bridging ligands (acetato, phenoxo and azido) while the interaction through the double end-on azido bridging ligand is strongly ferromagnetic.

Four new copper(II) complexes with 1,3-tpbd ligand: Synthesis, crystal structures, magnetism, oxidative and hydrolytic cleavage of pBR322 DNA

Four copper(II) complexes [Cu(2)(1,3-tpbd)Cl(4)].EtOH (1), {[Cu(2)(1,3-tpbd)(mu-Cl)(2)](ClO(4))(2)(H(2)O)(4.5) (NaClO(4))}(infinity) (2), [Cu(2)(1,3-tpbd)(1,10-phen)(2)(H(2)O)(2)](ClO(4))(4) (3) and [Cu(2)(1,3-tpbd)(2,2'-bpy)(2)(H(2)O)(2)](ClO(4))(4) (4) (1,3-tpbd=N,N,N',N'-tetrakis(2-pyridylmethyl)benzene-1,3-diamine) have been synthesized and characterized by X-ray single crystal structure analysis. Variable-temperature magnetic susceptibility studies (2-300K) indicate the existence of antiferromagnetic coupling between the copper(II) ions in complexes 2 and 3. The interactions of the four complexes with calf thymus DNA (CT-DNA) have been investigated by UV absorption, fluorescent spectroscopy, circular dichroism spectroscopy, viscosity and cyclic voltammetry, and the modes of CT-DNA binding to the complexes have been proposed. Furthermore, DNA cleavage activities by the four complexes were performed in the presence and absence of external agents, the results indicate that their cleavage activities have been promoted in the presence of external agents. Mechanism investigation shows that the four complexes could cleave DNA through both oxidative and hydrolytic processes. In the four copper(II) complexes, complex 2 showed highest cleavage activity with the pseudo-Michaelis-Menten kinetic paraments k(cat)=5.16h(-1) and K(m)=3.6x10(-5)M.

Generation of soluble oligomeric β-amyloid species via copper catalyzed oxidation with implications for Alzheimer’s disease: A DFT study

A mechanism for the oxidation of a dimeric beta-amyloid copper ion complex is proposed based on DFT calculations. It involves the Met35 residue, which is believed to be important in the neurotoxicity causing Alzheimer's disease. Oxidation of Met35 is found to proceed readily with dioxygen when two Met35 residues are close to each other and the copper ion. This indicates that oxidants, such as hydrogen peroxide, are not necessary for oxidation of beta-amyloid copper ion complexes. Understanding these processes could be pivotal in gaining more knowledge of this complex disease and for the development of therapeutic treatments.

Influence of chloride ions, pH and humic substances on complexation of cadmium(II) and copper(II)

An influence of chloride ions, pH and humic substances concentration on complexation of cadmium(II)and copper(II) ions with humic acids was studied by means of inversion-voltamperometry using the method of experimental design. Equations establishing dependences of concentrations of humate complexes of cadmium(II) and copper(II) on concentrations of chloride and humic substances and pH values too were derived.

A novel 1,2,4-triazole-based copper(II) complex: Synthesis, characterization, magnetic property and nuclease activity

A novel binuclear copper(II) complex [Cu(2)L(mu-SO(4))](PF(6))(2) (1) (L=3,5-bis (bis(pyridine-2-ylmethyl)amino)methyl)-4H-1,2,4-triazol-4-amine) has been synthesized and structurally characterized. X-ray structure shows that the two copper(II) atoms are bridged by one bidentate sulfate ion and the 1,2,4-triazole ring of L with Cu1cdots, three dots, centeredCu2 distance of 4.404A. Each copper(II) center has a distorted trigonal-bipyramidal configuration. Variable-temperature magnetic susceptibility studies (2-300K) indicate the existence of weak antiferromagnetic coupling between the copper(II) ions in complex 1. The interaction of complex 1 with calf thymus DNA (CT-DNA) has been studied by UV absorption, fluorescence spectroscopy, circular dichroism spectroscopy, viscosity and cyclic voltammetry. Furthermore, complex 1 was able to promote single and double strand DNA cleavage in both aerobic and anaerobic conditions, the pseudo-Michaelis-Menten kinetic parameters k(cat)=2.58h(-1) and K(m)=1.2x10(-4)M were obtained for 1. The hydrolytic cleavage of DNA by the complex was supported by the evidence from free radical quenching, anaerobic experiment, thiobarbituric acid-reactive substances (TBARS) assay.

Characterization of natural and synthetic humic substances (melanoidins) by chemical composition and adsorption measurements

Melanoidins, condensation products of sugars and amino acids, are thought to represent a key link in the transformation of polysaccharides and proteins to humic material in the marine environment. We investigated adsorption behaviour of melanoidins prepared in equimolar solutions of glucose and amino acids of choice (glutamic acid, valine and lysine) and pseudomelanoidins which were prepared from glucose only. Melanoidins were prepared using different condensation times (2, 4, 16 and 32 days). Synthesized melanoidins were separated into different molecular mass fractions. Fractionation of melanoidins by sorption on the macroreticular resin XAD-8 separated melanoidins into hydrophobic neutral, hydrophobic acid and hydrophilic fractions. Adsorption of melanoidins and their different fractions was studied at a mercury electrode by directly measuring the change of the double layer capacitance caused by the adsorption of organic molecules on the electrode surface through phase sensitive alternating current voltammetry. The hydrophobic acid fraction of melanoidins accounted for most of the adsorption behaviour of melanoidins. Consequently, the higher molecular mass fraction of melanoidins (>10 kDa) exhibits a stronger adsorption in comparison to the lower molecular mass fraction (<3 kDa) of the same melanoidin. The good fit of adsorption data of melanoidins and pseudomelanoidins to the same adsorption isotherm supports the idea that melanoidins are comprised of a sugar derived “backbone” that is responsible for the adsorption behaviour of melanoidin, while the presence of nitrogen atoms is responsible for the complexation of copper ions. Adsorption characteristics and complexation ability of melanoidins and natural organic matter were similar. Our results suggest that in the process of humification, selective adsorption of condensation products on aqueous surfaces may lead to a progressive immobilization of certain fractions, i.e., it is probable that higher molecular mass components accumulate at aquatic surfaces, while lower mass components remain in solution.

Copper complexing ligands and organic matter characterization in the northern Adriatic Sea

The study on dissolved organic ligands capable to complex copper ions (L T), surface-active substances (SAS) and dissolved organic carbon (DOC) in the Northern Adriatic Sea station (ST 101) under the influence of Po River was conducted in period from 2006–2008. The acidity of surface-active organic material (Ac r) was followed as well. The results are compared to temperature and salinity distributions. On that way, the contribution of the different pools of ligands capable to complex Cu ions could be determined as well as the influence of aging and transformation of the organic matter. The L T values in the investigated period were in the range of 40–300 nmol l −1. The range of DOC values for surface and bottom samples were 0.84–1.87 mg l −1 and 0.80–1.30 mg l −1, respectively. Total SAS concentrations in the bottom layer were 0.045–0.098 mg l −1 in equiv. of Triton-X-100 while those in the surface layer were 0.050–0.143 mg l −1 in equiv. of Triton-X-100. The majority of organic ligands responsible for Cu binding in surface water originate from new phytoplankton production promoted by river borne nutrients. Older, transformed organic matter, possessing higher relative acidity, is the main contributor to the pool of organic ligands that bind copper in the bottom samples. It was estimated that ∼9% of DOC in surface samples and ∼12% of DOC in the bottom samples are present as ligands capable to complex copper ions.

Synthesis, crystal structures, and magnetic properties of new tetranuclear Cu(II) complexes of bis-bidentate Schiff-base ligands

Two tetranuclear copper(II) complexes with long rigid Schiff-base ligands [Cu 4(bmsbd) 2]·2DMF [H 2bmsbd = N,N′-bis-(3-methoxy-salicylidene)benzene-1,4-diamine] ( 1) and [Cu 4(besbd) 2]·DMF·5H 2O [H 2besbd = N,N′-bis-(3-methoxy-salicylidene)benzene-1,4-diamine] ( 2) have been synthesised and characterized. Single X-ray diffraction analysis reveals that both complexes exhibit interesting [2 × 2] molecular grid-like configuration assembled by four organic ligands in a head-to-tail mode to bind four copper(II) ions. Magnetic property investigations reveal weak antiferromagnetic interaction via σ-bond pathway of long rigid Schiff-base ligand between the neighboring copper(II) ions in both complexes.

Synthesis, characterization and X-ray crystal structures of N-2-pyridinyl carbonyl-2-pyridine carboximidate copper(II) complexes

Two copper complexes, [Cu(bpca)(4,4′-bpyH)(H2O)(ClO4)]ClO4·H2O (1) and [Cu4(bpca)4(mpba)]·3H2O (2) [bpca = N-2-pyridinylcarbonyl-2-pyridine-carboximidate; mpba = 1,3-phenylenebis(oxamate)] were synthesized and characterized by physico-chemical and spectroscopic techniques. Complex 1 crystallizes in the Triclinic P-1 space group while complex 2 is in the Monoclinic space group C2/c. Bpca acts as a tridentate ligand through its three nitrogen atoms in these species. They exhibit 2D supramolecular architectures through hydrogen bonds and short-distance intermolecular interactions. Magnetic measurements in the range 2–300 K have shown weak antiferromagnetic interactions between the adjacent copper ions in complex 2.

Preparation of Some Novel Copper(I) Complexes and their Molar Conductances in Organic Solvents

Abstract Attempts have been made to prepare some novel copper(I) nitrate, sulfate, and perchlorate complexes. Molar conductances of these complexes have been measured in organic solvents like acetonitrile (AN), acetone (AC), methanol (MeOH), N,N-dimethylformamide (DMF), N,Ndimethylacetamide (DMA), and dimethylsulfoxide (DMSO) at 298 K. The molar conductance data have been analyzed to obtain limiting molar conductances (λ0) and ion association constants (KA) of the electrolytes. The results showed that all these complexes are strong electrolytes in all organic solvents. The limiting ionic molar conductances (λo ± ) for various ions have been calculated using Bu4NBPh4 as reference electrolyte. The actual radii for copper(I) complex ions are very large and different in different solvents and indicate some solvation effects in each solvent system

Electrodeposition of copper composites from deep eutectic solvents based on choline chloride

Here we describe for the first time the electrolytic deposition of copper and copper composites from a solution of the metal chloride salt in either urea-choline chloride, or ethylene glycol-choline chloride based eutectics. We show that the deposition kinetics and thermodynamics are quite unlike those in aqueous solution under comparable conditions and that the copper ion complexation is also different. The mechanism of copper nucleation is studied using chronoamperometry and it is shown that progressive nucleation leads to a bright nano-structured deposit. In contrast, instantaneous nucleation, at lower concentrations of copper ions, leads to a dull deposit. This work also pioneers the use of the electrochemical quartz crystal microbalance (EQCM) to monitor both current efficiency and the inclusion of inert particulates into the copper coatings. This technique allows the first in situ quantification or particulate inclusion. It was found that the composition of composite material was strongly dependent on the amount of species suspended in solution. It was also shown that the majority of material was dragged onto the surface rather than settling on to it. The distribution of the composite material was found to be even throughout the coating. This technology is important because it facilitates deposition of bright copper coatings without co-ligands such as cyanide. The incorporation of micron-sized particulates into ionic liquids has resulted, in one case, in a decrease in viscosity. This observation is both unusual and surprising; we explain this here in terms of an increase in the free volume of the liquid and local solvent perturbation.

Synthesis, structure, magnetic properties and DNA cleavage of binuclear Cu(ii) Schiff-base complexes

Five binuclear Schiff base copper(ii) complexes [Cu(2)(L)(OAc)].3DMF (), [Cu(2)(L)(OAc)](2).3DMF (), [Cu(2)(L)(BNPP)].3CH(3)CN (), [Cu(2)(L)(Fa)].2DMF () and [Cu(2)(L)(Pa)].DMF () (H(3)L = N,N'-bis(3,5-tert-butylsalicylidene-2-hydroxy)-1,3-propanediamine, OAc = acetic acid, BNPP = bis(4-nitrophenyl)phosphate, Fa = 2-tetrahydrofuroic acid, Pa = benzoic acid) have been synthesized and characterized by X-ray single-crystal structure analysis. Variable-temperature magnetic susceptibility studies (2-300 K) indicate the existence of ferromagnetic coupling between the copper(ii) ions in complexes and , and antiferromagnetic coupling in complexes and . The interaction of these complexes with CT-DNA has been studied by using absorption and emission spectral methods. The apparent binding constant (K(app)) values for complexes , , and are 4.67 x 10(5), 9.48 x 10(5), 4.30 x 10(5) and 3.90 x 10(5) M(-1), respectively, which show that the complexes bind to DNA by moderate intercalative binding modes. Furthermore, all these complexes can cleave plasmid DNA to nicked DNA in a sequential manner as the concentrations or reaction times are increased in the absence of reducing agent. Their cleavage activities are promoted in the presence of hydrogen peroxide. The cleavage mechanisms between the complexes and plasmid DNA are likely to involve singlet oxygen (1)O(2) and OH as reactive oxygen species.

Synthesis, X-ray crystal structures, magnetism, and DNA cleavage properties of copper(ii) complexes with 1,4-tpbd ligand

Four new copper(II) complexes, [Cu(1,4-tpbd)Br(2)] (), [Cu(2)(1,4-tpbd)(H(2)O)(4)](ClO(4))(4) (), [Cu(2)(1,4-tpbd)(1,10-phen)(2)(DMF)(2)](ClO(4))(4) () and [Cu(2)(1,4-tpbd)(2,2'-bpy)(2)(ClO(4))(2)](ClO(4))(2) (), [1,4-tpbd = N,N,N',N'-tetrakis(2-pyridylmethyl)benzene-1,4-diamine], have been synthesized to serve as artificial nucleases. Single crystal X-ray diffraction reveals that the copper(II) atom has a distorted intermediate between square pyramidal and trigonal bipyramidal configuration for and a distorted square pyramidal geometry for , while a distorted octahedral environment for and . Variable-temperature magnetic susceptibility studies (2-300 K) indicate the existence of antiferromagnetic coupling between the copper(II) ions in complex . The interactions of the four complexes with calf thymus DNA (CT-DNA) have been investigated by UV absorption, fluorescent spectroscopy and cyclic voltammetry, and the modes of CT-DNA binding for the complexes have been proposed. In the absence of external agents, supercoiled plasmid DNA cleavage by the complexes was performed under aerobic conditions, the influence on the DNA cleavage process of different complex concentrations, reaction times was also studied. The DNA cleavage mechanisms were demonstrated with radical scavengers and anaerobic conditions, indicating all complexes cleaved pBR322 DNA in 50 mM Tris-HCl/18 mM NaCl buffer (pH = 7.2) at 37 degrees C through a hydrolytic process. In the four copper(II) complexes, complex showed highest cleavage activity with the pseudo-Michaelis-Menten kinetic parameters k(cat) = 4.23 h(-1) and K(m) = 2.4 x 10(-5) M.