Cu(II)-3-(5-chlor-2-hydroxy-3-sulfophenylazo)-6-(2,4,6-tribromophenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic Acid-Co(II) binuclear complexation and its application to the selective determination of cobalt at ng/ml level.

The chromophore, 3-(5-chlor-2-hydroxy-3-sulfophenylazo)-6-(2,4,6-tribromophenylazo)-4,5-dihydroxynaphthalene-2,7-disulfonic acid (CSTDD) was used to complex Cu(II) and Co(II) in aqueous solution at pH 9.43. A binuclear complex of Cu-CSTDD-Co was formed and showed a high selectivity for the determination of Co(II). The spectral correction technique was applied to characterize the complexes. The results showed the formation of complexes of Cu(CSTDD), Co(CSTDD)3 and Cu2(CSTDD)2Co. The quantitative analysis of Co(II) at ng/ml level was carried out by the light-absorption ratio variation approach (LARVA). The results showed that the technique is satisfactory to determine Co(II) at trace level in water samples with a detection limit of 2.3 ng/ml.     

Determination of cobalt at ng ml(-1) level in water using the electrophilic substiution complexation between co(II) and chlorophosphonazo-p-CL-Cu(II) complex

The chromophore chlorophosphonazo-p-Cl (PCCPA) was used to complex Co(II) and Cu(II) at pH 9.18. The formation of Co(PCCPA)2 and Cu(PCCPA)2 complexes were characterized by the spectral correction technique. Co(II) could competitively substitute Cu(II) from the Cu(II)-PCCPA complex via electrophilic effect. With the assistance of the light-absorption ratio variation approach, the electrophilic substitution complexation showed a high selectivity and good sensitivity with 1.9 ng mL(-1) of LOD. The proposed method has been applied to the direct detection of Co(II) in surface water and wastewater with good percent of recovery.     

Application of light-absorption ratio variation approach as an optimum spectrophotometry to determination of Mn(II) in ng ml(-1) level using a competitive replacement complexation

The light-absorption ratio variation approach (LARVA) which produces an outstandingly increasing of analytical sensitivity was applied to the quantitative detection of ultramicro amounts of Mn(II) by light-absorption spectrometry using the competitive replacement complexation among 1,5-di(2-hydroxy-5-sulfophenyl)-3-cyanoformazan (DSPCF), Zn(II) and Mn(II) in the presence of o-phenanthroline (OPTL). Not only masks OPTL foreign metal ions but also seriously sensitize the competitive complexation. All the binary and ternary complexes were characterized by the break point approach. Results have shown that the limit of detection (3delta) of Mn(II) is only 0.7 ng ml(-1). This method has been applied to analysis of water quality with satisfactory results.     

Potential of Modified Multiwalled Carbon Nanotubes with 1-(2-Pyridylazo)-2-naphtol as a New Solid Sorbent for the Preconcentration of Trace Amounts of Cobalt(II) Ion

The present paper reports on the application of modified multiwalled carbon nanotubes (MMWCNTs) as a new, easily prepared and stable solid sorbent for the preconcentration of trace Co(II) in aqueous solution. Multiwalled carbon nanotubes (MWCNTs) were oxidized with concentrated HNO(3) and modified with 1-(2-pyridylazo)-2-naphtol (PAN), and were then used as a solid phase for the preconcentration of Co(II). Factors influencing the sorption and desorption of Co(II) were investigated. Elution was carried out with 0.5 mol L(-1) HNO(3). The amount of eluted Co(II) was measured using flame atomic absorption spectrometry. The effects of the experimental parameters, including the sample pH, sample flow rate, eluent flow rate and eluent concentration, were investigated. The effect of coexisting ions showed no interference from most ions tested. The proposed method permitted a large enrichment factor (about 300). The precision of the method was 1.63% (for eight replicate determination of 0.5 microg mL(-1) of Co(II)) and the limit of detection was 0.55 ng mL(-1). The method was applied to the determination of Co(II) in water, biological and standard samples.     

Reversed-phase HPLC determination of Co(II), Ni(II) and Fe(III) as their 2-(2-thiazolylazo)-5-dimethylaminophenol chelates

The optimum chromatographic separation conditions for Co(II), Ni(II), and Fe(III) chelates with 2-(2-thiazolylazo)-5-dimethylaminophenol (TAM) were investigated. The compositions of chelates were also determined by the HPLC method and thus the possible structure of chelates was given. A precolumn derivatization method was used, followed by separation on an octyl-bonded silica stationary phase with a methanol-tetrahydrofuran-water (40:9:51, v/v/v) mobile phase containing pH 5.8 acetate buffer and 1 x 10(-4)M TAM. The detection limits of Co(II), Ni(II), and Fe(III) at 560 nm are 0.03, 0.02 and 0.1 ng (S N = 2 ), respectively. They can be determined by means of the proposed method without interference from other common metal ions and have been determined in five standard alloys with satisfactory results.     

Dispersive liquid-liquid microextraction of Fe(II) and Cu(II) with diethyldithiocarbamate and their simultaneous spectrophotometric determination using mean centering of ratio spectra

A new dispersive liquid-liquid microextraction (DLLME) method for preconcentration of trace quantities of Fe(II) and Cu(II) followed by their spectrophotometric determination has been developed. For the extraction, an appropriate mixture of ethanol (the disperser solvent) and carbon tetrachloride (the extraction solvent) was injected rapidly into the water sample containing Fe(II) and Cu(II) after formation of complexes with diethyldithiocarbamate. Mean centering (MC) of ratio spectra has been used for simultaneous determination of Fe(II) and Cu(II). Linear range of the method is 1.0–100 ng/mL for Fe(II) and 0.3–100 ng/mL for Cu(II), the detection limit is 0.53 ng/mL and 0.14 ng/mL Cu(II), resp. The interference effect of some anions and cations is reported. The method was applied to the determination of Fe(II) and Cu(II) in well water samples.     

Determination of Cu(II) and Zn(II) using silica gel loaded with 1-(2-thiasolylazo)-2-naphthol

The silica gel with 1-(2-thiasolylazo)-2-naphthol adsorbed was obtained. The adsorption of Cu(II) and Zn(II) from an aqueous solution onto loaded silica gel was studied. The capabilities of 1-(2-thiasolylazo)-2-naphthol immobilized for Cu(II) and Zn(II) preconcentration, visual and diffusion reflectance spectroscopic detection was evaluated. The detection limits were 10 and 15 microg.l(-1), respectively. Visual test scales for metal ions determination in the range 0.65-13 microg per sample were worked out. The developed methods were applied to Cu(II) and Zn(II) determination in natural and tap water. The obtained results agreed well with the reported value.     

Synthesis and magnetic properties of heterometal cyclic tetranuclear complexes [Cu(II)LM(II)(hfac)]2 (M(II) = Zn,Cu, Ni,Co, Fe,Mn; H3L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane; Hhfac = hexafluoroacetylacetone)

A series of heterometal cyclic tetranuclear complexes [Cu(II)LM(II)(hfac)](2) (M(II) = Zn (1), Cu (2), Ni (3), Co (4), Fe(5), and Mn (6)) have been synthesized by the assembly reaction of K[CuL] and [M(II)(hfac)(2)(H(2)O)(2)] with a 1:1 mole ratio in methanol, where H(3)L = 1-(2-hydroxybenzamido)-2-((2-hydroxy-3-methoxybenzylidene)amino)ethane and Hhfac = hexafluoroacetylacetone. The crystal structures of 2, 4, and [Cu(II)LMn(II)(acac)](2) (6a) (Hacac = acetylacetone) were determined by single-crystal X-ray analyses. Each complex has a cyclic tetranuclear Cu(II)(2)M(II)(2) structure, in which the Cu(II) complex functions as a "bridging ligand complex", and the Cu(II) and M(II) ions are alternately arrayed. One side of the planar Cu(II) complex coordinates to one M(II) ion at the two phenoxo and the methoxy oxygen atoms, and the opposite side of the Cu(II) complex coordinates to another M(II) ion at the amido oxygen atom. The temperature-dependent magnetic susceptibilities revealed spin states of S(M) = 0, 1/2, 1, 3/2, 2, and 5/2 for the Zn(II), Cu(II), Ni(II), Co(II), Fe(II), and Mn(II) ions, respectively. Satisfactory fittings to the observed magnetic susceptibility data were obtained by assuming a rectangular arrangement with two different g-factors for the Cu(II) and M(II) ions, two different isotropic magnetic exchange interactions, J(1) and J(2), between the Cu(II) and M(II) ions, and a zero-field splitting term for the M(II) ion. In all cases, the antiferromagnetic coupling constants were found for both exchange interactions suggesting nonzero spin ground states with S(T) = 2/S(M) - S(Cu)/, which were confirmed by the analysis of the field-dependent magnetization measurements.     

The resonance Rayleigh scattering of the interaction of copper(II)-bleomycinA2 with DNA and its analytical application

The forming of bleomycinA2-Cu(II) cationic chelate and the interaction of the chelate with DNA have been investigated by using resonance Rayleigh scattering (RRS), molecular absorption and fluorescence spectra. The result shows that in aqueous solution, bleomycinA2 (BLMA2) can react with Cu(II) to form 1:1 cationic chelate which contributes to the changes of the absorption spectra and the quenched fluorescence of BLMA2. When the cationic chelate further bound with DNA to form ternary ion-association complexes, the remarkable enhancement of the RRS intensity was observed. In this work, the optimum conditions for the coordination reaction of BLMA2 with Cu(II) and some influencing factors have been investigated. The reaction mechanism of BLMA2-Cu(II) binding with DNA was suggested and a binding model was proposed. In addition, the fluorescence quenching type of BLMA2 was investigated. A highly sensitive, simple and rapid new method for the determination of DNA by using BLMA2-Cu(II) as RRS probe has been developed. The detection limits (3σ) are 7.2 ng/mL for ctDNA, 7.1 ng/mL for sDNA and 18 ng/mL for hsDNA. The method can be applied to the determination of trace amounts of DNA.     

Reversed-phase ion-pair high performance liquid chromatographic determination of Co(III)-, Ni(II)-, V(V)- and Fe(III)-2-(2-benzothiazolylazo)-5-(3-sulforpropyl)aminophenol chelates

The separation and determination of Co(III), Ni(II), V(V) and Fe(III) chelates with 2-(2-benzothiazolylazo)-5-(3-sulfopropyl)aminophenol (BTASPAP) by reversed-phase ion-pair HPLC was investigated. In the presence of the oxidant potassium iodate, BTASPAP reacts with Co(III), Ni(II), V(V) and Fe(III) to form stable, negatively charged, water-soluble chelates. The chelates were separated on a C(18) siloxane bonded phase and eluted within 7 min with acetonitrile-acetate-water (36:1:63 v/v) containing 0.2 mol 1(-1) acetic acid-sodium acetate buffer (pH 3.0) and 1.0 mmol 1(-1) tetrabutylammonium bromide. The detection limits of Co(III), Ni(II), V(V) and Fe(III) at 565 nm are 0.3, 0.8, 0.3 and 1.0 ng (signal-to-noise ratio = 2), respectively. The method was applied to the determination of Co, Ni, V and Fe in four samples of standard alloys.     

Adsorptive stripping voltammetric determination of copper(II) ion using phenyl pyridyl ketoneoxime (PPKO)

A sensitive and selective procedure is presented for the voltammetric determination of copper(II) ion. The procedure involves an adsorptive accumulation of Cu2+-PPKO on a hanging mercury drop electrode, followed by a stripping voltammetric measurement of reduction current of adsorbed complex at about -0.30 V (vs. SCE). The optimum conditions for the analysis of copper(II) ion include pH (5.8-7.0), 60 microgM PPKO and an accumulation potential of -0.5 V (vs. SCE). The peak current is proportional to the concentration of copper over the range 0.3-76 ng mL(-1) with a detection limit of 0.01ng mL(-1) with an accumulation time of 60 s. The speciation of different forms of complex between copper(II) ion and PPKO, using the Best (Martell program), followed pH measurement were examined. The method was applied to the determination of copper(II) ion content in real samples successfully.     

Amberlite XAD-7 impregnated with Xylenol Orange: a chelating collector for preconcentration of Cd(II), Co(II), Cu(II), Ni(II), Zn(II) and Fe(III) ions prior to their determination by flame AAS

A new chelating resin, Xylenol Orange coated Amberlite XAD-7, was prepared and used for preconcentration of Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) prior to their determination by flame atomic absorption spectrophotometry. The optimum pH values for quantitative sorption of Cd(II), Co(II), Cu(II), Fe(III), Ni(II) and Zn(II) are 4.5-5.0, 4.5, 4.0-5.0, 4.0, 5.0 and 5.0-7.0, respectively, and their desorptions by 2 mol L(-1) HCl are instantaneous. The sorption capacity of the resin has been found to be 2.0, 2.6, 1.6, 1.6, 2.6 and 1.8 mg g(-1) of resin for Cd, Co, Cu, Fe, Ni and Zn, respectively. The tolerance limits of electrolytes, NaCl, NaF, NaI, NaNO3, Na2SO4 and of cations, Mg2+ and Ca2+ in the sorption of the six metal ions are reported. The preconcentration factor was between 50 and 200. The t1/2 values for sorption are found to be 5.3, 2.9, 3.2, 3.3, 2.5 and 2.6 min for the six metals, respectively. The recoveries are between 96.0 and 100.0% for the different metals at preconcentration limits between 10 to 40 ng mL(-1). The preconcentration method has been applied to determine the six metal ions in river water samples after destroying the organic matter (if present in very large amount) with concentrated nitric acid (RSD < or = 8%, except for Cd for which it is upto 12.6%) and cobalt content of vitamin tablets with RSD of approximately 3.0%.     

Simultaneous spectrophotometric determination of trace amounts of cobalt, nickel, and copper using the partial least-squares method after the preconcentration of their 2-aminocyclopentene-1-dithiocarboxylate complexes on microcrystalline naphthalene

A spectrophotometric method for the determination of trace amounts of cobalt(II), nickel(II), and copper(II) after the adsorption of their 2-aminocyclopentene-1-dithiocarboxylate complexes on microcrystalline naphthalene has been developed. These complexes are adsorbed on microcrystalline naphthalene at pH 4.5 by shaking for 5 min. The formed solid mass is separated by filtration, and dissolved in dimethylformamide. The absorption spectra were processed using the partial least-squares multivarate calibration method for the analysis of a ternary mixture of Co(II), Ni(II), and Cu(II). The detection limits for Co(II), Ni(II), and Cu(II) were 3.3, 10.0, and 0.8 ng/mL, respectively. The total relative standard error for applying the method to 20 synthetic samples in the concentration ranges of 20–400 ng/mL Co(II), 60–400 ng/mL Ni(II), and 4–400 ng/mL Cu(II) was 1.53%. The proposed method was also successfully applied to the determination of Co(II), Ni(II), and Cu(II) in alloys. The text was submitted by the authors in English.     

Studies on Binuclear Co(II) and Cu(II) Complexes of Tridentate N-(2-Carboxyphenyl)Salicylideneimine

Homo Cu(II) and Co(II) binuclear complexes H[MLClMCl₂] formed by using the donor properties of the cis two oxygen atoms of the tridentate N-(2-carboxyphenyl)-salicylaldimine Schiff base derived from salicylaldehyde and anthranilic acid have been synthesized. It was found that the Cu(II) “complexed ligand” readily reacts with CoCl₂ to form mononuclear Co(II) and binuclear oxygen bridged Co(II) complex [Co₂-L₂](H₂O)₂. The structure of the so prepared complexes was investigated using microchemical analysis, molar conductance measurements as well as electronic and vibrational spectral studies. It was concluded that in the Cu(II) binuclear complex, the Cu(II) ion inside the “complexed ligand” has a planar structure while the other Cu(II) ion is distorted away from planarity. In the Co(II) binuclear complex, the Co atom of the “complexed ligand” is distorted from tetrahedral structure when it coordinates to the second Co atom.     

Continuous flow analysis combined with a light-absorption ratio variation approach for determination of copper at ng/ml level in natural water.

The complexation between Cu(II) and naphthochrome green (NG) is very sensitive at pH 4.09 with the formation of complex ion [Cu(NG)2(H2O)2](2-). It can thus used for the determination of Cu(II) by the light-absorption ratio variation approach (LARVA) with a good selectivity. Both the ordinary detection procedure and continuous flow analysis (CFA) were carried out, where the latter is fit for continuous and rapid analysis of samples. The limit of detection (LOD) of Cu(II) is only 1 ng/ml, which is favorable for direct monitoring of natural water. About 30 samples could be analyzed per hour by CFA. Cu(II) contents in Yangtze River, West Lake, Taihu Lake of China and seawater near Shanghai were determined with satisfactory results. The CFA-LARVA spectrophotometry was the first to be coupled and it will play an important role in the in-situ analysis of natural water quality.     

Simultaneous determination of copper(II) and cobalt(II) by ion chromatography coupled with chemiluminescent detection.

In the absence of any special luminescent reagents, a weakly chemiluminescent emission was observed during the decomposition of hydrogen peroxide, catalyzed by transition-metal ions, such as Cu(II) and Co(II), in basic aqueous solution. The chemiluminescent intensity was significantly enhanced by the addition of ethyldimethylcetylammonium bromide and uranine. The signal-to-noise ratio (S/N) was proportional to the concentrations of Cu(II) and Co(II). Based on these phenomena, a flow-injection chemiluminescent method for the simultaneous separation and determination of Cu(II) and Co(II) was developed. The detection limits of the present chemiluminescent method for Cu(II) and Co(II) were 7.5 and 0.01 ng/ml, respectively. After ion chromatographic separation of Cu(II) and Co(II) by an IonPac CS5A column with oxalic acid and lithium hydroxide monohydrate as the eluent, the present chemiluminescent system was used as a post-column detector for these two transition metal ions in natural water samples.     

A fluorescent chemosensor for copper(II) based on a carboxylic acid-functionalized tris(2,2'-bipyridine)-ruthenium(II) complex.

In this research, bis(2,2'-bipyridine)(4-methyl-2,2'-bipyridine-4'-carboxylic acid)ruthenium(II).2PF(6)- complex (1), was first used as a fluorescent chemosensor to recognize Cu(II) in EtOH/H(2)O (1:1, v/v) solution. The response of the sensor is based on the fluorescence quenching of complex 1 by binding with Cu(II). The analytical performance characteristics of the proposed Cu(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Cu(II) with a linear range covering from 5.0 x 10(-8) to 1.0 x 10(-4) M and a detection limit of 4.2 x 10(-8) M. The experiment results show that the response behavior of 1 to Cu(II) is pH independent in medium condition (pH 4.0 - 8.0), and show excellent selectivity for Cu(II) over other transition metal cations.     

Synthesis of bis(amino alcohol)oxalamides and their usage for the preconcentration of trace metals by cloud point extraction.

C(2)-Symmetric two bis(amino alcohol)oxalamides (diamidediols) were synthesized and fully characterized. A new method was developed and successfully applied for the simultaneous preconcentration of both trace and toxic metals in water, by using C(2)-symmetric compounds. Under the optimum experimental conditions (i.e. pH = 10.0 +/- 0.2, 2.75 x 10(-3) mol L(-1) N,N'-bis[(1R)-1-ethyl-2-hydroxyethyl]ethanediamide (DAD1), 1.75 x 10(-3) mol L(-1) N,N'-bis[(1S)-1-benzyl-2-hydroxyethyl]-ethanediamide (DAD2), 0.10% w/v octylphenoxy-polyethoxyethanol (Triton X-114)), calibration graphs were linear in the range of 2.5 - 25.0 ng mL(-1) for Cu and Cd, 5.0 - 25.0 ng mL(-1) for Co and Ni. The enrichment factors were 18, 23, 18 and 20 for Cd, Cu, Co and Ni in the case of DAD1, respectively; 20, 22, 17 and 20 for Cd, Cu, Co and Ni in the case of DAD2. The limits of detection for DAD1 were found to be 0.45, 0.50, 1.25 and 0.60 ng mL(-1) for Cd, Cu, Co and Ni, respectively, and for DAD2 were found to be 0.44, 0.25, 0.60 and 1.55 ng mL(-1) for Cd, Cu, Co and Ni, respectively. The developed method was applied to the determination of Cu, Cd, Co and Ni in water samples and certified reference materials with satisfactory results.     

A fluorescent chemosensor for cobalt ions based on a multi-substituted phenol-ruthenium(II) tris(bipyridine) complex

An amide-linked 2,6-bis{[(2-hydroxy-5-tert-butylbenzyl)(pyridyl-2-methyl)-amino]-methyl}-4-methylphenol-ruthenium(II) tris(bipyridine) 2PF₆⁻ complex, 1, was first used to recognize Co(II) in EtOH/H₂O (1:1, v/v) solution, with the ruthenium(II) tris(bipyridine) moiety selected as a fluorophore and the multi-substituted phenol unit chosen as a receptor. The fluorescence quenching of 1 was attributed to the formation of an inclusion complex between multi-substituted phenol unit and Co(II) by 1:1 complex ratio (K = 2.5 × 10⁵), which has been utilized as the basis of the fabrication of the Co(II)-sensitive fluorescent chemosensor. The analytical performance characteristics of the proposed Co(II)-sensitive chemosensor were investigated. The sensor can be applied to the quantification of Co(II) with a linear range covering from 1.0 × 10⁻⁷ to 5.0 × 10⁻⁵ M and a detection limit of 5 × 10⁻⁸ M. The experiment results show that the response behavior of 1 to Co(II) is pH-independent in medium condition (pH 4.5–9.5) and show excellent selectivity for Co(II) over transition metal cations except Cu(II). The chemosensor has been used for determination of Co(II) in water samples.     

Determination of platinum metals complexes with 2-(6-methyl-2-benzothiazolylazo)-5-diethylaminophenol by reversed-phase high performance liquid chromatography

The use of 2-(6-methyl-2-benzothiazolylazo)-5-diethylaminophenolas a precolumn derivatizing reagent in the reversed-phase high performance liquid Chromatographic separation and determination of Ru(III), Rh(III), Os(IV), Ir(IV), Pt(II), Co(II), Ni(II) and Cu(II) is reported. When the mobile phase consists of methanol-water (76/24% v/v) and 20 mmol/l (pH 5.0) acetate buffer, the eight complexes can be separated within 35 min on a C₈ column. The detection limits are Ru 7.0, Rh 5.1, Os 1.5, Ir 7.6, Pt 3.7, Co 0.62, Ni 0.14 and Cu 1.2 ng/ml, respectively, at a signal-to-noise ratio of 3. RSDs were typically Ca. 1%.