Photolysis of oxygen saturated ethers in the presence of Sn(Ⅱ) or Cu(Ⅱ) salts

Photolysis of diethyl ether-oxygen charge transfer complex in the presence of Sn(Ⅱ)or Cu(Ⅱ)salts gave higher yields of the oxidation products,ethyl acetate,acetaldehyde,ethanol,ethyl formate and methanol compared with those without the salts.In addition,the photolysis of an oxygen saturated te-trahydrofuran(THF)or dibutyl ether solution gave y-butyro-lactone or butanol and butyl butyrate as major products with small amounts of undetermined compounds,respectively.Their yields were also affected by the addition of Cu(Ⅱ)or Sn(Ⅱ)salts.     

Analytical Separation of Copper(II), Cobalt(II) and Nickel(II) Using Polymer Bound Anthrantic Acid

Abstract

The preferential complexing tendency of different nietal ions towards chelating agents anchored on a polymer has been used for separation of transition metals. the anthranilic acid group was anchored on the polymeric cellulose back-bone by successive coupling with trifunctional reagent cyanuric chloride, in diozane medium, at pH 7 and 9–10, respectively. This polymer bound chelating agent was used to separate copper(II), nickel(II) and cobalt(II) in the concentration range 1.0–0.1 mmol/L. the separation of a mixture of two components was quantitative using column chromatography.     

Spectroscopic evaluation of Co(II), Ni(II) and Cu(II) complexes derived from thiosemicarbazone and semicarbazone

Co(II), Ni(II) and Cu(II) complexes were synthesized with thiosemicarbazone (L(1)) and semicarbazone (L(2)) derived from 2-acetyl furan. These complexes were characterized by elemental analysis, molar conductance, magnetic moment, mass, IR, electronic and EPR spectral studies. The molar conductance measurement of the complexes in DMSO corresponds to non-electrolytic nature. All the complexes are of high-spin type. On the basis of different spectral studies six coordinated geometry may be assigned for all the complexes except Co(L)(2)(SO(4)) and Cu(L)(2)(SO(4)) [where L=L(1) and L(2)] which are of five coordinated square pyramidal geometry.     

Acid Dissociation Behaviour and Complexation with Nickel(II), Copper(II) and Zinc(II) for Two Conformational Isomers of Dicyclohexylcyclam

Abstract

Acid dissociation constants for two conformational isomers of dicyclohexylcyclam, cis-anti-cis, (P) and cis-syn-cis, (N) have been determined at 25, 35 and 40°C, and thermodynamic data are estimated. It was found that (N) shows very different behaviour from (P). Stability constants of (P) and (N) toward Ni(II), Cu(II) and Zn(II) have been determined by pH-titration at 25°C by using a ligand exchange reaction. It is found that the (P) complex is more stable for Ni(II) and the (N) complex is more stable for Cu(II). Contributions of the cyclohexyl group to the macrocyclic effect (ME) have been also estimated by considering basicity corrections. It is found that substitution of the cyclohexyl group in cyclam increases ME only for the Ni(II) complex of (P).     

Synthesis and characterization of Cu(II), Co(II) and Ni(II) coordination polymers containing bis(imidazolyl) ligands

Two structurally related flexible imidazolyl ligands, bis(N-imidazolyl)methane (L₁) and 1,4-bis(N-imidazolyl)butane (L₂), were reacted with Cu(II), Co(II) and Ni(II) salts of aliphatic/aromatic dicarboxylic acids resulting in the formation of a number of novel metal–organic coordination architectures, [CuB₂(ox)₂(L₁)₂(H₂O)₂] · 4H₂O (1) (ox = oxalate), [Cu(pdc)(L₂)_1.5] · 4H₂O (2, pdc = pyridine-2,6-dicarboxylate), [Co(L)₂(H₂O)₂](tp) · 4H₂O (3, tp = terephthalate), [Ni(L₁)₂(H₂O)₂](ip) · 5H₂O (4, ip = isophthalate), [Cu₂(L₁)₄(H₂O)₄](tp)₂ · 7H₂O (5), [Co(mal)(L₁)(H₂O)] · 0.5MeOH (6, mal = malonate), [Co(pdc)(L₁)(H₂O)] (7). All the complexes have been structurally characterized by X-ray diffraction analysis. The different coordination modes of the dicarboxylate anions, due to their chain length, rigidity and diimidazolyl functionality, lead to a wide range of different coordination structures. The coordination polymers exhibit 1D single chain, ladder, 2D sheet and 2D network structures. The aliphatic and aromatic dicarboxylates can adopt chelating μ₂ and chelating-bridging μ₃ coordination modes, or act as uncoordinated counter anions. The central metal ions are coordinated in N₂O₄, N₄O₂, N₂O₃ and N₃O₃ fashions, depending on the ancillary ligands. The topology of 1 gives rise to macrocycles which are connected through hydrogen bonds to form 1D chains, whereas compound 2 exhibits a 1D polymeric ladder in which the carboxylate acts as a pincer ligand. Compounds 3–5 show doubly bridged 1D chains, and the dicarboxylate groups are not coordinated but form 2D corrugated sheets with water molecules intercalated between the cationic layers. Compound 6 has a 2D network sheet structure in which each metal ion links three neighboring Co atoms by the bis(N-imidazolyl)methane ligand. The cobalt compound 7, with a 2D polymeric double sheet structure, is built from pincer carboxylate (pdc) and 1,4-bis(N-imidazolyl)methane ligands.     

Polarographic Studies of the Reduction of Sn(II) in Dimethylsulphoxide and its Mixtures with Water and Acetonitrile

Abstract

The polarographic reduction of Sn(II) in DMSO, H₂O-DMSO and AN-DMSO mixtures was characterized as being reversible. When the reduction was carried out in an the process was found to be irreversible and in this case the kinetic parameters were determined by Meites and Israel's method. the effect of DMSO on the reduction of Sn(II) in an shows that the Sn(II) forms six successive complexes with DMSO, whose stability constants were determined by Deford and Hume's method.

The Walden product was determined for the mixtures under study. In AN-DMSO it decreases up to 20 vol.% DMSO, and from there remains approximately constant. In the H₂O-DMSO mixtures the Walden product passes through a broad minimum between 60 and 70 vol.% DMSO. the free energy of transfer in the hydro-organic mixture changes gradually with the increase in DMSO content, whereas in the AN-DMSO mixture this energy increases rapidly in very low DMSO content mixtures.     

A Novel Fluorescent Aminoacid Designed for Fluorometric Detection of Cu(II)

IntroductionIthasbeenwellknownthatα aminoacidcouldeffi cientlychelateCu(II) .1 3Applicationsbasedonthisnovelbindingcharacterhavebeenreported ,forinstance ,thechiraldiscriminationofD andL aminoacidsinaCu(II) cyclodextrincomplex4 ,5andtherecoveryofpyrenefluores cencebyaminoacidfromapyrene Cu (II) cyclodextrincomposite .6 ItwasthusenvisagedthatarationaldesignwouldleadtoanaminoacidderivativethatcouldworkasanovelligandforefficientdetectionofCu(II) .Acombina tionoftheaminoacidwithafluoropho…     

Complex Formation of Acetic Acid with Ca(II) and Mg(II) Under Physiological Conditions

Potentiometric titrations of aqueous acetic acid alone and in the presence of Ca(II) or Mg(II) ions have been carried out under physiological conditions at the temperature 37 °C and ionic strength 0.15 mol⋅dm⁻³ (NaCl) at different ligand-to-metal ratios. Changes in pH were monitored with a glass electrode calibrated daily in terms of the hydrogen ion concentrations. Titration data within the pH range 2.5 to 6.6 were analyzed to determine stability constants using the SUPERQUAD program. Different combinations of complexes were considered during the calculation procedure for both systems, but evidence was found only for mononuclear ML and ML₂ species. Speciation calculations based on the corresponding constants were then used to simulate the species’ distributions.     

Enhanced Removal of Cu(II) and Pb(II) from Aqueous Solutions by Pretreated Biomass of Fusarium Solani

This study investigated the feasibility of Fusarium solani biomass as a biosorbent for Cu(II) and Pb(II) removal from aqueous solutions. Batch sorption experiments were carried out for Cu(II) and Pb(II) to quantify the sorption kinetics, pH, biosorbent dose and pretreatment of F. solani biomass. Biomass metal uptake clearly competed with protons present in the aqueous medium, making pH an important variable in the process. The maximum biosorption by F. solani biomass was obtained with solutions having pH 5 for both metal ions. An enhanced Cu(II) removal (96.53%) was observed for aluminum hydroxide pretreated biomass. Maximum Pb(II) removal (95.48%) was observed with native biomass. Time dependence experiments for the metal ions uptake showed that adsorption equilibrium reached almost 240 min after metal addition. The kinetic studies showed that the biosorption process followed the pseudo second‐order rate model for Cu(II) and Pb(II). The equilibrium data fitted well to the Langmiur isotherm model.     

Simultaneous spectrophotometric determination of Sn(II) and Sn(IV) by mean centering of ratio kinetic profiles and partial least squares methods

Two spectrophotometric methods are described for the simultaneous determination of binary mixtures of Sn(II) and Sn(IV) in water samples and fruit juice samples, without prior separation steps, using the mean centering of ratio kinetic profiles and partial least squares (PLS) methods. The methods are based on the difference in the rate of the reactions of Sn(II) and Sn(IV) with pyrocatechol violet at pH 4.0. The methods allow rapid and accurate determination of Sn(II) and Sn(IV). The analytical characteristics of the methods for the simultaneous determination of binary mixtures of Sn(II) and Sn(IV) were calculated. The results showed that the methods were capable to simultaneous determination of 0.1–1.80 mg L⁻¹ each of cations. The proposed methods were successfully applied to the simultaneous determination of Sn(II) and Sn(IV)in an orange juice sample.     

A Novel Fluorescent Aminoacid Designed for Fluorometric Detection of Cu （Ⅱ）

A fluorescent aminoacid was designed for selective and sensitive detection of Cu(II) in aqueous solution. The designing of this Cu(II) fluorescent chemosensing molecule, N ± (1‐naphthyl). aminoacetic acid (NAA), was based on the binding of Cu(II) to aminoacetic acid and the novel charge transfer photophysics of 1‐aminonaphthalenes. The fluorescence of NAA was found quenched by Cu (II) and several other metal ions of similar electronic structure such as Co(II), Ni(II) and Zn(II). The quenching was shown to occur via electron transfer within the metal‐NAA complex, which required an optimal combination of high binding affinity and favorable redox properties of the components in the metal‐NAA complex and hence afforded selective fluorometric detection of Cu(II). The calibration graph obeyed Stern‐Volmer theory and was shown for Cu(II) over the range of 0–2.75 ± 10–⁴ mol/L. The quenching constant of Cu(II) was measured as 8.0 ± 10³ mol/L that was two orders of magnitude higher than those of Co(II), Ni(II) and Zn(II). The 3SD limit of detection for Cu(II) was 8.00 ± 10^?6 mol/L with a coefficient of variation of 1.65%. Linear range for quantitative detection of Cu(II) was 2.67 ± 10^?5‐2.75 ± 10^?4 mol/L. The method was applied to synthetic sample measurements which gave recoveries of 105%‐112%.     

Behavior of Copper (II) Ion to Inosine

Abstract

The DC polarographic behavior of the Cu(II)-inosine complex was investigated, in aqueous solutions of inosine in Britton Robinson buffer solutions at pH's from 1.0 to 4.0. At low concentrations of free inosine ion, only one polarographic wave was found corresponding to a two-electron reduction.

Anisotropy of g/ = 2,039, g// = 2,287 and A// = 172G, A/= OG, was observed in the ESR spectrum of the Cu(II)/inosine complex. When the composition ratio of the complex was obtained by both polarography and ESR, it was found that the ratio Cu(II) to inosine was 1:2. The polarographic wave showed a two electron reduction wave.     

Cathodic Processes in Cu(II) Solutions Containing Glycolic Acid

Voltammetric data for Cu|Cu(II), glycolic acid system, obtained at pH < 4 under potential sweep conditions, is analyzed within a theoretical model describing the mass transport of chemically interacting particles. Accounting for the distribution of the system's components at the electrode surface makes it possible to construct linear Tafel plots normalized to the surface concentration of Cu²⁺ ions, which are treated as electrically active aqua-complexes. The rate of Cu(II) reduction involving two consecutive reactions (Cu²⁺ + e Cu⁺ and Cu⁺ + e Cu) is controlled by the transfer of the first electron with kinetic parameters _c1 = 0.27 ± 0.01 and k _s1 = (1.2 ± 0.2) × 10^–3 cm/s. Another cathodic reaction is observed at higher cathodic polarizations. Well-defined current peaks located at ca. –0.9 V (SHE) increase with both H⁺ and ligand concentration. This process presumably results from the reduction of hydronium ions involving glycolic acid as a labile donor of protons.     

Thermal behavior of Cu(II)-, Cd(II)-, and Hg(II)-exchanged montmorillonite complexedwith cysteine

The thermal behavior of montmorillonite and organically modified montmorillonite, both treated with heavy metal cations [Cu(II), Cd(II) and Hg(II)], was characterized via thermal analyses (TG, DTG and DTA) combined with evolved species gas mass spectrometry (MS-EGA), and X-ray diffraction at in situ controlled temperature (HTXRD). The reactions involving Cu(II)- and Cd(II)-montmorillonite samples are mostly related to H₂O and OH loss, unlike Hg(II)-montmorillonite, where effects associated to Hg(II) loss are also present. Finally reactions related to dehydration, dehydroxylation and to organic matter decomposition can be observed in montmorillonite samples treated with cysteine.     

Effect of pH on Competitive Adsorption of Cu(II), Ni(II), and Zn(II) from Water onto Chitosan Beads

The amounts of adsorption of Cu²⁺, Ni²⁺, and Zn²⁺ from single, binary, and tertiary nitrate solutions onto glutaraldehyde cross-linked chitosan beads were measured. The beads had an average particle size and pore volume of 2 mm and 0.06 cm³/g, respectively, and had a BET surface area of 60 m²/g. All experiments were performed at 298 K as a function of initial pH (2.0–5.0), total metal concentration (0.77–17.0 mol/m³), and molar concentration ratio (0.25–4) in the aqueous phase. It was shown that the amount of metal adsorption generally increased with increasing solution pH. Competitive adsorption was significant in binary and tertiary systems when Cu²⁺ was present. The selectivity factor reached maximum in an equilibrium pH range of 5.1–5.3 and 4.5–4.9 for the Cu-Ni and Cu-Zn binary systems, respectively. This adsorbent provided a possibility for selective separation of Cu²⁺ from such multi-component solutions.     

Hetero-binuclear chelates of Mn(II), Co(II) and Cu(II) o-cresolphthalein complexonates with other metal ions

Heterobinuclear metal chelates of Mn²⁺, Co²⁺ or Cu²⁺ and some transition metal ions with o-cresolphthalein complexone have been prepared and characterized. Elemental analyses are in agreement with proposed formulae. Thermal analyses (TGA and DTA) were used to determine the degradation products; some thermodynamic parameters were calculated. IR and UV-Vis spectra identified the mode of bonding between the metal ions and the ligand as well as its geometry. Magnetic moment determination and ESR spectra of the heterobinuclear complex revealed some antiferromagnetic interaction between the metal ions, which depends mainly on the two metal ions forming the chelate. Electrochemical studies of the complexes [DC-polarography and cyclic voltammetry (CV)] confirmed the existence and the nature of the metal ions in the chelate.     

Simultaneous kinetic spectrophotometric determination of Cu(II), Co(II) and Ni(II) using partial least squares (PLS) regression

A partial least squares (PLS-1) calibration model based on kinetic—spectrophotometric measurement, for the simultaneous determination of Cu(II), Ni(II) and Co(II) ions is described. The method was based on the difference in the rate of the reaction between Co(II), Ni(II) and Cu(II) ions with 1-(2-pyridylazo)2-naphthol in a pH 5.8 buffer solution and in micellar media at 25°C. The absorption kinetic profiles of the solutions were monitored by measuring the absorbance at 570 nm at 2 s intervals during the time range of 0–10 min after initiation of the reaction. The experimental calibration matrix for the partial least squares (PLS-1) model was designed with 30 samples. The cross-validation method was used for selecting the number of factors. The results showed that simultaneous determination could be performed in the range 0.1-2 μg mL⁻¹ for each cation. The proposed method was successfully applied to the simultaneous determination of Cu(II), Ni(II) and Co(II) ions in water and in synthetic alloy samples.