Copper Complexation with Soluble and Surface Freshwaters Ligands

Speciation of copper has been done using samples collected at different times of the year (December 92 and October 93) and in three sites of a polluted river (Este River, Northern Portugal). Filtered samples and the suspended particulate matter were titrated with metal ion and the labile metal concentrations measured by anodic stripping voltammetry (DPASV). An extra peak in the Cu voltammograms has been noticed when titrating filtered samples and its origin was investigated. Results have suggested that the extra peak is due to copper(I) stabilized by ligands adsorbed on the mercury electrode and a model for the electrochemical mechanism is proposed. From titrations of the same samples with zinc, cadmium and lead it has been concluded that there are two types of organics in the river water: macromolecules and small molecules with D_ML≈D_M with higher affinity for soft cations such as Cd(II) and Cu(I), that can be adsorbed on mercury electrode as anions.     

Labile metal content of sediments-fractionation scheme based on ion-exchange resins

The labile metal content of sediments can be evaluated by equilibrating sediment suspensions with ion-exchange resins. By use of a sequence of strong-acid and weak-acid cation-exchangers (H(+)- and Na(+)-form) and chelating resins, extraction can be performed at pH values ranging from 2 to 10. The results allow the total metal content to be subdivided into seven categories designated as (i) low-pH labile, (ii) weak-acid labile, (iii) exchangeable and readily desorbed at sediment-suspension pH, (iv) weak-base labile, (v) high-pH labile, (vi) non-labile soluble forms and (vii) detrital metal content. The sediment suspensions are mixed overnight with the different types of exchanger (held in porous containers) and the cations transferred from the sediment are subsequently back-extracted from the resins into 0.05M EDTA (pH 7.5). The EDTA extracts are analysed for Cu, Pb, Zn, Cd, Ca, Mg, Fe and Al. Analysis of the aqueous phase left in contact with the sediment residue gives the amount of non-labile species released. Eighteen sediments, containing various levels of metal contamination, and an effluent dam sludge have been examined by this technique. All the exchangers released Ca and Mg from the sediments, and the H(+)-form exchangers also released Fe and Al. Some of the Fe, Al and to a lesser extent Zn released by the sediment/exchanger interactions was present as non-labile "soluble" species. The advantages and limitations of this "labile metal" fractionation scheme have been considered.     

Voltammetric study of some macromolecule - metal complexes

The usefulness of a voltammetric model for studying macromolecule - metal complex systems is verified. Complexes formed by a metal ion (Zn(II), Cd(II), Pb(II) or Cu(II)) and a macromolecule (polymethacrylic (PMA), polyacrylic (PAA), alginic (AA) or polygalacturonic (PGA) acids) are investigated. Several voltammetric techniques have been used: sampled direct current polarography (DCP), normal pulse polarography (NPP), differential pulse polarography (DPP), reverse pulse polarography (RPP), cyclic voltammetry (CV) and differential pulse anodic stripping voltammetry (DPASV). Results confirm the validity of the model, in determining not only formation constants but also diffusion coefficients of the complexes. The behaviour of some systems agrees with that predicted by the model. Nonetheless, other systems only partially fulfil the predictions for different reasons, which are discussed.     

Application of potentiometric stripping analysis for speciation of copper complexes with a non-adsorbable ligand on a mercury electrode

Potentiometric stripping analysis (PSA) was used for determination of conditional stability constants (delta') of copper(II) complexes. Glycine was used as a model of a non-adsorbable ligand on the mercury electrode that forms well defined 1:1 and 1:2 copper(II)-glycine complexes, which are labile within the time scale of the analytical technique. The calculations were performed by the DeFord-Hume method, which was applied to the shifts in peak potential (dt/dE vs. E) provoked by the presence of different concentration of the ligand in the metal solution. For comparison purposes, the study was also carried out by differential pulse anodic stripping voltammetry (DPASV). The results obtained by PSA both at pH 6.0, logbeta'(1) = 5.0 +/- 0.2 and logbeta'(2) = 7.6 + 0.2, and at pH 6.5, logbeta'(1) = 5.7 +/- 0.6 and logbeta'(2) = 8.5 +/- 0.4 (standard deviations are given), were in agreement with those obtained by DPASV and from the literature, which indicates that PSA is suitable for this type of study.     

Symposium on Biomedical Polymers

ABSTRACT

Glycine functions were incorporated into 2–20 mol% N,N′-methylene-bis-acrylamide (NNMBA)-crosslinked polyacrylamides by transamidation with excess sodium salt of glycine. Complexation characteristics of glycine functions in different structural environments were investigated towards Co(II), Ni(II), Cu(II) and Zn(II) ions. The observed trend in complexation was found to be: Cu(II) > Ni(II) > Co(II) > Zn(II). The polymeric ligands and metal complexes were characterized by various spectral techniques. The polymeric ligands could be recycled several times and the metal ion desorbed resins showed specificity to the desorbed metal ion than other metal ions. This originates from the development of certain ‘pockets’ left by the desorbed metal ion or the ‘memory’ of the polymeric ligands for the desorbed metal ion. This lightly crosslinked systems showed much faster rebinding kinetics. The conditions of metal ion binding and rebinding were optimized to exploit the specific and selective separation of metal ions using metal ion desorbed systems. The specificity and selectivity characteristics depend on the degree of NNMBA crosslinking.     

Evaluation of metal fractions in river sediments and waters: application of chelation chromatography-differential pulse anodic stripping voltammetry

The ability of chelation chromatography in combination with differential pulse anodic stripping voltammetry (DPASV) to provide a simple, fast and reliable way of dealing with interionic interferences, competitive complexations, re-adsorption of released metal ions and sorption of spiking metal ions by organic/inorganic materials in the complex matrixes of real natural samples has been critically examined. The technique is based on the selective complexation of target metal fractions on some novel sorbents which are polymeric chelating resins doped on stationary supports (Whatman No. 1 paper and silica gel). The usual complications of leaching of the resin and/or the chelating ligand and colloid retention on the sorption bed at any stage of separation were largely obviated with these sorbents under the operational conditions of metal sorption. A detailed study on the application of such sorbents to the differentiation of ionic (free), labile (ionic plus weakly complexed) and bound (strongly complexed) metal fractions present in local river-sediment and water samples was carried out. Chelating resin-impregnated paper (CRIP) and chelating resin-immobilized silica gel column (CRISC) methods of chromatographic separation of analyte trace metals in combination with the follow-up 'standard addition' procedure of the DPASV technique were employed. A modest attempt has been made to formulate a speciation (fractionation) scheme for metal contents present in river-sediments and waters on the basis of selective retention of ionic and labile fractions on complexing resins.     

Evaluation of "labile" metal in sediments by use of ion-exchange resins

The metal content of a series of contaminated sediments has been determined by equilibrating ion-exchange resins of different types (held in porous cages) with aqueous suspensions of the sediments. H(+)-form exchangers took up high proportions of the Cu, Pb, Zn and Cd contents with recoveries depending on whether the acid functional groups were strong. Na(+)-form exchangers took up a smaller, loosely bound, labile fraction. The metal ions held on the exchangers were back-extracted into 0.05M EDTA and determined by flame AAS. Dissolution of sediment components led to the exchangers also taking up large amounts of Ca, Mg, Fe and Al. The exchange-resin technique provides an alternative means of subdividing the metal content of sediments into different "labile" or "available" fractions. Possible advantages include minimal re-adsorption of released metal ions by the sediment phases, retention of only "labile" species (ions or complexes), and a transfer mechanism which may resemble the action of plant roots more closely than chemical extractant processes do.     

Stripping Chronopotentiometry and Stripping Voltammetry of Mixtures of Heavy Metal Ions Producing Close Signals: The Cd(II)‐Pb(II)‐Phthalate System

The effects of the proximity of the signals of two heavy metal ions in stripping voltammetry (SV) and constant‐current stripping chronopotentiometry (SCP) is studied at mercury drop (HMDE) and mercury film (MFE) electrodes. For this purpose, the Cd(II)‐Pb(II)‐phthalate system is used, taking advantage of the approaching of the signals corresponding to Cd(II)‐phthalate and Pb(II)‐phthalate labile complexes as phthalate is added to mixtures of Cd(II) and Pb(II)‐ions. The results are compared with those obtained by differential pulse polarography (DPP) and by stripping measurements on the Pb(II)‐phthalate system alone, showing discrepancies in SCP data under nondepletive conditions and negligible differences in the other cases.     

Addressing lead toxicity: complexation of lead(II) with thiopyrone and hydroxypyridinethione O,S mixed chelators

The lead(II) ion is regarded as a serious environmental contaminant. A considerable need exists to develop selective ligands for remediation of this metal ion. Herein, the coordination chemistry of lead(II) is investigated with three O,S donor ligands: thiomaltol, 3-hydroxy-1-methyl-2(1H)-pyridinethione (3,2-HOPTO), and 3-hydroxy-1,2-dimethyl-4(1H)-pyridinethione (3,4-HOPTO). The X-ray structures of [Pb(thiomaltolato)(2)] and [Pb(3,4-HOPTO)(2)] have been solved, revealing the expected 4-coordinate geometries. Electronic spectra have been obtained for the lead(II) complexes with all three ligands. Preliminary solution studies show that the thiomaltol ligand binds lead(II) preferentially over magnesium(II) and calcium(II); however, [Pb(thiomaltolato)(2)] is not stable in the presence of 1 equiv of EDTA. Tetradentate ligands derived from these O,S chelators are expected to generate higher affinity ligands for lead(II) sequestration.     

EFFECT OF THE DEGREE OF DVB CROSSLINKING ON THE METAL ION SPECIFICITY OF POLYACRYLAMIDE-SUPPORTED GLYCINES

Metal ion specificity studies of divinylbenzene (DVB)-crosslinked polyacrylamide-supported glycines in different structural environments were investigated. The effect of the degree of crosslinking on the specific rebinding of the desorbed metal ion was investigated towards Co(II), Ni(II), Cu(II), and Zn(II) ions. The metal ion-desorbed resins showed specificity for the desorbed metal ion and the specificity characteristics increases with an increasing degree of the crosslinking agent. The polymeric ligands and metal complexes were characterized by IR, UV-visible and EPR spectra, and by SEM analysis. The swelling and solvation characteristics of the crosslinked polymers, polymeric ligands and metal complexes, the effect of the pH dependence on metal ion binding and rebinding and the kinetics of metal ion binding and rebinding were also followed. The complexation resulted in the downfield shift of the carboxylate peak in the IR spectra. The EPR parameters are in agreement with a distorted tetragonal geometry. The Cu(II) ion-desorbed resins selectively rebinds Cu(II) ions from a mixture of Cu(II) and Co(II) and Cu(II) and Ni(II) ions. The resin could be regenerated several times without loss of capacity and effective for the specific and selective rebinding of Cu(II) ions.     

Synthesis and Complexing Properties of <Emphasis Type="Italic">p</Emphasis>-Toluensulfonylamido and Phosphorylamido Derivatives of Second-Generation Hyperbranched Polyester

Hyperbranched polyesters containing terminal p-toluenesulfonylamido and diethoxyphosphorylamido groups have been synthesized, and their complexes with copper(II) and cobalt(II) ions have been prepared. The thermal stability of the ligands and their metal complexes has been studied by differential scanning calorimetry.     

Speciation of Cu(II) with a flow-through permeation liquid membrane: discrimination between free copper, labile and inert Cu(II) complexes, under natural water conditions

Metal toxicity is not related to the total metal ion concentration, but to those of some specific Cu(II) species. The Permeation Liquid Membrane technique is based on the carrier-mediated transport of the test metal across a hydrophobic membrane and enables discrimination between various trace metal species in solution. The present work shows how the labile and inert Cu(II) complexes can be determined selectively, by varying the flow-rate of the test solution, in a flow-through cell. A mathematical model of metal flux through the PLM, based on diffusion-limited transport under steady-state conditions, is described. The model and the performance of the technique were studied in well-defined synthetic solutions containing simple organic hydrophilic ligands forming either inert (nitrilotriacetic acid), or labile complexes with Cu(II) (tartaric acid, malonic acid). The results were compared with theoretical predictions of thermodynamic species distribution in solution. Uncertainties on stability constants for copper speciation calculation were taken into account. The detection limits of the device are discussed. This work demonstrates that the flow-through cell is a reliable tool for copper speciation measurements in natural waters.     

Subtractive differential pulse anodic stripping voltammetry at a stationary mercury-coated glassy carbon electrode

The application of subtractive mode differential pulse anodic stripping voltammetry (SDPASV) at a stationary mercury-coated glassy carbon electrode for the analysis of labile Zn(II), Cd(II), Pb(II) and Cu(II) is described. It is shown that the method has an improved sensitivity to Cu(II) owing to elimination of high background currents normally encountered in normal mode DPASV at the TFME. The sensitivity limits of the present method to Cd(II) and Cu(II) is estimated to be 0.025 and 0.067 ppb respectively, when a 2 min deposition time is used. It is suggested that the high sensitivity of the method coupled to the relative simplicity of the stationary electrodes could make the method useful in environmental and natural water studies.     

Mononuclear metal complexes of organic carboxylic acid derivatives: synthesis, spectroscopic characterization, thermal investigation and antimicrobial activity

Two Schiff base ligands bearing organic acid moiety, vis., N-(2-thienylmethylidene)-2-amino-4-chlorobenzoic acid (HL(1)) and N-(2-hydroxybenzylidene)-2-amino-4-chlorobenzoic acid (H(2)L(2)) have been synthesized by the interaction of 2-thiophenecarboxaldehyde and 2-hydroxybenzaldehyde with 2-amino-4-chlorobenzoic acid. Co(II), Ni(II), Cu(II) and Zn(II) complexes of these ligands have been prepared. They are characterized on the basis of analytical data, molar conductance, IR, (1)H NMR, UV-vis, mass spectra, magnetic measurements, thermal analysis and X-ray powder diffraction technique. The molar conductance data reveal that these complexes are non-electrolytes. The ligands are coordinated to the metal ions in a terdentate manner with ONO/ONS donor sites of the carbonyl oxygen, azomethine nitrogen and phenolic oxygen or thiophenic sulphur. An octahedral structure is proposed for the prepared metal complexes and some ligand field parameters (D(q), B and beta) in addition to CFSE were calculated. The thermal stability of the metal complexes is evaluated. The Schiff base ligands and their metal complexes have been tested against four species of bacteria as well as four species of fungi and the results have been compared with some known antibiotics.     

A new pyridine-based 12-membered macrocycle functionalised with different fluorescent subunits; coordination chemistry towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II)

The coordination chemistry of the new pyridine-based, N2S2-donating 12-membered macrocycle 2,8-dithia-5-aza-2,6-pyridinophane (L1) towards Cu(II), Zn(II), Cd(II), Hg(II), and Pb(II) has been investigated both in aqueous solution and in the solid state. The protonation constants for L1 and stability constants with the aforementioned metal ions have been determined potentiometrically and compared with those of ligand L2, which contains a N-aminopropyl side arm. The measured values show that Hg(II) in water has the highest affinity for both ligands followed by Cu(II), Cd(II), Pb(II), and Zn(II). For each metal ion considered, 1:1 complexes with L1 have also been isolated in the solid state, those of Cu(II) and Zn(II) having also been characterised by X-ray crystallography. In both complexes L1 adopts a folded conformation and the coordination environments around the two metal centres are very similar: four positions of a distorted octahedral coordination sphere are occupied by the donor atoms of the macrocyclic ligand, and the two mutually cis-positions unoccupied by L1 accommodate monodentate NO3- ligands. The macrocycle L1 has then been functionalised with different fluorogenic subunits. In particular, the N-dansylamidopropyl (L3), N-(9-anthracenyl)methyl (L4), and N-(8-hydroxy-2-quinolinyl)methyl (L5) pendant arm derivatives of L1 have been synthesised and their optical response to the above mentioned metal ions investigated in MeCN/H2O (4:1 v/v) solutions.     

Investigation of disulfonamide ligands derived from o-phenylenediamine and their Pb(II) complexes by electrospray ionization mass spectrometry

An electrospray ionization mass spectrometry (ESI-MS) method, in both positive and negative ion modes, was developed for characterization of disulfonamide ligands derived from o-phenylenediamine and their Pb(II) complexes. For the ligands, negative ion mode ESI-MS in methanolic solutions gave simple and easily interpretable mass spectra. However, the spectra of Pb complexes were not readily interpretable under the same conditions. Protonated ligands and their Pb(II) complexes were observed in methanolic solutions by ESI-MS in positive ion mode. The formation of Na(+), K(+), or NH(4) (+) adducts was also observed, complicating the mass spectra and decreasing the signal intensity. In order to optimize the detection of the ligands and the Pb complexes, a method was developed by adding NaOAc in the solutions. The presence of 0.2 mM NaOAc simplified the mass spectra of the ligands and the Pb complexes, and significantly increased sensitivity in both negative and positive ion modes. This modification makes ESI-MS in both modes suitable for characterization of sulfonamide ligands and their Pb complexes, thus providing a potentially powerful tool for evaluating formation of metal complexes and screening combinatorial ligand libraries.     

Rapid analysis of trace organics in aqueous solutions by enrichment in uncoated capillary columns

Summary A novel technique has been developed for the analysis of trace organics in aqueous solutions. Concentration of organics is effected by passage of the solution being analysed through uncoated plastic or metal capillaries as reported. The concentrated organics are then desorbed from the capillary using an organic solvent, and the desorbed solution is subsequently analysed by gas chromatography. Organics trapped inside a variety of columns have been recovered by solvent desorption in this manner using a number of different solvents, mixed solvents, different solvent volumes, different solvent flow rates through the capillary column and at different desorption temperatures, and the effects of these variables on the efficiency of desorption are discussed.     

Gas-phase study of the chemistry and coordination of lead(II) in the presence of oxygen-, nitrogen-, sulfur-, and phosphorus-donating ligands

Using a pickup technique in association with high-energy electron impact ionization, complexes have been formed in the gas phase between Pb(2+) and a wide range of ligands. The coordinating atoms are oxygen, nitrogen, sulfur, and phosphorus, together with complexes consisting of benzene and argon in association with Pb(2+). Certain ligands are unable to stabilze the metal dication, the most obvious group being water and the lower alcohols, but CS(2) is also unable to form [Pb(CS(2))(N)](2+) complexes. Unlike many other metal dication complexes, those associated with lead appear to exhibit very little chemical reactivity following collisional activation. Such reactions are normally promoted via charge transfer and are initiated using the energy difference between M(2+) + e(-) --> M(+) and L --> L(+) + e(-), which is typically approximately 5 eV. In the case of Pb(2+), this energy difference usually leads to the appearance of L(+) and the loss of a significant fraction of the remaining ligands as neutral species. In many instances, Pb(+) appears as a charge-transfer product. The only group of ligands to consistently exhibit chemical reactivity are those containing sulfur, where a typical product might be PbS(+)(L)(M) or PbSCH(3)(+)(L)(M).     

Heterogeneity and liability of Pb(II) complexation by humic substances: practical interpretation tools

The complexation of Pb(II) by natural organic matter (NOM) is better described by taking into account the dependence of the strength of binding on metal loading conditions. The utility of a linear differential equilibrium function for interpretation of metal ion binding data is demonstrated. This approach considers the binding intensity (log K*) as a function of metal ion loading (theta = bound metal/binding site concentration). Three methods for calculating this function are presented: -direct calculation from metal titration curves, -direct calculation from polarograms, and -compilation of data derived from interpretation of complexation in terms of one- or two- binding sites (e.g. Scatchard analysis), i.e. Cc (complexation capacity = effective site concentration)-K pairs. Heterogeneity also impacts on the apparent lability of complexes; complexes formed at the lowest metal loadings are the least labile.     

Effets stéréosélectifs dans les réactions des complexes métalliques. I. Stéréosélectivité de la réaction de l'anion D-N-(hydroxy-2-éthyl)-propylènediaminetriacétatoferrate (III) avec quelques dérivés d'acides aminés

A chromatographic method for studying small effects of ligand stereoselectivity in the formation of labile metal complexes has been developed. It is shown that unidentate ligands can react stereospecifically with labile optically active metal complexes. An anion-exchanger charged with an optically active form of Fe^III-N-(2-hydroxy-ethyl)-propylenediamine triacetate is used as a support in chromatography of N-acylated amino acids, and differences in retentions have been measured by elution and by frontal analysis.