Competitive adsorption behavior of heavy metals on kaolinite

Polluted and contaminated soils can often contain more than one heavy metal species. It is possible that the behavior of a particular metal species in a soil system will be affected by the presence of other metals. In this study we have investigated the adsorption of Cd(II), Cu(II), Pb(II), and Zn(II) onto kaolinite in single- and multi-element systems as a function of pH and concentration, in a background solution of 0.01 M NaNO3. In adsorption edge experiments, the pH was varied from 3.5 to 10.0 with total metal concentration 133.3 microM in the single-element system and 33.3 microM each of Cd(II), Cu(II), Pb(II), and Zn(II) in the multi-element system. The value of pH50 (the pH at which 50% adsorption occurs) was found to follow the sequence Cu相似文献   

Mechanistic studies of metal ion binding to water-soluble polymers using potentiometry

A method for elucidating metal ion binding mechanisms with water-soluble polymers has been developed in which the polymer is treated as a collection of monomeric units. Data obtained from potentiometric titrations are analysed by the ESTA library of programs and apparent formation constants may be calculated. From this information, predictions may be made as to metal ion separation using complexation-ultrafiltration techniques. The polymer used in this study was Polymin Water-Free and its complexation with Hg(II), Cd(II), Pb(II), Co(II) and Ni(II) was successfully modelled.     

The reactions of diphenylcarbazide and diphenylcarbazone with cations : Part V. Extraction dissociation constants of the carbazone complexes

Extraction experiments in the system water-toluene on the diphenylcarbazone complexes of Mn(II), Fe(II) and (III). Co(II), Ni(II), Cu(ll), Zn(ll), Cd(II), Hg(I) and (II), Sn(II) and Pb(II) are described. Only uncharged complexes are formed, the formulae of which are for mercury HgD, Hg(HD)₂, Hg₂D and Hg₂(HD)₂ and for the other ions mentioned M(HD)_n, depending on the valence _n of the cation. The extraction dissociation constants, the molar extinction coefficients and the partition coefficients of the complexes funned by the cations studied were obtained, The complexes prove to be far less stable than the corresponding dithizone compounds so that diphenylcarbazone is less suitable for general analytical use than its sulphur analogue.     

Viscoelastic dilatation processes of fluid/fluid interfaces: time-domain representation

Dynamic interfacial phenomena are shown to be most satisfactorily interpreted within the general framework of the theory for system analysis. All time-dependent dilational behaviours of interfaces can be quantitatively predicted from knowledge of the dilational modulus, that is, of the transfer function of the interfacial system.The unifying mathematical formalism allows traditional experiments, known in the literature, to be connected one to another.The presented relationships are also the foundations of the transient techniques for the measurement of interfacial quantities.Problems involving diffusive surface relaxation in quiescent hydrodynamic conditions are easily analytically or numerically solved. Other complex relaxation mechanisms introduce no additional conceptual complication.     

Approach combining on-line metal exchange and tangential-flow ultrafiltration for in-situ characterization of metal species in humic hydrocolloids

This paper deals with the development and optimization of an analytical procedure using ultrafiltration and a flow-injection system, and its application in in-situ experiments to characterize the lability and availability of metal species in humic-rich hydrocolloids. The on-line system consists of a tangential flow ultrafiltration device equipped with a 3-kDa filtration membrane. The concentration of free ions in the filtrate was determined by atomic-absorption spectrometry, assuming that metals not complexed by aquatic humic substances (AHS) were separated from the complexed species (M–AHS) retained by the membrane. For optimization, exchange experiments using Cu(II) solutions and AHS solutions doped with the metal ions Ni(II), Mn(II), Fe(III), Cd(II), and Zn(II) were carried out to characterize the stability of the metal–AHS complexes. The new procedure was then applied in-situ at a tributary of the Ribeira do Iguape river (Iguape, São Paulo State, Brazil) and evaluated using the ions Fe(III) and Mn(II), which are considered to be essential constituents of aquatic systems. From the exchange between metal–natural organic matter (M–NOM) and the Cu(II) ions it was concluded that Cu(II) concentrations >485 μg L^?1 were necessary to obtain maximum exchange of the complexes Mn–NOM and Fe–NOM, corresponding to 100% Mn and 8% Fe. Moreover, the new analytical procedure is simple and opens up new perspectives for understanding the complexation, transport, stability, and lability of metal species in humic-rich aquatic environments.     

Selective separation of copper with Lix 864 in a hollow fiber module

The transfer and separation of Cu(II), Co(II), Ni(II) and Zn(II) ions across a hollow fiber supported liquid membrane containing LIX 864 as the mobile carrier dissolved in kerosene solvent has been investigated. The flux and selectivity for copper has been studied as a function of the feed flow, the carrier concentration in the liquid membrane and the extraction solution acidity. A maximum copper recovery at 30% of LIX (v/v) in the diluent was obtained. The permeation experiments showed that at pH 2 in the extraction solution a highly selective separation of Cu over the other cations can be achieved. Increasing the acidity of the extraction solution copper selectivity decrease and the grade of recuperation sequence is Cu>Co>Ni>Zn. These results suggest that in selected situations, this membrane system can be competitive with the conventional liquid-liquid extraction process, in particular in leaching solutions with low metal concentration.     

Mechanistic studies of Cu(II) binding to amyloid-beta peptides and the fluorescence and redox behaviors of the resulting complexes

Due in large part to the lack of crystal structures of the amyloid-beta (Abeta) peptide and its complexes with Cu(II), Fe(II), and Zn(II), characterization of the metal-Abeta complex has been difficult. In this work, we investigated the complexation of Cu(II) by Abeta through tandem use of fluorescence and electron paramagnetic resonance (EPR) spectroscopies. EPR experiments indicate that Cu(II) bound to Abeta can be reduced to Cu(I) using sodium borohydride and that both Abeta-Cu(II) and Abeta-Cu(I) are chemically stable. Upon reduction of Cu(II) to Cu(I), the Abeta fluorescence, commonly reported to be quenched upon Abeta-Cu(II) complex formation, can be regenerated. The absence of the characteristic tyrosinate peak in the absorption spectra of Abeta-Cu(II) complexes provides evidence that the sole tyrosine residue in Abeta is not one of the four equatorial ligands bound to Cu(II), but remains close to the metal center, and its fluorescence is sensitive to the copper oxidation state and perturbations in the coordination sphere. Further analysis of the quenching and Cu(II) binding behaviors at different Cu(II) concentrations and in the presence of the competing ligand glycine offers evidence supporting the operation of two binding regimes which demonstrate different levels of fluorescence recovery upon addition of the reducing agent. We provide results that suggest the fluorescence quenching is likely caused by charge transfer processes. Thus, by using tyrosine to probe the coordination site, fluorescence spectroscopy provides valuable mechanistic insights into the oxidation state of copper ions bound to Abeta, the binding heterogeneity, and the influence of solution conditions on complex formation.     

Automatic polarographic elucidation of electrode mechanisms by means of a knowledge-based system : Part 1. Sampled d.c. polarography

A knowledge-based system has been developed for the automatic elucidation of electrochemical mechanisms. The system is based on sampled direct current (or Tast) polarography at a dropping mercury electrode as a technique for collecting experimental information and consists of a general expert system shell for the reasoning process, the specific set of rules and experimental modules. The set of rules allows the elucidation of eight relatively simple electrode reaction mechanisms fully atomatically. The computer system has been validated with chemical systems the electrochemical behaviour of which is well established. All parts of the program are written in FORTH language for Apple II microcomputers. This expert system has an open character and new rules can be added to extend the set of mechanisms that can be determined.     

Fluorescence studies of the kinetics of binding and removal of metal ions in proteins

Fluorescence-quenching studies involving native protein fluorescence are used to monitor the rates of binding and removal of Hg(II), Cu(II), Ag(I), methylmercury(I), and p-chloro-mercuribenzoate in various protein systems (ovalbumin, bovine serum albumin, myoglobin, lysozyme, and insulin). In some cases, the fluorescence quenching as a function of time can be used to evaluate the rate constants for the binding of a particular metal ion to a protein. In many cases, multiple binding sites with different rate constants can be differentiated. The restoration of fluorescence vs. time on addition of various chelating agents (BAL, EDTA, cysteine and penicilamine) to the metal/protein system can be used to monitor metal ion removal. Multiple binding sites also can be differentiated kinetically in the removal experiments. In some cases, the appearance of multiple steps in the binding or removal or a metal or ion could be explained by small conformational changes. The rates of removal can help in estimating the effectiveness of various reagents as models for drugs in the treatment of heavy-metal poisoning.     

Metal Ion Controlled Self-Assembly of a Chemically Reengineered Protein Drug Studied by Small-Angle X-ray Scattering

Precise control of the oligomeric state of proteins is of central importance for biological function and for the properties of biopharmaceutical drugs. Here, the self-assembly of 2,2'-bipyridine conjugated monomeric insulin analogues, induced through coordination to divalent metal ions, was studied. This protein drug system was designed to form non-native homo-oligomers through selective coordination of two divalent metal ions, Fe(II) and Zn(II), respectively. The insulin type chosen for this study is a variant designed for a reduced tendency toward native dimer formation at physiological concentrations. A small-angle X-ray scattering analysis of the bipyridine-modified insulin system confirmed an organization into a novel well-ordered structure based on insulin trimers, as induced by the addition of Fe(II). In contrast, unmodified monomeric insulin formed larger and more randomly structured assemblies upon addition of Fe(II). The addition of Zn(II), on the other hand, led to the formation of small quantities of insulin hexamers for both the bipyridine-modified and the unmodified monomeric insulin. Interestingly, the location of the bipyridine-modification significantly affects the tendency to hexamer formation as compared to the unmodified insulin. Our study shows how combining a structural study and chemical design can be used to obtain molecular understanding and control of the self-assembly of a protein drug. This knowledge may eventually be employed to develop an optimized in vivo drug release profile.     

Mechanistic insight into N=N cleavage by a low-coordinate iron(II) hydride complex

The reaction pathways of high-spin iron hydride complexes are relevant to the mechanism of N2 reduction by nitrogenase, which has been postulated to involve paramagnetic iron-hydride species. However, almost all known iron hydrides are low-spin, diamagnetic Fe(II) compounds. We have demonstrated that the first high-spin iron hydride complex, LtBuFeH (LtBu = bulky beta-diketiminate), reacts with PhN=NPh to completely cleave the N-N double bond, giving LtBuFeNHPh. Here, we disclose a series of experiments that elucidate the mechanism of this reaction. Crossover and kinetic experiments rule out common nonradical mechanisms, and support a radical chain mechanism mediated by iron(I) species including a rare eta2-azobenzene complex. Therefore, this high-spin iron(II) hydride can break N-N bonds through both nonradical and radical insertion mechanisms, a special feature that enables novel reactivity.     

On the selectivity of the biomimetic oxidation of the saturated hydrocarbon 1,3-dimethyladamantane in a Gif-type system containing a Fe2+ salt, picolinic acid, and pyridine

The effects of the composition of a heterogeneous catalytic system based on Fe₂SO₄ · 7H₂O, picolinic acid (pyridine-2-carboxylic acid), and pyridine and system preparation procedures on the selectivity of oxidation of 1,3-dimethyladamantane (1,3-DMA) with an aqueous 30% hydrogen peroxide solution in an aqueous acetonitrile solvent at room temperature and ambient pressure were studied. The yields of 1,3-DMA oxidation products were increased from fractions of a percent in initial experiments to the tens of percent under new catalytic conditions of final experiments. It was found that three different mechanisms can occur in the test system under various conditions; conceivably, these are radical, ion-molecule, and radical-cation mechanisms. In the first case, a statistical mixture of the products of 1,3-DMA oxidation at tertiary and secondary C-H bonds was formed. In the second and third cases, oxidation occurred only at secondary and tertiary C-H bonds, respectively. Unlike the first two cases, the selectivity of 1,3-DMA oxidation to a tertiary alcohol under conditions of the Gif-type test system corresponds to the selectivity of biological oxidation and, to the best of our knowledge, is the first example of this kind.     

Generalized composite degradation kinetics for polymeric systems under isothermal and nonisothermal conditions

A composite degradation methodology is extended to the conversion-dependence function in order to explain the importance of multiple reaction mechanisms which might be considered to be involved in degradation processes. Based on two elementary reaction mechanisms, a specific form of the model equation is derived, which is capable of describing various types of degradation behavior showing sigmoidal rate as well as deceleratory rate. The conversion-dependence function is derived to be independent of the Arrhenius-type reaction constant or temperature, and thus the kinetic parameters are determined by analytic methods that have been developed for isothermal and dynamic-heating experiments without any modification or additional assumptions. The developed model equation is tested by predicting the isothermal master curve of polyether-ether-ketone (PEEK), which is used as a model system in this study. The activation energies of the model system are analyzed using comparable methods for isothermal and dynamic experiments, which compare favorably in terms of the activation energy as a function of conversion. The resulting model equation, based on the kinetic parameters determined by isothermal experiments, can accurately predict both isothermal and dynamic-heating thermogravimetry utilizing the same constants and identical reaction mechanisms without additional assumption.     

Use of methyliminodiacetic acid bound to cellulose for preconcentration and determination of trace-metal cations

Methyliminodiacetic acid immobilized on a cellulose support can be conveniently utilized for trace-metal uptake. Capacities and uptake yields as a function of pH have been evaluated for Pb(II), Cu(II), Mg(II), Ca(II), Cd(II), Zn(II), Co(II), Ni(II) and Hg(II) and the results compared with those predicted from the stability constants for the same systems in homogeneous solution. The immobilization of the ligand increases its co-ordinating ability. The applicability to speciation studies is considered.     

Electrochemical detection of scDNA cleavage in the presence of macrocyclic hexaaza-copper(II) complex

The hexaaza macrocyclic copper(II) complex Cu(II)L(L=1,8-Dihydroxyethyl-1,3,6,8,10,13-hexaazacyclotetradecane), which has octahedral structure similar to some natural complexes, is synthesized and purified. In this study, oxidative breakage DNA by the reaction of Cu(II)L with H2O2 and ascorbate has been investigated by gel electrophoresis experiments. In electrochemical experiments, the on scDNA-modified glassy carbon electrode(GCE) is cleaved by the Cu(II)L and redox changing of the metal catalyst without adding any other reagents. Above all, the need for concentration of scDNA is much lower than that of gel electrophoresis experiments and the process of the performance is easy. Furthermore, Cyclic Voltammetry (CV) and A.C. Impedance, which are performed to monitor scDNA cleavage at the scDNA-modified glassy carbon electrode (GCE), are fast, simple and highly efficient. The mechanism of the damage can be suggested: Fenton.     

Reverse flow injection analysis of complexing agents and its application to estimation of complexing capacity

A redox reaction of copper(II) with iron(II) proceeds slowly in the presence of neocuproine, although the reaction would not take place in its absence. This reaction is accelerated by the presence of complexing agents such as EDTA, DTPA, CyDTA, EDTA-OH, NTA, citrate, pyrophosphate, producing a copper(I)-neocuproine complex (lambda(max) = 454 nm). A reverse flow injection analysis (r-FIA) method is presented for the determination of trace amounts of complexing agents by measuring the increase in absorbance at 454 nm. Complexing agents at the 10(-6)M level can be determined at a rate of 120 samples/hr. By using this r-FIA system, a new procedure for the measurement of complexing capacity with metal ions such as Al(III), Cu(II), Zn(II), Cd(II) and Pb(II) has been developed. Complexing capacity for each metal ion can be measured at a rate of 120 samples/hr.     

The mechanism of the modified Ullmann reaction

The copper-mediated aromatic nucleophilic substitution reactions developed by Fritz Ullmann and Irma Goldberg required stoichiometric amounts of copper and very high reaction temperatures. Recently, it was found that addition of relatively cheap ligands (diamines, aminoalcohols, diketones, diols) made these reactions truly catalytic, with catalyst amounts as low as 1 mol% or even lower. Since these catalysts are homogeneous, it has opened up the possibility to investigate the mechanism of these modified Ullmann reactions. Most authors agree that Cu(I) is the true catalyst even though Cu(0) and Cu(II) catalysts have also shown to be active. It should be noted however that Cu(I) is capable of reversible disproportionation into Cu(0) and Cu(II). In the first step, the nucleophile displaces the halide in the LnCu(I)X complex forming LnCu(I)ZR (Z = O, NR′, S). Quite a number of mechanisms have been proposed for the actual reaction of this complex with the aryl halide: 1. Oxidative addition of ArX forming a Cu(III) intermediate followed by reductive elimination; 2. Sigma bond metathesis; in this mechanism copper remains in the Cu(II) oxidation state; 3. Single electron transfer (SET) in which a radical anion of the aryl halide is formed (Cu(I)/Cu(II)); 4. Iodine atom transfer (IAT) to give the aryl radical (Cu(I)/Cu(II)); 5. π-complexation of the aryl halide with the Cu(I) complex, which is thought to enable the nucleophilic substitution reaction. Initially, the radical type mechanisms 3 and 4 where discounted based on the fact that radical clock-type experiments with ortho-allyl aryl halides failed to give the cyclised products. However, a recent DFT study by Houk, Buchwald and co-workers shows that the modified Ullmann reaction between aryl iodide and amines or primary alcohols proceeds either via an SET or an IAT mechanism. Van Koten has shown that stalled aminations can be rejuvenated by the addition of Cu(0), which serves to reduce the formed Cu(II) to Cu(I); this also corroborates a Cu(I)/Cu(II) mechanism. Thus the use of radical clock type experiments in these metal catalysed reactions is not reliable. DFT calculations from Hartwig seem to confirm a Cu(I)/Cu(III) type mechanism for the amidation (Goldberg) reaction, although not all possible mechanisms were calculated.     

Capillary gas chromatographic analysis of highly brominated fire retardant compounds

We report the development of a capillary gas chromatographic method, superior to existing packed column methods, for the analysis of highly brominated additive fire-retardants, including decabromodiphenyl ether (1) and decabromodiphenoxyethane (II). Neither compound has been analyzed previously by capillary GC, and there are no published methods for (II). For (I), the new method is 5–10 times faster than an analogous packed column method, and it has 100 times lower detection limits and twice the precision of a gas chromatographic/mass spectrometric method. For (II), the capillary method is 30–50% faster than an unpublished liquid chromatographic method. The greater efficiency of the capillary method makes possible the complete resolution (R ≥ 1.25) of structurally very similar compounds (e.g. compound (II) and its Br₉Cl₁ and Br₈Cl₂ analogues). With the new method, commercial preparations of (I) and (II) can be rapidly analyzed, and samples from combustion and pyrolysis experiments can be evaluated for compositional changes.     

A continuous flow system design for simultaneous determination of heavy metals in river water samples

A new design of a continuous flow system applied to the simultaneous determination of the concentration of zinc(II), cadmium(II), lead(II), copper(II), nickel(II), cobalt(II) and chromium(VI) in river water is described. A flow cell made in the laboratory, which has been patented, based on a 'wall-jet' configuration with a three-electrode system is described. Optimum conditions for the determination of the metal ions are reported. The detection limits and relative standard deviation values were 4.01x10(-9) M and 0.078 for Zn(II), 1.76x10(-10) M and 0.056 for Cd(II), 4.69x10(-10) M and 0.134 for Pb(II), 2.29x10(-10) M and 0.138 for Cu(II), 1.61x10(-9) M and 0.093 for Ni(II), 1.91x10(-9) M and 0.113 for Co(II), and 1.35x10(-9) M and 0.081 for Cr(VI). The procedure was applied to a sample of water from the Arlanzón river and the results were compared with inductively coupled mass plasma spectrometry (ICP-MS) as reference method. The final aim of this work is to design a flow system, which can be automated.     

Multielement preconcentration of trace metals from natural waters by solvent extraction with an alkylated oxine derivative

Kelex 100, a commercially available alkylated oxine derivative, is shown to be effective, in purified form, for the simultaneous extraction of trace levels of Cd(II), Co(II), Cu(II), Mn(II), Ni(II), Pb(II), and Zn(II) from natural waters into toluene. The high lipophilicity of the extractant and its chelates affords large preconcentration factors in a single batch-extraction. Back-extraction with a small volume of nitric acid provides additional enrichment for subsequent determination of total (soluble) metal by graphite-furnace atomic-absorption spectrometry (GFAAS). Calibration with standard solutions can be used, which has advantages over the method of standard additions.