Complexes de l'europium(II) avec les acides iminodiacétique et nitrilotriacétique en solution aqueuse

The dissociation constants of iminodiacetic acid and nitrilotriacetic acid have been determined in sodium perchlorate medium (μ = 0.5) at 25°. A potentiometric study of the europium(II) complexes of these acids has indicated the formation of 1:1 and 1:2 species; the formation constants have been determined. A MHA complex is formed in acidic medium in the presence of nitrilotriacetic acid. The polarographic reduction of europium(III) in the presence of these complexing acids is irreversible; in the presence of iminodiacetic acid, the reaction at the electrode is preceded by dissociation of the

complex.     

Complexing polymer sorbents and metal polymer complex catalysts with specially designed structure of active centres

A new approach to a problem of preparation, regulation of properties and formation of three-dimensional structure of complexing polymer sorbents and metal polymer complex catalysts with specially designed structure of active centres has been developed. The main principle is based on the use of “memory” of polymer composition and consists in prearrangement of macromolecules of initial complexing polymer or metal polymer complex catalyst to sorbing metal or hydrocarbon substrate followed by fixation of optimum for particular substrate conformation by intermolecular crosslinking. Using this principle a number of crosslinked complexing polymer sorbents and metal polymer complex catalysts containing phosphorylic, carboxylic, pyridine, amine and imine functional groups have been prepared. It has been shown that prearrangement leads to essential improvement of basic sorption and catalytic properties of the crosslinked complexing polymers - sorption capacity, the rate of uptake, selectivity and catalytic activity.     

Usage of Empore™ membrane in alcoholic media for copper(II) distribution studies

The sorption of copper(II) on a solid, iminodiacetic based, chelating material, the Empore™ membrane, in alcoholic solutions is considered. Determination of the acid-base properties, kinetic of metal sorption and complexing properties, in solutions with different percentages of ethanol, ranging from 0 to 40% is undertaken. The results are compared with those obtained using the classical iminodiacetic resin Chelex 100 in beads. No significant differences are found in the thermodynamic properties, but the kinetics of the metal sorption on the membrane is slower and a dependence of the process rate with the alcoholic content is observed. In the present investigation, the detection of copper(II) species both in alcoholic Italian distillate “grappa” and in its intermediate product (“flemma”), is carried out by the Resin Titration (RT) method using, as competitive reagent, the Empore™ membrane. To validate the procedure, synthetic solutions containing different percentages of ethanol are analysed.     

Design of Enzyme-like Complexing Polymer Sorbents and Metal-Polymer Complex Catalysts with Memory to Substrates

Summary: A new principle of design of enzyme-like complexing polymer sorbents and metal polymer complex catalysts has been developed. The principle is based on the use of memory of polymer composition and consists in conformational prearrangement of macromolecules of noncrosslinked complexing polymer favorable for sorbing metal ions and/or catalyzing substrate position followed by intermolecular crosslinking. It has been shown that prearranged polymer sorbents and catalysts demonstrate significantly improved sorption and catalytic properties.     

Palladium cluster catalysts supported on chelate resin-metal complexes

The dry beads of chelate resin-metal complexes have been prepared from metal ions and the chelate resin containing iminodiacetic acid moieties. The surface area of the chelate resin can be increased both by washing with an organic solvent miscible with water and by complexing with multi-valent cations. Palladium clusters are supported on the chelate resin-metal complexes by two methods, in which the order is reversed between “complexing of metal ions” and “supporting of palladium clusters”. The supported palladium clusters catalyze the hydrogenation of C=C bonds, and the catalytic activity greatly depends on the metal ions used for the complexation. In the case of typical metal ions, the complexing of metal ions after supporting of palladium clusters makes the surface area of the resin increase, but makes the catalytic activity decrease compared with the reverse order. In the case of lanthanoid ions, on the other hand, the same order makes both the surface area and the catalytic activity increase.     

Physicochemical properties of complexing para-substituted polystyrene sorbents containing functional amino groups

The acid-base properties of the analytical functional groups of complexing polymer sorbents based on aminopolystyrene and the sorption capacity of the sorbents were investigated. The influence of various substituents on the acid-base properties of the sorbents was studied.     

Use of complexing reagents as additives to the eluent for optimization of separation selectivity in high-performance chelation ion chromatography

This paper details a study of the selectivity characteristics of high-performance chelation ion chromatography when separating a range of metal ions with a number of complexing eluents. It shows that exploitation of competitive metal complexation between ligands in the eluent and surface bonded chelating groups allows a wide range of control over the retention order and selectivity coefficients of groups of metal ions for specific applications. An indication of the metal separation characteristics found for simple non-complexing eluents on iminodiacetic acid (IDA) silica bonded substrates is given first, followed by an illustration of the selectivity changes that can be achieved by using complexing eluents. Using a novel approach, plots of logbeta(1) of the metal complexes of a chosen eluent ligand against the surface bonded IDA metal complexes were found to be useful indicators of which metals may show unusual selectivity changes during separation. Example chromatograms of metal separations are given for three selected complexing eluent reagents, namely, oxalic acid, picolinic acid, and chloride, either singly or in admixture. For special mention it was found that very specific retention control could be achieved for Cu(II) with picolinic acid, Fe(III) and Fe(II) speciation with oxalic acid, Pb with dipicolinic acid and Cd with chloride.     

Semiconducting polymers based on charge-transfer complexes. III. Complexing and chemical stability of charge-transfer complexes in solution

10-Methylphenothiazine and p-(methylthio)anisole were compared to polymers which contained these donor molecules on the side chains of N-acyl-substituted polyethylenimines. Charge-transfer absorption spectra were compared for these donors with the acceptors: dichlorodicyanobenzoquinone, tetracyanoquinodimethane, tetracyanoethylene, and 2,4,5,7-tetranitrofluorenone. Benesi-Hildebrand plots show that the formation of the polymer complexes have 3 to 50 times higher equilibrium constants than those of the corresponding model complexes. This can be explained by complexing parallel to the polymer backbone. The polymer has the proper geometry for complexing (6.4 Å, repeat distance in the polymer backbone), and an acceptor molecule can therefore be inserted between two adjacent donor molecules for increased stability. Shifts of the absorption maxima to longer wavelength for some of the polymer complexes can be rationalized by the probability that in the polymer, an acceptor is sandwiched between two donors and thus forms 2:1 complexes; the extra resonance energy may shift the absorption maximum to longer wavelength. A second possible explanation is based on solvation of the complex which reduces the energy of the excited state. Polymers absorb mainly in the complex form. Model compounds absorb mainly by contact charge transfer, which is nonsolvated and thus occurs at higher energy or shorter wavelength. Extinction coefficients are higher for the model complexes than for the polymer complexes. Contact charge transfer, which can contribute in greater proportion to the model than to the polymer complexes, explains this. The amount of contact charge transfer can be calculated simply from the probability of a donor being in the solvent shell of an acceptor. Complex decomposition rates were determined based on measuring changes in the intensities of the charge-transfer absorption spectra. Dichlorodicyanoquinone complexes were unstable, while the other complexes were stable.     

Surface modification of synthetic and natural fibres by fixation of cyclodextrin derivatives

It is demonstrated that cyclodextrin derivatives can be fixed permanently onto polymer surfaces by functional groups using conventional technologies of textile processing. As a result of the modification process some properties of the fibres are directly influenced. But also special effects may be obtained by complexing specific chemical substances, because the fixed cyclodextrin cavities do not loose their complexing power. Conceivable fields of application are medical or technical textiles and textiles for clothing.     

Complexing Polymer Films in The Preparation of Modified Electrodes for Detection of Metal Ions

Summary: The complexing properties of poly (3-(pyrrol-1-yl)propylmalonic acid) (poly1) and poly(N,N′-ethylenebis[N-[(3-(pyrrole-1-yl)propyl) carbamoyl) methyl]-glycine (poly2) coated electrodes (C|poly1 and C|poly2) towards Cu(II), Pb(II), Hg(II) and Cd(II) cations using the open circuit chemical preconcentration-anodic stripping technique were studied. Sorption process of metal cations onto complexing surfaces was readily investigated through the combination of a chemical pre-concentration-anodic stripping technique with a Langmuir isotherm model. The modified electrodes were used for the voltammetric determination of Cu(II), Pb(II), Hg(II) and Cd(II) ions, giving low detection limits for Cu(II) (5 × 10⁻⁹ mol L⁻¹) and Pb(II) (5 × 10⁻¹⁰ mol L⁻¹). The ability of the modified electrodes to analyze Cu(II) ions in natural sample has been demonstrated by the analysis of a tap water sample. The results of the preconcentration process under competitive conditions clearly shows that the selectivity of complexing molecular electrode materials can be subtly tuned upon playing on the accumulation time, polymer thickness and/or memory effect of the binding polymers, opening up new avenues towards evolutive and efficient smart sensing materials.     

Determination des constantes de stabilite des complexes des lanthanides trivalents avec les macrocycles polyaza polycarboxyliques : Etude des Propriétés Complexantes de la Résine Chélatante Chelite-N vis-à-vis des Lanthanides Trivalents

(Determination of the stability constants of trivalent lanthanide complexes with polyazapolycarboxylic macrocycles. Study of the complexing properties of the chelating resin Chelite-N for trivalent lanthanides.)The complexing properties of the chelating resin Chelite-N, which is characterized by amidoxime-type functional groups, for neodymium and holmium are described. The conditioning of the resin, its chelating capacity and its acid-base properties are examined first. To evaluate the formation constants of trivalent lanthanide complexes with the chelating resin, the resin is equilibrated with the lanthanide ions and then with an aqueous solution of ethylenediaminetetraacetic acid.     

多嵌段聚醚氨酯脲为基质的新型高分子固态离子导体

本文合成了一系列聚乙二醇型多嵌段聚醚氨酯脲，而且用这类聚醚氨酯甩与高氯酸锂制得了一种新型的高分子固态离子导体复合物。在室温和50℃之间，其电导率比聚环氧乙烷为基质的固体电解质的高一到二个数量级，它还具有优良的综合性能。因此，对于室温薄膜蓄电池来说，这种新型的固体电解质是一类良好的候选材料。     

Copolymerisation alternee du methacrylate de methyle et du styrene complexes par du Chlorure de Zinc en milieu aqueux

In this paper we present some of our copolymerization results of methyl methacrylate with styrene in the presence of a complexing agent, zinc chloride. The reaction rates were studied as function of the level of complexing agent, water and time. It was found that the complexing agent level and the water level have opposite effect on the reaction yield, the reaction yield increasing as the level of the complexing agent is increased. The reaction time has also a positive effect on the yield. Using the interrelations between the various factors affecting the reaction an equation was derived; it relates the reaction yield with the following variables: monomers, complexing agent and water concentration as well as the reaction time. The experimental results were compared with theoretical values obtained from this equation and it showed a good fit.     

Synthesis,crystal structure and magnetic properties of [Mn(LH)2(H2O)2] n with a two-dimensional layered structure and three-dimensional hydrogen bonding network

A new manganese polymer [Mn(LH)₂(H₂O)₂] _n (LH₂ = iminodiacetic acid) (1) has been prepared and structurally and magnetically characterized. The polymer has a two-dimensional (2D) layered structure with the unique Mn atom on an inversion center, surrounded by six oxygen atoms. In each layer, all iminodiacetic acid entities are coordinated to Mn atoms in a bridging/bidentate mode, thus linking the [Mn(LH)₂(H₂O)₂] monomeric units together to form a 2D layered polymer. Hydrogen bonding is responsible for an extended three-dimensional network. Analysis of variable-temperature magnetic susceptibility data (2–300) K shows that the polymer displays weak antiferromagnetic exchange interaction with a coupling constant, J = –0.28 cm^–1.     

The influence of chitosan on cyclodextrin complexing and solubilizing abilities towards drugs

The present work was performed to investigate the effect of chitosan, a well known hydrophilic polymer with both enhancer and solubilizing properties, on the solubilizing and complexing abilities of cyclodextrins towards drugs. With this aim, phase-solubility studies were carried out with a series of model drugs, both of acid and basic nature and with different water-solubility and lipophilicity values, in the presence of chitosan and cyclodextrin (ß- or hydroxypropyl-ß-cyclodextrin), both separately (binary systems) and in combination (ternary systems). Unexpectedly, differently from the favorable effect reported in literature for various hydrophilic polymers, the addition of chitosan to the cyclodextrin complexation medium caused a decrease in the cyclodextrin complexing power towards all the examined drugs, independent from their very different physicochemical properties. On the contrary, the influence of the polymer on the cyclodextrin solubilizing efficiency was found to be dependent on the type of drug and both positive, or negative or non-significant effects were observed. The overall results are explained in terms of a common basic mechanism due to the presence of chitosan–cyclodextrin interactions, which hindered the drug–cyclodextrin complex formation, thus causing the binding constant reduction; the simultaneous presence of drug–chitosan and/or chitosan–(drug–cyclodextrin complex) interactions, different from drug to drug, were considered responsible for the distinct (and sometimes opposite) effects observed in the drug solubilizing efficiency of ternary systems.     

A Novel Biodegradable Carboxy‐Functional Lactose Copolymer

The synthesis of the first lactose main‐chain copolymer was achieved by means of solution polyreaction of ethylenediaminetetraacetic acid dianhydride with D ‐lactose. The water‐soluble carboxy‐functional material based on EDTA with a high molar mass is shown to be biodegradable. The metal complexing properties of the polymer based on the liquid‐phase polymer‐based retention (LPR) method showed a strong interaction with Cr(III), Fe(III), and Sr(II) ions.     

吸附树脂和离子交换树脂研究的新进展——介绍南开大学高分子化学研究所的部分工作

本文介绍了南开大学高分子化学研究所近年来在吸附树脂、离子交换树脂和某些具有络合基因的树脂的合成、性能和应用方面的最新研究成果。     

Hybrid polyion complex micelles formed from double hydrophilic block copolymers and multivalent metal ions: size control and nanostructure

Hybrid polyion complex (HPIC) micelles are nanoaggregates obtained by complexation of multivalent metal ions by double hydrophilic block copolymers (DHBC). Solutions of DHBC such as the poly(acrylic acid)-block-poly(acrylamide) (PAA-b-PAM) or poly(acrylic acid)-block-poly(2-hydroxyethylacrylate) (PAA-b-PHEA), constituted of an ionizable complexing block and a neutral stabilizing block, were mixed with solutions of metal ions, which are either monoatomic ions or metal polycations, such as Al(3+), La(3+), or Al(13)(7+). The physicochemical properties of the HPIC micelles were investigated by small angle neutron scattering (SANS) and dynamic light scattering (DLS) as a function of the polymer block lengths and the nature of the cation. Mixtures of metal cations and asymmetric block copolymers with a complexing block smaller than the stabilizing block lead to the formation of stable colloidal HPIC micelles. The hydrodynamic radius of the HPIC micelles varies with the polymer molecular weight as M(0.6). In addition, the variation of R(h) of the HPIC micelle is stronger when the complexing block length is increased than when the neutral block length is increased. R(h) is highly sensitive to the polymer asymmetry degree (block weight ratio), and this is even more true when the polymer asymmetry degree goes down to values close to 3. SANS experiments reveal that HPIC micelles exhibit a well-defined core-corona nanostructure; the core is formed by the insoluble dense poly(acrylate)/metal cation complex, and the diffuse corona is constituted of swollen neutral polymer chains. The scattering curves were modeled by an analytical function of the form factor; the fitting parameters of the Pedersen's model provide information on the core size, the corona thickness, and the aggregation number of the micelles. For a given metal ion, the micelle core radius increases as the PAA block length. The radius of gyration of the micelle is very close to the value of the core radius, while it varies very weakly with the neutral block length. Nevertheless, the radius of gyration of the micelle is highly dependent on the asymmetry degree of the polymer: if the neutral block length increases in a large extent, the micelle radius of gyration decreases due to a decrease of the micelle aggregation number. The variation of the R(g)/R(h) ratio as a function of the polymer block lengths confirms the nanostructure associating a dense spherical core and a diffuse corona. Finally, the high stability of HPIC micelles with increasing concentration is the result of the nature of the coordination complex bonds in the micelle core.     

Synthesis and Crystal Structure of a Two-dimensional Silver Framework Constructed by H2idc (H2idc = Iminodiacetic Acid)

1 INTRODUCTION Self-assembly supramolecular architectures are currently of great interest due to their intriguing net- work topologies and potential applications in micro- electronics, nonlinear optics, porous materials, and other applications[1]. However, the rational design of these materials is complicated because of the un- certain coordination propensity of metal ion, which is influenced by factors such as counter ion, solvent and ligand geometry[2]. Proper selection of metal ions an…     

Solvatation preferentielle dans les systemes ternaires polyvinylpyrrolidone/solvant halogene/solvant donneur de proton—III: Confrontation des resultats obtenus par diffusion de la lumiere et par spectroscopie infra-rouge

We have compared the experimental results of study of the preferential solvation of polyvinylpyrrolidone in halogenated solvent/proton-donor solvent mixtures, obtained by light scattering and i.r. spectroscopy and described in the two preceding papers. The preferential adsorption of the proton-donor solvent is explained by the formation of a hydrogen-bond complex of polymer with proton-donor solvent, on which other proton-donor molecules are bound by induced autoassociation. This complexing occurs even in mixtures where the “inert” solvent (1,2-dichloroethane) is preferentially adsorbed; this is experimental proof of a differing solvation of the chains in their close neighbourhood and within short range of them.