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.     

Use of tetracyanoplatinate (ii) for the luminescent detection of metalions

The tetracyanoplatinate(II) (TCP) ion forms insoluble fluorescent compounds with many metal ions. This property has not hitherto been exploited for analytical use. The soluble sodium TCP salt has been applied as a reagent for metal ion detection. Fluorescent precipitates useful for detection of the metal ions were obtained with Y(III), Zr(IV), Ag(I), Zn(II), Cd(II), Hg(I), Hg(II), A1(III), Pb(II), La(III) and Th(IV). Limits of detection ranged from 5 to 200 ppm. With ammonium acetate as a masking agent, selective detection of 10 ppm of silver was achieved in the presence of the other metal ions. As little as 20 ppm of zirconium can be detected in the presence of hafnium, which yields a non-fluorescent precipitate.     

Synthesis of porphyrin-incorporated polymers and their application for simultaneous detection of multimetal components by using spectrophotometry

For the purpose of detection of multimetal components in environment, alteration of the spectrophotometrical metal sensitivity of porphyrin was attempted. Two porphyrin-incorporated polymers were newly synthesized by the free radical copolymerization of protoporphyrin IX disodium salt and vinyl monomers, and their metal sensitivities were examined by measuring the difference absorption spectra. These porphyrin-incorporated polymers showed different metal sensitivities and their sensitivities were altered by change of pH. Three measuring reagents, which were different in the combination of the porphyrin-incorporated polymers and pH, were used for the simultaneous detection of multimetal components in metal ion mixtures. The difference spectra of these reagents showed the separate peaks corresponding to six metal ions, Bi(III), Co(II), Cu(II), Mn(II), Pb(II), and Zn(II). The spectra were acquired reproducibly by using standard normal variate (SNV) transformation. Furthermore, this method was applied to detect multimetal components in water samples such as tap water and industrial effluent.     

N-vinylcarbazole polymerization by 13X molecular sieve exchanged with Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)

The polymerization of N-vinylcarbazole by 13X molecular sieves modified by five different transition metal ions, viz. Mn(II), Co(II), Ni(II), Cu(II) and Zn(II), has been studied under various conditions. The order of reactivity follows the trend: Mn(II) ≈ Cu(II) > Co(II) > Zn(II) > Ni(II) at pH ∼ 3.55 and an exchange level of 30% of the metal ion. The polymerizations are believed to occur by a dual-ion-initiation mechanism in which both metal ions and proton centres participate. The overall energy of activation (E_a) for each system decreases with decreasing pH of the exchanging salt solution. Average activation energy on proton centre (E_H) and that on metal ion centre (E_a) have been evaluated for each system. E_a, E_H and E_c have been shown to correlate with one another. The molecular weights and their distributions are affected by the nature of the metal ion and also by the protonic centres. The possibility of a correlation of the catalytic activity of the modified 13X with ionic radius, electronegativity and normal co-ordination number has been examined.     

Determination of the glycosylation site of flavonoid monoglucosides by metal complexation and tandem mass spectrometry

Metal complexation and tandem mass spectrometry were used to differentiate C- and O-bonded flavonoid monoglucoside isomers. Electrospray ionization of solutions containing a flavonoid glycoside and a metal salt led to the generation of the key [M(II) (L) (L-H)](+) complexes, where M is the metal ion and L is the flavonoid glycoside. Thirteen flavonoid monoglucosides were examined in combination with Ca(II), Mg(II), Co(II), Ni(II), and Cu(II). Collisional activated dissociation (CAD) of the [M(II) (L) (L-H)](+) complexes resulted in diagnostic mass spectra, in contrast to the CAD mass spectra of the protonated, deprotonated, and sodium-cationized flavonoid glucosides. Five common sites of glycosylation could be predicted based on the fragmentation patterns of the flavonoid glucoside/magnesium complexes, while flavonoid glucoside/calcium complexes also were effective for location of the glycosylation site when MS(3) was employed. Cobalt, nickel and copper complexation had only limited success in this application. The metal complexation methods were also applied for characterization of a flavonoid rhamnoside, and the dissociation pathways of the metal complexes indicate that flavonoid rhamnosides have distinctive dissociation features from flavonoid glucosides.     

On-line coupling of supercritical fluid extraction with high-performance liquid chromatography for the determination of explosives in vapour phases

An investigation into the selectivity of an iminodiacetic acid (IDA) modified silica gel column for transition and heavy metal ions using non-chelating inorganic eluents has been carried out. A number of eluent parameters were investigated to determine the exact retention mechanism taking place and to control selectivity. The parameters studied were eluent ionic strength and the nature of the inorganic salt used, eluent pH and eluent temperature. The results obtained showed how despite certain metal ions exhibiting similar stability constants with the bonded IDA groups, careful control of each of the above parameters, in particular eluent chloride ion concentration and eluent temperature, could result in large changes in selectivity. Optimal conditions for the isocratic and gradient separation of Mg(II), Ca(II), Mn(II), Cd(II), Co(II), Zn(II) and Pb(II) were determined. An isocratic method using a 0.035 M KCl, 0.065 M KNO3 (pH 2.5) eluent was successfully applied to the determination of Mn(II), Cd(II), Co(II) and Zn(II) at concentrations between 20 and 121 microg/l in a freshwater certified reference material (NIST 1640).     

Growth of layered basic zinc acetate in methanolic solutions and its pyrolytic transformation into porous zinc oxide films

Photo-induced reduction of gold and platinum metal salt solutions was carried out using viologen graft copolymerized on low-density polyethylene (LDPE) films and viologen-containing poly(vinylidene fluoride) (PVDF-PVBV) microporous membranes. The effects of the UV irradiation time and concentration of the metal salt solutions on the metal ion reduction process and the resultant metal deposition on the polymeric substrates were investigated. The metal-polymer composites were characterized using X-ray photoelectron spectroscopy (XPS), scanning and transmission electron microscopy (SEM and TEM), atomic force microscopy (AFM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and UV-visible absorption spectroscopy. The amount of metal uptake, the state of the metal, and the size of the metal particles were found to be strongly dependent on the UV irradiation time and the type and concentration of the metal salt solution. The microporous structure and the high viologen content of the PVDF-PVBV membrane constitute an effective matrix for metal ion reduction and preparation of metal nanoparticles.     

Synthesis of narrowly size-distributed metal salt/poly(HEMA) hybrid particles in inverse miniemulsion: versatility and mechanism

Hybrid particles containing different hydrophilic metal salts such as tetrafluoroborates of iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), and nitrates of cobalt(II), nickel(II), copper(II), zinc(II), and iron(III), and cobalt(II) chloride were synthesized via inverse miniemulsion polymerization of 2-hydroxyethyl methacrylate (HEMA). All salts delivered narrowly size-distributed hybrid particles with the exception of iron(III), where only the nitrate salt could be successfully employed. The size and size distribution of the hybrid particles were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The particle morphology and the distribution of salt in the dried particles were observed by TEM. The influences of the type of metal salts and salt content on the particle size distribution were extensively investigated.     

Enhanced swelling and adsorption properties of AAm‐AMPSNa/clay hydrogel nanocomposites for heavy metal ion removal

Novel type hydrogel‐clay nanocomposites based on the acrylamide (AAm)‐ 2‐acrylamido‐ 2‐methylpropane sulfonic acid (AMPS) sodium salt and clay were synthesized via in situ copolymerization in aqueous solution. Samples were characterized by determining total basic group (TGB) content and swelling degree, XRD analysis, and FTIR spectroscopy. Effects of monomer ratio and clay amount on the swelling properties of the samples were investigated. It was found that the hydrogel/clay nanocomposites exhibited improved swelling capacity compared with the hydrogels. Samples were used to remove heavy metal ions (Cu (II), Cd (II), and Pb (II)) from aqueous solution in competitive and non‐competitive conditions for the first time. The effects of time and pH of the initial metal ion solution on the adsorption capacity were investigated and selectivity properties of the samples were evaluated. It was found that incorporation of a low amount of clay (10% (wt)) into the polymer structure increased the heavy metal ion adsorption capacity of the sample. It was concluded that the AAm‐AMPS/clay nanocomposites could be used as novel type, fast‐responsive, and high capacity sorbent materials in heavy metal removing processes. Copyright © 2007 John Wiley & Sons, Ltd.     

The use of amidoximated cellulose for the removalof metal ions and dyes from waste waters

The adsorption of metal ions such as Cu(II), Cr(III), Cd(II) and Ni(II)and dyes such as Acid Blue 25, Calmagite and Eriochrome Blue Black Bis performed onto amidoximated cellulose (Am-Cell). Different ways are possible for theadsorption of these pollutants onto Am-Cell : adsorption of each pollutantaloneon the support, or cumulative adsorption of both metal ions and dyes on the samesupport. In the last case, the pollutants may be adsorbed simultaneously from aunique solution, or successively from two different solutions, whatever theorder. Am-Cell loaded or not with metal ions shows a high capacity for dyeadsorption. Ternary complexes involving metal/dye/amidoxime are formed. Theobserved stoichiometries are 1/1/1 with Cu(II), Cr(III) and Cd(II) ions and1/1/2with Ni(II) ion. A quasi-total and specific desorption of either metal ions (bytreatment with ethylenediaminetetracetic salt) or of dyes (by heating inaqueoussolution) is possible from these ternary complexes. Concerning the dyes, manysuccessive adsorption/desorption cycles are possible without a noticeablechange in the adsorption capacity.     

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.     

Functional Water Soluble Polymers with Ability to Bind Metal Ions

Water-soluble polymers containing amine, carboxylic acid, and sulfonic acid groups were investigated as polychelatogens through the liquid phase polymer-based retention, LPR technique, under different experimental conditions. The metal ions investigated are: Ag(I), Cu(II), Co(II), Ni(II), Ca(II), Hg(II), and Cr(III). An important effect of the pH and the ligand type was observed on the metal ion retention. As the pH increases the metal ion retention increases. Two types of metal ion interactions are involved: coordination and electrostatic.     

Crystallographic analysis of metal-ion binding to human ubiquitin

The metal-binding ability of human ubiquitin (hUb) towards a selection of biologically relevant metal ions and complexes has been probed. Different techniques have been used to obtain crystals suitable for crystallographic analysis. In the first type of experiments, crystals of hUb have been soaked in solutions containing copper(II) acetate and two metallodrugs, Zeise salt (K[PtCl(3)(η(2)-C(2)H(4))]·H(2)O) and cisplatin (cis-[PtCl(2)(NH(3))(2)]). The Zeise salt is used in a test for hepatitis, whereas cisplatin is one of the most powerful anticancer drugs in clinical use. The Zeise salt readily reacts with hUb crystals to afford an adduct with three platinum residues per protein molecule, Pt(3)-hUb. In contrast, copper(II) acetate and cisplatin were found to be unreactive for contact times up to one hour and to cause degradation of the hUb crystals for longer times. In the second type of experiments, hUb was cocrystallized with a solution of copper(II) or zinc(II) acetate or cisplatin. Zinc(II) acetate gives, at low metal-to-protein molar ratios (8:1), crystals containing one metal ion per three molecules of protein, Zn-hUb(3) (already reported in previous work), whereas at high metal-to-protein ratios (70:1) gives crystals containing three Zn(II) ions per protein molecule, Zn(3)-hUb. In contrast, once again, copper(II) acetate and cisplatin, even at low metal-to-protein ratios, do not give crystalline material. In the soaking experiment, the Zeise anion leads to simultaneous platination of His68, Met1, and Lys6. Present and previous results of cocrystallization experiments performed with Zn(II) and other Group 12 metal ions allow a comprehensive understanding of the metal-ion binding properties of hUb with His68 as the main anchoring site, followed by Met1 and carboxylic groups of Glu16, Glu18, Glu64, Asp21, and Asp32, to be reached. In the case of platinum, Lys6 can also be a binding site. The amount of bound metal ion, with respect to that of the protein, appears to be a relevant parameter influencing crystal packing.     

Metal complexes of poly(acrylic acid): synthesis, characterization and thermogravimetric studies

Thermogravimetric studies of the sodium salt of poly(acrylic acid), its modified sodium salt and its various metal complexes were made. The thermal stabilities of the various systems decreased in the order: poly(acrylic acid) > Ni(II) > Co(II) > Zn(II) > Fe(III) > Cu(II) > polymeric sodium salt. The higher thermal stabilities of the polymer-metal complexes result from the development of stable ring structures in the polymer matrix upon coordination with metal ions. The metal-ion complexation of carboxylate ligands of linear poly(acrylic acid), optimization of the complexation conditions and infra-red and ultraviolet-visible spectrometric characterizations are also illustrated.     

Water-soluble Polyelectrolytes Contaning Sulfonic Acid Groups with Metal Ion Binding Ability by Using the Liquid Phase Polymer Based Retention Technique

Water-soluble polyelectrolytes from 2-acrylamido-2-methyl-1-propane sulfonic acid (APSA) were obtained by radical polymerization with different comonomers which contain weak acid and neutral groups. These copolymers were investigated as polyelectrolytes and polychelatogens, in view of their metal ion binding properties using the liquid-phase polymer-based retention (LPR) technique under different experimental conditions. The metal ions investigated were: Ag(I), Co(II), Cu(II), Zn(II), Cd(II), and Pb(II). APSA allowed increase metal ion interaction of weak acid, meanwhile did not improve the metal ion interaction of neutral monomers at these experimental conditions. Results indicated that retention capability depended strongly on the structure of the polyelectrolyte, arrangement of comonomers at main chain, pH, and the filtration factor, Z.     

Surface layer-by-layer chemical deposition reaction for thin film formation of nano-sized metal 8-hydroxyquinolate complexes

The feasibility of a novel and simple layer-by-layer chemical deposition method for the preparation of nano-sized metal 8-hydroxyquinolate complexes has been investigated and reported. Uniform nanocrystalline films have been synthesized via dipping a substrate alternately in metal ion solution followed by ligand solution. The stoichiometry of the as-grown anhydrous Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complex crystals were confirmed from the metal analysis and molar stoichiometric ratio of metal ion to 8-hydroxyquinoline. This was characterized as 1:2 for the Co(II), Ni(II), Cu(II) and Zn(II)–quinolate complexes. The Fe(III)–quinolate thin film was found to exhibit a 1:3 ratio. Electron impact-mass spectra (EI-MS) of all the synthesized thin film metal quinolate complexes were recorded and the results refer to the existence of the molecular ion peak at the corresponding m/z values. Confirmation of such stoichiometric 1:2 and 1:3 ratios were also evident from the (EI-MS) study. The deposited thin films were also subjected to analysis by a scanning electron microscope (SEM) and a particle size ?50 nm was detected. FT-IR and UV–Vis spectroscopy were further used to confirm the structure of the metal 8-hydroxyquinolate complexes. Thermal gravimetric analysis (TGA) was also used to follow up the possible thermal decomposition steps and to calculate the thermodynamic parameters of the nano-sized metal complexes.     

Oxidation of cyclohexane catalyzed by metal-ion-exchanged zeolites

The ion-exchange rates and capacities of the zeolite NaY for the Cu(II), Co(II), and Pb(II) metal ions were investigated. Ion-exchange equilibria were achieved in approximately 72 h for all the metal ions. The maximum ion exchange of metal ions into the zeolite was found to be 120 mg Pb(II), 110 mg Cu(II), and 100 mg Co(II) per gram of zeolite NaY. It is observed that the exchange capacity of a zeolite varies with the exchanged metal ion and the amount of metal ions exchanged into zeolite decreases in the sequence Pb(II) > Cu(II) > Co(II). Application of the metal-ion-exchanged zeolites in oxidation of cyclohexane in liquid phase with visible light was examined and it is observed that the order of reactivity of the zeolites for the conversion of cyclohexane to cyclohexanone and cyclohexanol is CuY > CoY > PbY. It is found that conversion increases by increase of the empty active sites of a zeolite and the formation of cyclohexanol is favored initially, but the cyclohexanol is subsequently converted to cyclohexanone.     

Synthesis,Spectral and Magnetic Studies of Mononuclear and Binuclear Mn(Ii), Co(Ii), Ni(Ii) and Cu(Ii) Complexes with Semicarbazone Ligands Derived from Sulfonamide

Mononuclear and binuclear Mn(II), Co(II), Ni(II) and Cu(II) complexes of new semicarbazone ligands derived from sulfonamide were synthesized and characterized by elemental analysis and IR spectra. In mononuclear complexes, the semicarbazone behaves as a monoanionic terdentate or neutral terdentate ligand towards the metal ion. However, in binuclear complexes, it behaves as a monoanionic terdentate towards one of the bivalent metal ions and monoanionic bidentate ligand towards the other metal ion in the same complex. Electronic spectra and magnetic susceptibility measurements of the solid complexes indicated octahedral geometry around Mn(II), Co(II) and Ni(II) and square planar around the Cu(II) ion. These geometries were confirmed by the results obtained from thermal analyses. The antifungus properties of the ligands and their complexes were investigated.     

Ordering double perovskite hydroxides by kinetically controlled aqueous hydrolysis

The precipitation of crystals with stoichiometric and ordered arrangements of distinct metal cations often requires carefully designed molecular precursors and/or sufficient activation energy in addition to the necessary mass transport. Here, we study the formation of ordered double perovskite hydroxides, MnSn(OH)(6) and CoSn(OH)(6), of the generic chemical formula, BB'(OH)(6) (no A site), using kinetic control of aqueous hydrolysis from simple metal salt solutions. We find that the precipitation yields ordered compounds only when the B ion is Mn(II) or Co(II), and not when it is any other divalent transition metal ion, or Zn(II). The key step in forming the compounds is the prevention of rapid and uncontrolled hydrolysis of Sn(IV), and this is achieved by a fluoride counteranion. The two compounds, MnSn(OH)(6) and CoSn(OH)(6), are studied by high-resolution synchrotron X-ray diffraction and from the temperature dependence of magnetic behavior. From maximum entropy image restoration of the electron density and from Rietveld analysis, the degree of octahedral distortion and tilting and the small extent of anti-site disorder are determined. From the nonoverlapping electron density, we infer strongly ionic character of bonding. As the first magnetic study of such materials, we report simple paramagnetic behavior with no long-range magnetic order down to 2 K for the Mn(II) compound, while the cobalt compound presents uncompensated antiferromagnetic interactions, attributed to the single-ion anisotropy of octahedral Co(II).     

Poly(N‐acetyl‐α‐acrylic acid): Synthesis,Characterization and Chelation Properties through Liquid Phase Polymer‐Based Retention Technique

The synthesis and characterization of the water‐soluble poly(N‐acetyl‐α‐acrylic acid) by radical polymerization were carried out. The polymer was characterized by Fourier Transform Infrared (FT‐IR), ¹H NMR and ¹³C NMR spectroscopies, and thermogravimetric analysis (TGA). The metal ion binding properties for the metals Cu(II), Co(II), Ni(II), Cd(II), Zn(II), Pb(II), Hg(II), Cr(III) in the aqueous phase were studied using the liquid‐phase polymer‐based retention technique. The metal ion interactions with the hydrophilic polymer were determined as a function of pH and of the filtration factor. The polychelatogen showed a high affinity for metal ions and higher selectivity for Cr(III) at pH = 3.