Binding of metal ions by polyethylenimine and its derivatives

Measurements have been made of the binding of divalent metal ions, Cu²⁺, Ni²⁺, Co²⁺, and Zn²⁺ ions, by polyethylenimine (PEI) and its acetyl or alkyl derivatives by the equilibriumdialysis technique. These metal ions, in particular the Cu²⁺ ion, exhibited tremendously remarkable binding affinity toward PEI. The extent of complexation of the polymer with the metal ions was decreased markedly by acetylation or alkylation of the polymer. PEI with no primary amine showed an appreciable decrease in its affinity for the metal ion. These results indicate the participation of the primary amine of the polymer in the formation of the complex. A cooperative binding isotherm was observed in PEI–metal ion complex formation, suggesting swelling or conformational change of the polymer induced by this coordination process. Binding of the Cu²⁺ ion by PEI was found to be essentially independent of temperature over the range 5–35°C.     

Complexation of poly(ethyleneimine) with copper(II) and nickel(II) ions in 0.5 M KNO3 solution

Complexation of poly(ethyleneimine) (PEI) with copper(II) and nickel(II) ions was studied in a 0.5M aqueous KNO₃ solution. The potentiometrically determined logarithm of the three successive formation constants (log k_J) were 8.14, 7.96, and 7.37 for Cu⁺²-PEI complexation and 6.74, 6.52, and 6.23 for Ni⁺²–PEI complexation at 25°C, according to Bjerrum's modified method. The maximum average coordination number was 3.2 for the Cu⁺²–PEI system and 3.7 for the Ni⁺²–PEI system. An entropy effect was observed in the third coordination. The wavelengths of maximum absorption of the complexes and the continuous variation method showed that at least two coordination sites of Cu⁺² ion and three coordination sites of Ni⁺² ion were occupied immediately by PEI as the solutions of PEI and the metal ions were mixed.     

Preparation of Immobilized Metal Affinity Chromatographic Packings Based on Monodisperse Hydrophilic Non‐porous Beads and Their Application

Three hydrophilic immobilized metal affinity chromatographic packings for HPLC have been synthesized by chemical modification of 3.0 µm monodisperse non‐porous poly(glycidyl methacrylate‐co‐ethylenedimethacrylate) (P_GMA/EDMA) beads. The retention behavior of proteins on the metal ion chelated columns loaded with copper(II), nickel(II) and zin(II) ion was studied. The effect of pH on the protein retention was investigated on both the naked and metal ion chelated columns in the range from 4.0 to 9.0. Four proteins were quickly separated in 3.0 min with linear gradient elution at a flow rate of 3.0 mL/min by using the synthesized Ni²⁺‐IDA (iminodiacetic acid) packings. The separation time was shorter than other immobilized metal affinity chromatography reported in the literature. Purification of lysozyme from egg white and trypsin on the commercially available trypsin was performed on the naked‐IDA and Cu²⁺‐IDA columns, respectively. The purities of the purified trypsin and lysozyme were more than 92% and 95%, respectively.     

Self-optimization of binding sites by Ni(II) ion on carboxypyrazine-containing poly(ethylenimine)

To test the concept of self-optimization of own binding site by a metal ion, host molecules for Ni(II) ion were built on poly(ethylenimine) (PEI) by using the ethylenediamine portions of PEI and 2-carboxypyrazinyl (CP) group. Two derivatives of PEI containing CP were prepared: one by random acylation of PEI with pyrazine-2,5-dicarboxylic acid mono-(2,5-dioxo-pyrrolidin-1-yl) ester (PC-DP), and the other by acylation of PEI with PC–DP in the presence of Ni(II) ion. Between these two CP derivatives of PEI, Ni(II) binding ability was more than 10³ times greater for the latter. Optimization by Ni(II) ion of its own binding site built on the polymer was attributed to the preassemblage of PC–DP and PEI with Ni(II) ion and the subsequent attack at PC–DP by an amino group of PEI located in an optimal position. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 533–537, 1997.     

Fluorescence properties of polyacrylic acid derivative–Eu3+ ion–low molecular ligand complexes

The polyacrylic acid derivative, the copolymer (PABAM) of acrylic acid (AA) and p-benzoic acid acrylamide (BAM) were prepared by polymeric reaction. The coordinate structure of the polymer–Eu³⁺ complexes was characterized by X-ray photoelectron spectroscopy. The fluorescence intensity of the PABAM–Eu³⁺ complex was enhanced because of introduction of a BAM unit in the polyacrylic acid and reached a maximum when the mole ratio of AA to BAM was about 1 : 1. The ternary complexes of Eu³⁺–polymer–1,10-phenanthroline (PRL), or 2,2-bipyridine (BPD) were synthesized. The polymers used were PABAM and polyacrylic acid (PAA). The fluorescence intensity of the polymer–Eu³⁺ complexes was increased by 5∼21 times owing to the introduction of PRL and BPD.     

Purification of papain by metal affinity partitioning in aqueous two‐phase polyethylene glycol/sodium sulfate systems

A simple and inexpensive aqueous two‐phase affinity partitioning system using metal ligands was introduced to improve the selectivity of commercial papain extraction. Polyethylene glycol 4000 was first activated using epichlorohydrin, then it was covalently linked to iminodiacetic acid. Finally, the specific metal ligand Cu²⁺ was attached to the polyethylene glycol‐iminodiacetic acid. The chelated Cu²⁺ content was measured by atomic absorption spectrometry as 0.88 mol/mol (polyethylene glycol). The effects on the purification at different conditions, including polyethylene glycol molecular weight (2000, 4000, and 6000), concentration of phase–forming components (polyethylene glycol 12–20% w/w and sodium sulfate 12–20%, w/w), metal ligand type, and concentration, system pH and the commercial papain loading on papain extraction, were systematically studied. Under optimum conditions of the system, i.e. 18% w/w sodium sulfate, 18% w/w polyethylene glycol 4000, 1% w/w polyethylene glycol‐iminodiacetic acid‐Cu²⁺ and pH 7, a maximum yield of 90.3% and a degree of purification of 3.6‐fold were obtained. Compared to aqueous two phase extraction without ligands, affinity partitioning was found to be an effective technique for the purification of commercial papain with higher extraction efficiency and degree of purification.     

Fabrication of polymer‐modified magnetic nanoparticle based adsorbents for the capture and release of quinolones by manipulating the metal–coordination interaction

Functional polymers with a metal–coordination interaction have been fabricated for sample pretreatment. Poly(N‐4‐vinyl‐benzyl iminodiacetic acid‐co‐methacrylic acid‐co‐styrene)‐modified magnetic nanoparticles were prepared and used as solid‐phase extraction adsorbents for the analysis of quinolones by tuning the metal–coordination interaction. In the construction of the polymer‐based adsorbents, functional monomer (N‐(4‐vinyl)‐benzyl iminodiacetic acid) and comonomers (methacrylic acid and styrene) were fabricated onto the magnetic nanoparticles by free radical polymerization. Factors affecting the performance of the adsorbents were investigated, and the results revealed that Fe³⁺ played a vital role in the formation of metal–coordination adsorbents. Compared with other compounds, the resultant adsorbents displayed good selectivity to quinolones due to the metal–coordination complex (N‐4‐vinyl‐benzyl iminodiacetic acid‐Fe³⁺‐quinolones). Interestingly, the captured quinolones could be rapidly released by manipulating the metal–coordination interaction with Cu²⁺. The linearity range for analysis of the test quinolones was 0.025–2.0 μg/mL (R² > 0.999), and the recovery varied from 80.0 to 100.7%. Further, the proposed adsorbents were combined with high‐performance liquid chromatography for the analysis of quinolones in real urine samples. The results demonstrated that the prepared adsorbents have good selectivity and sensitivity for quinolones, showing great potential for drug analysis in real samples.     

NMR relaxation study of the reaction of 3-hydroxypyridine with macromolecules in solutions

The concentration dependences of the rates of¹³C nuclei spin-lattice relaxation in molecules of 3-hydroxypyridine (HP), pyridine (P), and phenol (Ph) in aqueous solutions of polyethylenimine (PEI) and polyacrylic acid (PAA) were obtained. The average complexing constants of HP with these polymers were calculated with the experimental data and the anisotropy of rotation of molecules of HP, P, and Ph in aqueous solutions and in complexes with PAA and PEI were determined. A comparative analysis of the change in the anisotropy of rotation of the molecules and efficiency of formation of hydrogen bonds by different groups was conducted. The expediency of using HP as a probe for studying the complexing capacity of different molecular groups in the chains of polymers was demonstrated.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2751–2756, December, 1990.     

Molecular Dynamics Simulations of Metal Ion Binding to the His‐tag Motif

In our previous study, we have observed that the chelation of various metal ions to the His‐tag motifs mostly involves the i and i+2 His residues for Ni²⁺, Cu²⁺, Zn²⁺ and Co²+. In the present study, various 200 ps molecular dynamics simulations were further conducted to investigate the chelating pathway of various metal ions to the His‐tag motif with 6 His residues (His‐tag6) and the binding affinities of these metal binding pockets towards these metal ions. The results indicate that His‐tag6 with the chelated metal ion located in positions His(2,4) or His(3,5) exhibits the strongest affinity for Ni²+ and Cu²+.K⁺ was found to be preferred to chelate in His(1,3) and His(3,5) coordinations. However, Fe³+ was found to have higher affinity towards His(1,3) and His(2,4) binding pockets. Our results also suggest that Ni²⁺ exhibits the highest binding affinity towards His‐tag6 over the other metal ions. Most of the structural variations of the His‐tag6 motif were from the Histidyl side chains during metal ion binding. In addition, there is an inverse linear correlation between the final chelated distance and the charge/volume ratio of metal ion. There is a negative correlation between the metal binding affinity and the averaged potential energy generated from the MD simulations.     

Water-Soluble Polyacids with Capability to Remove Metal Ions in Homogenous Phase by Using the Liquid Phase Polymer-Based Retention Technique

Water-soluble polymers containing carboxylic acid and sulfonic acid groups were investigated as polychelatogens under different experimental conditions in view to study their metal ion binding properties, using the liquid-phase polymer-based retention technique. The divalent metal ions investigated were: Co²⁺, Cu²⁺, Zn²⁺, and Cd²⁺. When the pH increased above 3, and especially at pH 5, metal ion retention capability increased as the majority of the functional groups are carboxylate, which can form more stable complexes with the metal ions. The retention capability also depended on the structure of the polyacid and the filtration factor, Z.     

Metal‐Chelated Polymer Nanodiscs for NMR Studies

Paramagnetic relaxation enhancement (PRE) is commonly used to speed up spin lattice relaxation time (T₁) for rapid data acquisition in NMR structural studies. Consequently, there is significant interest in novel paramagnetic labels for enhanced NMR studies on biomolecules. Herein, we report the synthesis and characterization of a modified poly(styrene‐co‐maleic acid) polymer which forms nanodiscs while showing the ability to chelate metal ions. Cu²⁺‐chelated nanodiscs are demonstrated to reduce the T₁ of protons for both polymer and lipid‐nanodisc components. The chelated nanodiscs also decrease the proton T₁ values for a water‐soluble DNA G‐quadruplex. These results suggest that polymer nanodiscs functionalized with paramagnetic tags can be used to speed‐up data acquisition from lipid bilayer samples and also to provide structural information from water‐soluble biomolecules.     

Selective extraction and release using (EDTA-Ni)-layered double hydroxide coupled with catalytic oxidation of 3,3′,5,5′-tetramethylbenzidine for sensitive detection of copper ion

Copper is an important heavy metal in various biological processes. Many methods have been developed for detecting of copper ions (Cu²⁺) in aqueous samples. However, an easy, cheap, selective and sensitive method is still desired. In this study, a selective extraction-release-catalysis approach has been developed for sensitive detection of copper ion. Ethylenediaminetetraacetic acid (EDTA) chelated with nickel ion (Ni²⁺) were intercalated in a layered double hydroxide via a co-precipitation reaction. The product was subsequently applied as sorbent in dispersive solid-phase extraction for the enrichment of Cu²⁺ at pH 6. Since Cu²⁺ has a stronger complex formation constant with EDTA, Ni²⁺ exchanged with Cu²⁺ selectively. The resulting sorbent containing Cu²⁺ was transferred to catalyze the 3,3′,5,5′-tetramethylbenzidine oxidation reaction, since Cu²⁺ could be released by the sorbent effectively and has high catalytic ability for the reaction. Blue light emitted from the oxidation product was measured by ultraviolet–visible spectrophotometry for the determination of Cu²⁺. The extraction temperature, extraction time, and catalysis time were optimized. The results showed that this method provided a low limit of detection of 10 nM, a wide linear range (0.05–100 μM) and good linearity (r² = 0.9977). The optimized conditions were applied to environmental water samples. Using Cu²⁺ as an example, this work provided a new and interesting approach for the convenient and efficient detection of metal cations in aqueous samples.     

Modeling manganese removal in chelating polymer-assisted membrane separation systems for water treatment

The removal of manganese from groundwater, using water-soluble chelating polymers such as polyacrylic acid (PAA) in combination with ultrafiltration (UF), was investigated. The effects of the solution pH and polymer dosages on the manganese removal were evaluated, and the removal efficiency was modeled considering the relevant chemical equilibria. In the absence of polymer, manganese removal with UF membranes alone was negligible at acidic pH values, but the removal increased substantially when polyacrylic acid (PAA) was added to the feed solution. The increase can be attributed to the formation of Mn²⁺–PAA chelates which are rejected by the membranes. A mathematical model was developed to explain this phenomenon based on chemical equilibria, including complex formation and precipitation. The chelation number (i.e., the number of carboxyl groups in the PAA binding to a single metal ion) and the equilibrium constants for metal–PAA chelation reactions were obtained by fitting experimental data at acidic pH in single-divalent metal systems. The model was able to predict Mn removal in chelation/UF systems at various pH levels and polymer dosages, and to account for the competitive interactions of PAA with the target (Mn²⁺) and background species (Ca²⁺, Mg²⁺) in multi-component systems. The predicted Mn removal efficiency was most sensitive to the chelation number.     

Preparation and reactivity of metal containing monomers

The preparation of HTSC ceramics based on Y^III and Bi^III was studied. The polymers were obtained by two methods: by the reaction of preliminarily synthesized polyacrylic acid (PAA) or polyacrylamide (PAAm) with Y^III, Ba^II, and Cu^II nitrates or by copolymerization of metal containing monomers (metal (Y^II, Ba^II, and Cu^II) acrylates or acrylamide complexes of metal (Bi^III, Ca^II, Sr^II, Pb^II, and Cu^II) nitrates). The copolymerization was carried out in solution, in the solid phase, or using spontaneous polymerization, which has been previously discovered by the authors. The properties of the HTSC ceramics obtained are improved when the products of copolymerization of metal containing monomers are used.For part 41, seeIzv. Akad. Nauk, Ser. Khim., 1995, 885 [Russ. Chem. Bull., 1995,44, 858 (Engl. Transl.)].Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1096–1101, June, 1995.The authors wish to thank V. N. Topnikov and M. K. Makova for measuring the characteristics of HTSC ceramics and V. A. Zhorin for conducting copolymerization of metal containing monomers under high pressures combined with shear strains.The work was carried out with financial support of the International Science Foundation (Grant NJB 000).     

Simultaneous dual wavelength spectrophotometric determination of citric and ascorbic acids using an artificial neural network

In this study, a very simple spectrophotometric method for the simultaneous determination of citric and ascorbic acid based on the reaction of these acids with a copper(II)-ammonia complex is presented. The Cu²⁺-NH₃ complex (with λ_max = 600 nm) was decomposed by citrate ion and formed a Cu²⁺-citrate complex (with λ_max = 740 nm). On the other hand, during the reaction of ascorbic acid with copper(II)-ammonia complex, ascorbic acid is oxidized and the copper(II)-ammonia complex is reduced to the copper(I)-ammonia complex and the absorbance decreases to 600 nm. Although there is a spectral overlap between the absorbance spectra of complexes Cu²⁺-NH₃ and Cu²⁺-citrate, they have been simultaneously determined using an artificial neural network (ANN). The absorbances at 600 and 740 nm were used as the input layer. The ANN architectures were different for citric and ascorbic acid. The output of the citric acid ANN architecture was used as an input node for the ascorbic acid ANN architecture. This modification improves the capability of the ascorbic acid ANN model for the prediction of ascorbic acid concentrations. The dynamic ranges for citric and ascorbic acid were 1.0–125.0 and 1.0–35.0 mM, respectively. Finally, the proposed method was successfully applied to the determination of citric and ascorbic acids in vitamin C tablets and some powdered drink mixes. The text was submitted by the authors in English.     

Concentration–polarization effect of poly(sodium styrene sulfonate) on size distribution of colloidal silver nanoparticles during diafiltration experiments

Polyelectrolyte (PEL)-based dual systems and nanoparticles (NPs) are two topics which have generated great interest as a result of their many and novel applications. Here, PEL–NPs system which appears transitorily when a high molecular weight PEL solution is mixed with metal NP colloidal dispersions during diafiltration is studied. The aim of this paper was to analyze the concentration–polarization effect of PEL molecules on size distribution of NPs capable to pass through the ultrafiltration membrane. Poly(sodium styrene sulfonate) (PSSNa) and silver nanoparticles (AgNPs) were used as PEL and metal NP colloidal dispersion, respectively. It was seen that particle size decreased from 42.4?±?37.8 to 10.1?±?0.7 nm in the presence of PSSNa and concentration–polarization. In addition, our results indicate that polarization–concentration phenomenon can be used to modify the size distribution of NP colloidal dispersions, that by changes of polarization–concentration features is possible the modification of NP size in the permeate during diafiltration experiments and that in presence of concentration–polarization, PSSNa was only a modifier factor of medium. In addition, it was observed that exclusion size of ultrafiltration membrane is an important element for establishing of particle size in the permeate.     

Studies on the oxygen atom transfer reactions of peroxomonosulfate: Oxidation of glycolic acid

The kinetics of oxidation of glycolic acid, an α‐hydroxy acid, by peroxomonosulfate (PMS) was studied in the presence of Ni(II) and Cu(II) ions and in acidic pH range 4.05–5.89. The metal glycolate, not the glycolic acid (GLYCA), is oxidized by PMS. The rate is first order in [PMS] and metal ion concentrations. The oxidation of nickel glycolate is zero‐order in [GLYCA] and inverse first order in [H⁺]. The increase of [GLYCA] decreases the rate in copper glycolate, and the rate constants initially increase and then remain constant with pH. The results suggest that the metal glycolate ML⁺ reacts with PMS through a metal‐peroxide intermediate, which transforms slowly into a hydroperoxide intermediate by the oxygen atom transfer to hydroxyl group of the chelated GLYCA. The effect of hydrogen ion concentrations on k_obs suggests that the structure of the metal‐peroxide intermediates may be different in Ni(II) and Cu(II) glycolates. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 41: 160–167, 2009     

Competitive heavy metal removal by poly(2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid‐co‐itaconic acid)

The competitive removal of Pb²⁺, Cu²⁺, and Cd²⁺ ions from aqueous solutions by the copolymer of 2‐acrylamido‐2‐methyl‐1‐propane sulfonic acid (AMPS) and itaconic acid (IA), P(AMPS‐co‐IA), was investigated. Homopolymer of AMPS (PAMPS) was also used to remove these ions from their aqueous solution. In the preparation of AMPS–IA copolymer, the molar percentages of AMPS and IA were 80 and 20, respectively. In order to observe the changes in the structures of polymers due to metal adsorption, FTIR spectra by attenuated total reflectancetechnique and scanning electron microscopy (SEM) pictures of the polymers were taken both before and after adsorption experiments. Total metal ion removal capacities of PAMPS and P(AMPS‐co‐IA) were 1.685 and 1.722 mmol Me²⁺/g_polymer, respectively. Experimental data were evaluated to determine the kinetic characteristics of the adsorption process. Competitive adsorption of Pb²⁺, Cu²⁺, and Cd²⁺ ions onto both PAMPS and P(AMPS‐co‐IA) was found to fit pseudo‐second‐order type kinetics. In addition, the removal orders in the competitive adsorption of these metal ions onto PAMPS and P(AMPS‐co‐IA) were found to be Cd²⁺ > Pb²⁺ > Cu²⁺ and Pb²⁺ > Cd²⁺ > Cu²⁺, respectively. Copyright © 2008 John Wiley & Sons, Ltd.     

Self-assembly of inner skin hollow fiber polyelectrolyte multilayer membranes by a dynamic negative pressure layer-by-layer technique

In the past studies, electrostatic layer-by-layer (LbL) adsorption of oppositely charged polyelectrolytes has proven to be a promising method for the preparation of polyelectrolyte multilayer membranes (PEMMs). Till now, this method was mainly used to assemble flat sheet and tubular membranes. Since hollow fiber membrane has some advantages such as high-packing density, self-contained mechanical support and hence the consequent economical superiority, this study therefore seeked to assemble inner skin hollow fiber PEMMs by using a dynamic LbL adsorption technique. The assembly process was successfully accomplished by alternatively dynamically filtrating polyacrylic acid (PAA) and polyethyleneimine (PEI) on a hydrolyzed hollow fiber polyacrylonitrile (PAN) membrane under a negative pressure condition. In the case of pervaporation separation of 95 wt.% ethanol–water mixture (50 °C), the membrane obtained with only 4.5 and 6.5 bilayers had separation factor of 245 and 1338 while the permeate fluxes were 290 and 120 g/(m² h), respectively. The pervaporation separation behavior of various alcohol/water mixtures with the alcohols being t-butanol, 2-propanol and ethanol were also investigated. Finally, scanning electron microscopy and atomic force microscopy clearly confirms a uniform and defect-free layer formed on the inner surface of hollow fiber support. Since different polyelectrolyte pairs could be used to assemble PEMMs for different uses, it was expected that the dynamic negative pressure LbL adsorption technique could also potentially be used to prepare many types of PEMMs in other fields.     

PREPARATION AND CHARACTERIZATION OF POLYSULFONE AND POLYETHERSULFONE MEMBRANES FOR CALCIUM (Ca2+) AND MAGNESIUM (Mg2+) SEPARATION BY COMPLEXATION ULTRAFILTRATION

ABSTRACT

Asymmetric ultrafiltration membranes were synthesized from locally available polysulfone and polyethersulfone polymers using aprotic solvents and organic additives by the phase inversion method. The membranes were characterized in terms of pure water permeability, separation behavior with respect to polyethylene glycols of various molecular weights and electrolytes. The suitability of using polyethyleneimine (PEI) for selective removal of calcium and magnesium salts by an ultrafiltration process was studied in terms of optimum polymer loading at reasonable permeate flux, irreversible adsorptive fouling of the macromolecular ligand on the polymer as functions of solution pH and ionic strength, and metal ion separation as a function of concentration and pressure. Direct electron microscopic observation of fresh, as well as fouled, membranes are presented.