Synthesis of a polyacrylamide chelating resin and applications in metal ion extractions

A series of differently crosslinked polyacrylamide chelating resins were prepared, using N,N′-methylene-bis-acrylamide as the crosslinking agent. The crosslinked resins were functionalized by the reaction with ethylene diamine to get amino group capacities varying from 4.2 to 1.1 mequiv/g. The maximum adsorption capacities of the lightly crosslinked resin for Fe³⁺, Fe²⁺, Ni²⁺, and Cu²⁺ are 3.62, 4.22, 1.48, and 1.67 mequiv/g, respectively. The adsorbed metal ions can be quantitatively desorbed. The adsorption rate and the influence of pH on the adsorption of metal ions were examined. The resins can be used for the separation between different metal ions as well as the ions in different valence states (e.g., Fe³⁺ and Fe²⁺). The resin is amenable for continuous process and can be regenerated several times.     

Infrared spectroscopy of ion-exchange resins.: Determination of amino acids ionic form in the resin phase

The paper shows the applicability of IR spectroscopy to investigate the ionization of sorbates in the resin phase. Amino acids sorbed by sulphuric polystyrene-divinylbenzene cation-exchange resin were used as example. Charge changes in the resin phase accompanies sorption of amino acid ions. The average charge of the ions in the cation-exchanger phase is more positive than in the surrounding solution. Only the sorption of the most positively charged ions is not accompanied with recharging. The charge changing is the reason for ion-exchange sorption of amino acids by cation-exchange resins at high pH. A complete interpretation of the IR spectra for systems containing different lysine and tyrosine ions was done also. The quantitative estimation of the charge changing can be done through the comparison of the spectral lines intensity. The ratios Lys²⁺/Lys⁺ and Tyr⁺/Tyr^± in the resin phase were calculated as an example.     

Preparation and adsorption properties of poly(N‐vinylformamide/acrylonitrile) chelating fiber for heavy metal ions

In this article we report a new chelating fiber that was prepared from a hydrolyzate of poly(N‐vinylformamide/acrylonitrile) by a wet‐spinning method. This fiber contains chelating groups, such as amidine groups, amino groups, cyano groups, and amide groups, with high densities. We examined the chelating abilities for several metal ions with this fiber, and present the morphological merit of the fibrous product compared with the globular resin. Based on the research results, it is shown that the fiber has higher binding capacities and better adsorption properties for heavy metal ions than the resin. The pH value of the metal ion solution shows strong influences on the adsorption of the metal ions. The maximum adsorption capacities of the fiber for Cu²⁺, Cr³⁺, Co²⁺, Ni²⁺, and Mn²⁺ are 112.23, 88.11, 141.04, 108.06, and 73.51 mg/g, respectively. In mixed metal ions solution, the fiber adsorbs Cr³⁺, Cu²⁺ and Co²⁺ efficiently. The adsorbed metal ions can be quantitatively eluted by hydrochloric acid. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 1378–1386, 2002     

Modeling of Sorption Dynamics in Transition Metal Ion–Weak-Base Ion Exchanger Systems in Terms of Surface Complexation Theory

A model is constructed for sorption dynamics in multicomponent ion-exchange systems with a weak-base ion exchanger. The model is based on computer-solved nonlinear material balances and internal-diffusion kinetic equations. The multicomponent equilibria involving a weak-base ion exchanger are described in terms of surface complexation theory. According to this theory, the fixed amino groups of the ion exchanger (Lewis bases) and sorbate anions form complexes with metal cations (Lewis acids). These complexes are located in different Stern layers at different distances from the surface. Sorption dynamics models are considered for the frontal ion-exchange chromatographic separation of the H⁺/A/B/X (A, B; = Cu²⁺, Zn²⁺, Ni²⁺, Cd²⁺; X = Cl^–, SO ₄ ^2– ) systems on the amino-containing weak-base ion exchangers Purolite A-109 and Fuji PEI-CS-07. Frontal ion-exchange chromatograms are compared for a number of multicomponent systems.     

Studies of Retention and Reusable Capacities of Melamine Formaldehyde Based Terpolymer Against Some Toxic Metal Ions by Batch Equilibrium Method

Chelating terpolymer resin was synthesized and characterized by elemental, physico-chemical, spectral, SEM, XRD, and GPC to elucidate the structure and properties of the terpolymer. Ion-exchange analysis involving evaluation of metal ion uptake in different electrolyte concentrations, pH, and time have been studied to assess the retention capacities of the terpolymer for the metal ions viz. Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, and Pb²⁺. The adsorption isotherm was evaluated using the Langmuir and Freundlich isotherms models and the results were found best fitting with each other. The resin can be successfully used in the field of recovery of metal ions from effluents and contaminated water.     

Oxidation of Amino Acids,Peptides and Proteins by Ozone: A Review

The kinetics and products of the reaction of ozone with specific amino acids, peptides, and proteins are reviewed based on studies reported in the literature. Ozone reacts mainly with the unprotonated amino group of the acids and the second-order ozone rate constants for these reactions, except for cysteine, methionine, and tryptophan, vary by about two-orders from 2.6?×?10⁴ to 4.4?×?10⁶ M^?1s^?1. The site of attack on cysteine and methionine by O₃ is at the sulfhydryl rather than the amino group to give sequential O-atom addition products. The order of reactivity for the oxidation of amino acids by O₃ at pH 8 is cysteine > tryptophan ≈ methionine > phenylalanine ≈ histidine > others, with half-lives mostly in the range of milliseconds to tens of seconds (1 mg L^-1 O₃ dose). Reactions of O₃ with aliphatic amino acids form nitrate, ammonia, and one or two carbon atom-containing carbonyl and carboxylic byproducts. In the ozonolysis of peptides and proteins, oxidation by O₃ occurs at the tyrosine, tryptophan, histidine, cysteine, and methionine residues. Oxidation of proteins results in changes in their folding ability and tertiary structures.     

Study on the adsorption–desorption behaviours of La3+, Sm3+, and Y3+ by HEHEHP extraction resin in chloride medium

The adsorption–desorption behaviours of La³⁺, Sm³⁺, and Y³⁺ on 2-ethylhexylphosphonic acid mono-2-ethyl hexyl ester (HEHEHP) extraction resin were investigated in a chloride medium. The effects of reaction time, pH, hydrochloric acid concentration, flow rate, and adsorption mechanism were studied in detail using static and dynamic experimental methods. The results show that La³⁺ is the first to reach adsorption equilibrium, followed by Sm³⁺ and Y³⁺; the highest adsorption capacities of La³⁺, Sm³⁺, and Y³⁺ are obtained at solution pH of 4 and in the order of Y³⁺ > Sm³⁺ > La³⁺. La³⁺, Sm³⁺, and Y³⁺ can be eluted by 0.3, 0.5, and 3 mol/L hydrochloric acid, respectively, indicating that La³⁺ elutes most easily, and Y³⁺ is difficult. Moreover, the flow rate has little effect on the peak of rare earth desorption. The adsorption process is chemisorption; the slope method indicates that for each mol Sm³⁺ or Y³⁺ ion adsorbed, 3 mol H⁺ ions are simultaneously released, but two for La³⁺ under the given pH conditions. It is expected to provide theoretical and technical support for preparation of ultra-high purity rare earth by HEHEHP extraction resin.     

Amino acid sensing by impedance of porous monolith-type ion exchanger

A biological and chemical sensor with rapid response at the microlevel is required for health and environmental monitoring. To develop a high-performance sensor, we use a porous monolith-type ion exchanger having three-dimensional acceptors to sense chemical substances. This porous monolith-type ion exchanger has an open-cellular structure with 5-50-μm diameter pores. The concentration of amino acids in the solution can be detected by measuring the impedance of the monolith-type ion exchanger. The novel ion exchanger has a high-exchange rate and high-electrical conductivity compared with that of the conventional ion-exchange resins. It is found that the impedance of the porous ion exchanger varies widely, depending on the amino acids such as glycine, asparatic acid, lysine, and phenylalanine. The impedance of anion exchanger had the highest value for phenylalanine with a benzene ring. OH-ion conduction is suppressed possibly due to the phenylalanine molecules stabilized by the hydrophobic interaction with the anion exchanger. In addition, we succeeded in sensing amino acid ions with concentration as low as 10⁻⁷ mol. The porous ion exchanger has the potential of a high-performance device for biological and chemical sensing.     

Linear Aliphatic Dialkynes as Alternative Linkers for Double‐Click Stapling of p53‐Derived Peptides

We investigated linear aliphatic dialkynes as a new structural class of i,i+7 linkers for the double‐click stapling of p53‐based peptides. The optimal combination of azido amino acids and dialkynyl linker length for MDM2 binding was determined. In a direct comparison between aliphatic and aromatic staple scaffolds, the aliphatic staples resulted in superior binding to MDM2 in vitro and superior p53‐activating capability in cells when using a diazidopeptide derived from phage display. This work demonstrates that the nature of the staple scaffold is an important factor that can affect peptide bioactivity in cells.     

Synthesis and adsorption properties of macroporous cross‐linked polystyrene that contains an immobilizing 2,5‐dimercapto‐1,3,4‐thiodiazole with tetraethylene glycol spacers

A novel chelating resin macroporous cross‐linked polystyrene immobilizing 2,5‐dimercapto‐1,3,4‐thiodiazole via a hydrophilic tetraethylene glycol spacer (PS‐TEG‐BMT) is synthesized and the structure is characterized by means of Fourier transform infrared spectroscopy (FTIR), energy dispersive X‐ray microanalysis (EDX), and elementary analysis. Its adsorption capacity for several metal ions such as Hg²⁺, Ag⁺, Ni²⁺, Pb²⁺, Cd²⁺, Fe³⁺, Bi³⁺, Zn²⁺, and Cu²⁺ are investigated. The initial experimental result shows that this resin has higher adsorption selectivity for Hg²⁺ and Ni²⁺ than for the other metal ions and the introduction of hydrophilic TEG spacer is beneficial to increase adsorption capacities. The result also shows that the Langmuir model is better than the Freundlich model to describe the isothermal process of PS‐TEG‐BME resin for Hg²⁺. Five adsorption‐desorption cycles demonstrate that this resin are suitable for reuse without considerable change in adsorption capacity. POLYM. ENG. SCI., 45:1515–1521, 2005. © 2005 Society of Plastics Engineers     

Removal of amino acids from water by adsorption on polystyrene resins

The adsorption of eight amino acids, L ‐asparagine, D,L ‐threonine, L ‐lysine, L ‐leucine D,L ‐methionine, L ‐tyrosine, L ‐phenylalanine and D,L ‐tryptophan, on the non‐polar macroporous adsorbents Amberlite XAD‐2 and XAD‐4 (polystyrene–divinylbenzene copolymers) was studied. Equilibrium adsorption experiments were conducted to estimate the types of isotherm and their parameters. The effect the chemical composition and structure of the amino acids on the efficiency of adsorption was evaluated. The influence of pH and ionic strength was also studied. The data of adsorption isotherms of the examined amino acids seemed generally to approach the Freundlich isotherm model. Tryptophan isotherm adsorption data could match in some cases the Langmuir model. The majority of the adsorption isotherms were almost linear. In terms of adsorbed amino acid on both resin surfaces, the amino acids can be ranked thus: D,L ‐tryptophan > L ‐phenylalanine > D,L ‐methionine, L ‐tyrosine > L ‐leucine > L ‐lysine > D,L ‐threonine > L ‐asparagine. In low pH solution, adsorption was generally higher than that at intermediate and high pH values. Generally, as the ionic strength increases, the adsorption of the amino acids increases. © 2001 Society of Chemical Industry     

Preparation,characterization, and adsorption properties for metal ions of a novel chelating resin containing sulfoxide and diethylene glycol

A novel chelating resin containing sulfoxide and diethylene glycol, poly{4‐vinylbenzyl‐[2‐2‐(hydroxyethyl)ethoxyl]sulfoxide} (PVESO) was synthesized using chloromethylated polystyrene (PS‐Cl) as material. Its structure was characterized by elemental analysis, infrared spectra, and scanning electron microscopy (SEM). The adsorption capacities of the resin for Hg²⁺, Ag⁺, Cu²⁺, Zn²⁺, and Pb²⁺ at various pH values were determined. The maximum adsorption capacities for Hg²⁺ and Ag⁺ were 1.56 and 0.75 mmol g^?1 respectively. The resin had high selectivity for Hg²⁺ and Ag⁺ over the pH range 1.0–7.0. The adsorption capacities for Hg²⁺ and Ag⁺ under competitive condition were also determined by batch experiment method. In addition, the adsorption kinetics of the resin towards Hg²⁺ at different temperatures was also investigated. The results showed that the adsorption rate was governed by film diffusion at 20°C and 25°C, by particle diffusion at 30°C and 35°C. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 6054–6059, 2006     

Multi-ion migration of Ca2+, Mg2+, Na+ and K+ in the CREDI process

In this paper, the migration of Ca²⁺, Mg²⁺, Na⁺ and K⁺ in cation-bed electrodeionisation was studied. The results showed that it was longer for divalent cations to be balanced compared with monovalent cations. At relatively low current densities, the membrane fluxes of monovalent cations were higher than that of divalent cations, whereas the results were reversed at relatively high current densities. In the resin phase, it was observed that the ionic transport was in relation to various hydration ionic radii. The reaction orders for Ca²⁺, Mg²⁺, Na⁺ and K⁺ were 2, 2, 1 and 1.5, respectively.     

Conversion of soybean oil into ion exchange resins: Removal of copper (II), nickel (II), and cobalt (II) ions from dilute aqueous solution using carboxylate‐containing resin

An ion‐exchange resin containing carboxylic acid groups was prepared by reaction of epoxidized soybean oil with triethylene tetramine, followed by hydrolysis of glycerides by using sodium hydroxide solution. The cation exchange capacity of the resins was determined to be 3.50 mequiv/g. The adsorption capacity for Cu²⁺, Ni²⁺, and Co²⁺ on the obtained resin at pH 5.0 was found to be 192, 96, and 78 mg/g, respectively. Effect of pH on the adsorption capacity for copper (II), nickel (II), and cobalt (II) ions were also studied. Cu²⁺, Ni²⁺, and Co²⁺ were adsorbed at a pH above 3. These metal ions adsorbed on the resin are easily eluted by using 1N HCl solution. The selectivity of the resin for Cu²⁺ from mixtures containing Cu²⁺/Co²⁺/Ni²⁺ ions in the presence of sodium chloride was also investigated © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2386–2396, 2002     

Effect of adsorbed metal ions and buffer nature on IgG separation from human plasma by column chromatography using an ion exchange resin,Amberlite IRC‐718

Fractionation of human plasma on ion exchanger resin was performed on Amberlite IRC‐718 saturated with metal ions. Depletion of human immunoglobulin G was carried out by column chromatography using Tris‐HCl, pH 7 at different concentrations. Results showed that, when Cu⁺² and Ni⁺² were adsorbed on the resin, one or two fractions of purified IgG were obtained, respectively. Whereas Fe⁺² and Zn⁺², both retain IgG and serum albumin or serum albumin alone. Furthermore, the Ni⁺²‐resin retention of serum proteins is too strong that the use of 700 mMTris‐HCl cannot liberate any other proteins than nonadsorbed serum albumin. In conclusion, this investigation demonstrates that immobilized metal ion affinity chromatography with Cu²⁺, Ni²⁺, and Fe²⁺ immobilized on Amberlite IRC‐718 has the potential to be developed as part of a process to purify IgG out of untreated human plasma as acceptable adsorption and elution levels of IgG could be achieved. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Synthesis,characterization, and properties for Hg2+ of new chelating resin containing sulfoxide and 3‐aminopyridine

A new chelating resin (PVESO‐AP) containing sulfoxide and 3‐aminopyridine (AP) was synthesized by using chloromethylated polystyrene‐co‐divinylbenzene (PS‐Cl) as material. Its structure was characterized by infrared spectra and elemental analysis. The adsorption capacities of the newly formed resin for Hg²⁺, Ag⁺, Cu²⁺, Zn²⁺, Cd²⁺, and Ni²⁺ were determined at pH 2 and 5. In addition, the adsorption selective coefficients for Hg²⁺ in several binary mixture systems were investigated by batch experiment method. The results showed that this resin had high adsorption selectivity for Hg²⁺. The adsorption kinetics and isothermal of PVESO‐AP for Hg²⁺ at different temperatures were also investigated. The adsorption kinetics showed that the apparent activation energy E_a was 13.71 kJ/mol. The results also showed that the Langmuir model was better than the Frundlich model to describe the isothermal process of PVESO‐AP resin for Hg²⁺. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Synthetic resins. XIII. Synthesis and characterization of the resins derived from quinacetophenone/substituted benzoic acid/furfuraldehyde

Some resins have been synthesized by reacting quinacetophenone with substituted benzoic acids and furfuraldehyde in the presence of basic catalysts. The resins have been characterized by IR spectra of the characteristic groups. The number average molecular weights of the resins have been evaluated by the conductance method. The solubility and viscosity behaviors of the resin copolymers have been determined. Cu⁺², Ni⁺², Co⁺², Mn⁺², and Mg⁺² chelates have been prepared. The resins were shown to be selective ion-exchange resins for certain metal ions. A batch equilibrium method was used for studying the selectivity of the metal ions. The thermal behavior of the resins has been determined and the values of energy of activation of the resins were computed by using the Freeman–Anderson and Broido methods. The biological assays of some of the resin copolymers were found to be highly sensitive.     

Composite cation exchangers

Sulfonated phenol formaldehyde resins containing different amounts of sulfonated sawdust were prepared. The thermal and chemical stabilities, scientific weight capacity, and apparent capacities for the exchange of Na⁺, Ca²⁺, and Mg²⁺ at different concentrations were detemined for both H⁺ and Na⁺ forms of resins. Composites containing up to 30%–50% of sawdust, while being very much cheaper, are comparable in their properties to the pure polymeric resin. Thus, cheaper exchangers can be prepared by substituting part of the polymer by sawdust.     

Selective and rapid uptake of Cu(II) by bis(benzimidazole) modified oxirane and thiirane resins

The benzimidazole containing ligand 1,3-bis(benzimidazol-2-yl)propylamine (bbpaH) was anchored onto poly(glycidyl methacrylate-co-trimethylolpropane trimethacrylate) (GMT) and onto the thiirane analogue of poly(glycidyl methacrylate-co-ethylene glycol dimethacrylate) (GME-S). Abbreviations of the modified polymers are GMT-bbpaH and GME-S-bbpaH. A multistep synthesis was applied in an attempt to increase the ligand concentration on the polymer GMT, This resulted in the resin GMT-bbpaH(ind) of which the solid state CP MAS ¹³C-NMR data showed that in this case only a monobenzimidazole was formed, i.e. only the 3-benzimidazole group was formed.Batch extraction capacities were determined for the chloride salts of Cu²⁺, Ni²⁺, Co²⁺, Cd²⁺, Zn²⁺ and Ca²⁺ in the pH range 0.9–6.0 in buffered solutions at room temperature. All three resins show a high selectivity for Cu²⁺ under competitive conditions, with maximum ligand occupations of 54%, 64% and 27% for GMT-bbpaH, GME-S-bbpaH and GMT-bbpaH(ind), respectively. The resin GMT-bbpaH also takes up some Zn²⁺ ions at pH > 4.5, the maximum ligand occupation being 17%. The resin GME-S-bbpaH shows some affinity for Zn²⁺ and Cd²⁺ ions in this pH range, with ligand occupations of 17% and 7%, respectively. Only GMT-bbpaH(ind) shows complete selectivity for Cu(II) at pH > 3, although the maximum Cu²⁺-uptake capacity is rather low.Kinetic experiments showed that the oxirane derivative exhibits a faster uptake kinetics compared with the thiirane analogue. Incomplete stripping of the Cu(II)-loaded ion-exchange resins and loss of Cu(II)-uptake capacity was observed during the regeneration experiments.     

Synthesis of polystyrene‐supported glucosamine resin and its adsorption properties for metal ions

A novel chelating resin polystyrene‐supported glucosamine was prepared by the reaction of chloromethylated polystyrene with glucosamine hydrochlorate, using anhydrous potassium carbonate as catalyst and dimethylformamide as solvent. Infrared spectra and elementary analysis were used to confirm its structure. The adsorption of the resin for Cu²⁺, Ni²⁺, Hg²⁺, Co²⁺, Cd²⁺, and Pb²⁺ was investigated, as well as various factors affecting the adsorption such as time, temperature, ion concentration, and pH. The results showed that the resin had good adsorption capacities for Cu²⁺, Ni²⁺, and Hg²⁺. The adsorption was controlled by liquid film diffusion and adsorption isothermal data could be well interpreted by the Freundlich equation. Values of adsorption activation energy and adsorption Gibbs free energy were calculated. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 890–896, 2005