High-performance collection of palladium ions in acidic media using nucleic-acid-base-immobilized porous hollow-fiber membranes

We prepared nucleic-acid-base-immobilized porous membranes of a hollow-fiber form with pore size, porosity, and thickness of 0.2 μm, 70%, and approximately 0.7 mm, respectively. Glycidyl methacrylate was graft-polymerized onto a polyethylene-made porous hollow-fiber membrane, followed by ring-opening of the epoxy group with the amino groups of adenine, guanine, and cytosine. The collection of palladium ions was achievable during the permeation of palladium chloride solution through the adenine-immobilized porous hollow-fiber membrane. The diffusional mass-transfer resistance of palladium ion to immobilized adenine was negligible because palladium ion was transported by permeative flow through the pores. The adenine-immobilized porous membrane with an immobilization density of 0.85 mol/kg of the membrane exhibited the highest molar binding ratio of palladium ion to immobilized adenine of 0.31 in 1 M hydrochloric acid. In addition, a quantitative elution with 4 M hydrochloric acid was experimentally demonstrated.     

High-throughput solid-phase extraction of metal ions using an iminodiacetate chelating porous disk prepared by graft polymerization

A chelating porous sheet for use in solid-phase extraction was prepared by radiation-induced graft polymerization and subsequent chemical modifications. An epoxy-group-containing vinyl monomer was graft-polymerized onto a porous sheet made of polyethylene. The produced epoxy group of the graft chain was converted into an iminodiacetate group. The chelating porous sheet with a density of the iminodiacetate group of 2.1 mol/kg was cut into disks 13 mm in diameter to fit an empty cylindrical cartridge with a capacity of 6 mL. Breakthrough curves using the chelating-porous-disk-packed cartridge overlapped irrespective of the flow rate of the solution ranging up to 1500 mL/h because of negligible diffusional mass-transfer resistance of the copper ions to the iminodiacetate group of the graft chain.     

Concentration of heavy metal ions in water using thermoresponsive chelating polymer

Thermoresponsive polymers, poly(N-isopropylacrylamide) (PNIPAAm), having chelating functionalities were synthesized. PNIPAAm-imidazole (-Im) was precipitated and formed a gum-like aggregate in the neutral pH region at 50 °C, while PNIPAAm-carboxylic acid (---COOH) and PNIPAAm-iminodiacetic acid (-IDA) remained soluble even at pH 7. An addition of a paired ion, dodecyltrimethylammonium ion, was effective for inducing the precipitation of those polymers. PNIPAAm-Im was useful for collecting copper(II), nickel(II), cobalt(II), and lead(II), but was ineffective for cadmium(II) recovery. In contrast, PNIPAAm-COOH collected cadmium(II), while insufficiently recovered cobalt(II) and nickel(II). PNIPAAm-IDA was the best choice for collecting all metal ions in neutral pH's. After 20-folds concentration, the metal ions in river and seawater were successfully determined by graphite furnace atomic absorption spectrometry (GFAAS).     

Potentiometric responses of polymeric liquid membranes based on hydrophobic chelating agents to metal ions.

The effect of hydrophobicity of acidic chelating agents as sensing materials on the potentiometric responses of polymeric liquid membranes was investigated. The chelating agents tested were 8-quinolinol (HOx), dithizone (HDz), 1-(2-pyridylazo)-2-naphthol (PAN) and their alkylated analogues, 5-octyloxymethyl-8-quinolinol (HO8Q), di(phexylphenyl)thiocarbazone (C6HDz), 7-pentadecyloxy-1-(2-pyridylazo)-2-naphthol (C15PAN) and a series of N-alkylcarbonyl-N-phenylhydroxylamines (CnPHA, n = 3, 6, 9, 12). The distribution coefficients between membrane solvent and water were determined to evaluate the hydrophobicity of the agents. The potential-pH profiles of the membranes containing hydrophobic chelating agents demonstrated the generation of potentiometric responses, while less hydrophobic agents gave no response. A possible model for the generation of membrane potential is proposed. The charge separation is attained by the permselective uptake of metal cations by the chelating agent anion at membrane/solution interface, where the high hydrophobicity of the agent enables the anionic or deprotonated form of the agents to remain at the membrane/solution interface.     

Extraction and preconcentration of toxic metal ions from aqueous solution using benzothiazole-based chelating resins

Polystyrene-divinylbenzene resin (PS-DVB) was functionalized with a benzothiazole group. PS-DVB with amino group was initially prepared by nitration and reduction reactions and subsequently treated with ethyl 2-benzothiazolylacetate (BA) to obtain the chelating resin with an amide linkage (BA-PS-DVB). Meanwhile, the amino-PS-DVB was diazotized and coupled with BA to obtain the chelating resin with an azo linkage (azo-BA-PS-DVB). The resins were characterized by elemental analysis and infrared spectroscopy and evaluated for their extraction of Cd(II), Cu(II) and Pb(II) ions in water before their determinations by flame atomic absorption spectrometry (FAAS). Extraction conditions were optimized for batch method such as the pH of the solution, the extraction time and the adsorption isotherm. The optimum pH for the extraction of Cd(II), Cu(II) and Pb(II) are 8.0, 7.0 and 6.0, respectively, while the equilibrium time of all ions was reached within 10-20 min. The adsorption behavior of all the metal ions followed the Langmuir adsorption isotherm. In the column method, the optimum flow rates of metal sorption onto BA-PS-DVB and azo-BA-PS-DVB columns were 2.5 and 4.0 mL min^− 1. Metal ions sorbed onto columns were eluted by 0.5 to 2.0 M HNO₃. The preconcentration factors of Cd(II) and Cu(II) on azo-BA-PS-DVB and Cu(II) on BA-PS-DVB were 50, 50, and 20, respectively. The present column method gave acceptable validation results: 71.2 and 74.0% recovery for Cd(II) and Cu(II) and an overall relative standard deviation (R.S.D) less than 10% (n = 15). The proposed method was applicable for determining Cu(II) in drinking water.     

Permeability control of metal ions using temperature- and pH-sensitive gel membranes

Temperature- and pH-sensitive copolymer gels were synthesized by the simultaneously occurring radiation-induced polymerization and self-bridging of acryloyl- -proline methyl ester (A-ProOMe) with acrylic acid (AAc) in aqueous solutions. The gel swelling behavior and the metal permeation characteristic of its gel membrane were investigated with regard to very slight changes of temperature and pH. The pH threshold of the swelling of a copoly(A-ProOMe/AAc, 70/30 mol%) gel in the range of 5–30°C lay in the region between pH 4.0 and 5.0. The permeability results of metal ions showed that at 40°C the gel membrane blocks the permeation of lithium (Li) and cesium (Cs) ions at pH values lower than 4.75 and 4.60, respectively. The permselectivity (P_Li/Cs value) of the two metal ions at 30°C was also studied and, as a result, its value was obtained to be 1.33 at pH 4.65 and 30°C. This permeation study indicates that the selective metal separation of copoly(A-ProOMe/AAc) gel membranes can be controlled by changing temperature and pH values.     

Sorption investigation on the removal of metal ions from aqueous solutions using chelating terpolymer resin

A novel chelating terpolymer resin has been synthesized from anthranilic acid, phenylhydrazine, and formaldehyde by condensation in glacial acetic acid. The structure of the chelating resin was clearly elucidated by use of a variety of spectral techniques, for example FTIR, and ¹H and ¹³C NMR spectroscopy. The average molecular weight of the terpolymer resin was determined by gel-permeation chromatography. The empirical formula and empirical weight of the resin were determined by elemental analysis. The physicochemical properties of the terpolymer resin were determined. Scanning electron microscopy was used to establish the surface features of the chelating resin. The ion-exchange behaviour of the resin for specific metal ions, viz. Fe³⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, and Pb²⁺, was evaluated by a batch equilibrium method. The study was extended to three variations: evaluation of metal ion uptake in the presence of different electrolytes at different concentrations; evaluation of metal ion uptake at different pH; and evaluation of metal ion uptake at different times. Further, the reusability of the resin was also determined to assess the efficiency of the resin after a few cycles of sorption. From the results it was observed that the resin acts as an effective chelating ion-exchanger.     

o-hydroxyaroyl-isonicotinoyl hydrazones as chelating agents with divalent transition metal ions

Summary Two series of bivalent metal complexes of the type M(Sal)· xH₂O and M(Naph) have been synthesized; where M = Co, Ni, Cu, Zn, Pd and Cd, and H₂-Sal and H₂-Naph are salicylaldehyde and o-hydroxynaphthaldehyde isonicotinoyl hydrazones which acted as dibasic terdentate ligands. The polymeric nature and coordination sites of the complexes have been characterized by elemental, d.t.a. and t.g.a analyses, molar conductance, pH, room temperature magnetic susceptibility and spectral (i.r., ¹H n.m.r, u.v.) measurements. The protonation constants of the ligands have been determined potentiometrically at different temperatures, ionic strengths and at different EtOH-H₂O compositions.     

Fast removal of heavy metal ions and phytic acids from water using new modified chelating fiber

The graft copolymerization of acrylic acid(AA) onto polyethylene glycol terephthalate(PET) fiber initialed by benzoy peroxide (BPO) was carried out in heterogeneous media.Moreover,modification of the grafted PET fiber(PET-AA) was done by changing the carboxyl group into acylamino group through the reaction with dimethylamine.The modified chelating fiber(NDWJN1) was characterized using elementary analysis,SEM and FT-IR spectroscopy.Adsorption kinetic curves indicated that NDWJNl could fast remove heavy metal ions and phytic acids from water effectively.Furthermore,batch kinetic studies indicated that heavy metal ions adsorbed to NDWJNl could be filted well by both pseudo-first-order and pseudo-second-order adsorption equations,but the intra-particle diffusion played a dominant role in the adsorption of phytic acids.     

High-speed recovery of antimony using chelating porous hollow-fiber membrane

A porous hollow-fiber membrane containing an iminodiethanol (IDE) group as the chelate-forming group was applied to the recovery of antimony in the permeation mode. An antimony solution was forced to permeate through the pores of the chelating porous hollow-fiber membrane, driven by a transmembrane pressure. The membrane with a thickness of 0.7 mm and a porosity of 70% had an iminodiethanol group of 1.6 mol/kg of the membrane and a water flux of 0.95 m/h at 0.1 MPa and 298 K. The breakthrough curves of antimony overlapped irrespective of the permeation rate of the antimony solution ranging from 2 to 20 ml/min, i.e. the residence time across the membrane thickness ranging from 3.4 to 0.34 s, because of negligible diffusional mass-transfer resistance of the ionic species of antimony to the iminodiethanol group. At antimony concentrations below 10 mg/l (pH 4.0), a linear adsorption isotherm was obtained. The adsorbed antimony was quantitatively eluted by permeation of 2 M hydrochloric acid through the pores of the membrane.     

Confirmation of heavy metal ions in used lubricating oil from a passenger car using chelating self-assembled monolayer

In order to prevent engine failure, the oil must be changed before it loses its protective properties. It is necessary to monitor the actual physical and chemical condition of the oil to reliably determine the optimum oil-change interval. Our study focuses on the condition of the lubricating oil in an operated car engine. Shear stress curves and viscosity curves as a function of the shear rate for fresh and used lubricating oil were examined. Metal nitrate was detected in the lubricating oil from the operated car engine through the use of a chelating self-assembled monolayer.     

Solid phase extraction and determination of metal ions in aqueous samples using Quercetin modified Amberlite XAD-16 chelating polymer as metal extractant

A new chelating polymer has been developed using Amberlite XAD-16 anchored with Quercetin. The modified polymer was characterised by Fourier Transform Infra Red (FTIR) spectroscopy, thermogravimetric analysis, surface area analysis and elemental analysis. The Quercetin anchored polymer showed superior binding affinity for Cr(III), Mn(II), Fe(III), Co(II), Ni(II) and Cu(II) with greater than 95% adsorption under optimum conditions. The optimum pH conditions for the quantitative sorption of metal ions were studied. The developed method showed superior extraction qualities with high metal loading capacities of 387, 313, 195, 473, 210 and 320 µmol g^?1 for Cu(II), Co(II), Cr(III), Fe(III), Mn(II) and Ni(II), respectively. The rate of metal ion uptake i.e. kinetics studies performed under optimum levels, showed t _1/2 for Co(II), Cu(II), Cr(III), Fe(III), Mn(II) and Ni(II) is 20, 15, 25, 10, 30 and 15 min, respectively. Desorption of metal ions was effective with 10 mL of 2 M HCl prior to analysis using flame atomic absorption spectrophotometer. The chelating polymer was highly ion selective in nature even in the presence of interferent ions, with a high preconcentrating ability for the metal ions of interest. The developed chelating polymer was tested on its utility with synthetic and real samples like river, tap water samples and also with multivitamin tablets. It showed relative standard deviation (R.S.D.) values of/less than 3.0% reflecting on the accuracy and reproducibility of data using the newly developed chelating polymer.     

Pore-functionalized polymer membranes for preconcentration of heavy metal ions

Functionalized membranes containing carboxylate, phosphate and sulfonate groups were prepared by UV-initiator induced graft polymerization of the functional monomer (acrylic acid, ethylene glycol methacrylate phosphate (EGMP) and 2-acrylamido-2-methyl-1-propane sulfonic acid) with a crosslinker (methylenebisacrylamide) in the pores of poly(propylene) host membranes. The functionalized membranes thus obtained were characterized by gravimetry, FTIR spectroscopy, radiotracers and scanning electron microscopy for the degree of grafting and water uptake, presence of functional groups, ion-exchange capacity, and physical structure of the membranes, respectively. The uptakes of Cs⁺, Ag⁺, Sr²⁺, Cd²⁺, Hg²⁺, Zn²⁺, Eu³⁺, Am³⁺, Hf⁴⁺ and Pu⁴⁺ ions in the functionalized membranes were studied as a function of acidity of the equilibrating aqueous solution. Among the functionalized membranes prepared in the present work, the EGMP-grafted membrane (with phosphate groups) showed acid concentration dependent selectivity towards multivalent metal ions like Eu³⁺, Am³⁺, Hf⁴⁺ and Pu⁴⁺. The solvent extraction studies of EGMP monomer in methyl isobutyl ketone (MIBK) solvent indicated that divalent and trivalent metal ions form complexes with EGMP in 1:2 proportion, but the distribution coefficients of trivalent metal ions were significantly higher that for the divalent ions. The uptakes of Eu³⁺ ions in monomeric EGMP (dissolved in MIBK) and polymeric EGMP (in the forms of crosslinked gel and membrane) were studied as a function of concentration of H⁺ ions in the equilibrating solution. This study indicated that polymeric EGMP has better binding ability towards Eu³⁺ as compared to monomeric EGMP. The variation of distribution coefficients of Eu³⁺/Am³⁺ in gel and membrane as a function of H⁺ ion concentration in the equilibrating aqueous solution indicated that ionic species held in the membrane and gel were not same. These results indicated that proximity of functional groups (phosphate) plays an important role in metal ion binding with polymeric EGMP.     

Preconcentration of metal ions using microbacteria

This review (160 refs). covers the current state of the art of microbacteria-based sorbents for preconcentration of metal ions at trace levels. We highlight advantages and major challenges of the techniques and discuss future perspectives of both batch and column-based methods. Particular attention is paid to the preconcentration of metal ions using resin-immobilized microbacteria for solid phase extractions. We also discuss detection methods including UV–vis spectrophotometry, FAAS, ICP-OES and ICP-MS. Analytical figures of merit are compared, and examples are given for the application to a variety of samples including food, beverages, alloys, water, soil, and geological samples.

Synthesis of thiol chelating resins and their adsorption properties toward heavy metal ions

A series of chelating resins, derived from a macroreticular styrene-divinylbenzene (2%) copolymer beads grafted with various poly(ethylene glycols) HO? (? CH₂? CH₂? O? )_n? H(n = 0, 4, 9, 13) and containing thiol groups as chelating functions, have been synthesized in a three-step reaction sequence. The structure of the functionalized resins was confirmed by IR spectrophotometry, elemental analysis, and differential scanning calorimetry. The complexation behavior of these thiol resins was investigated towards Hg(II), Cu(II), and Pb(II) ions in aqueous solution by a batch equilibration technique. The influence of pH on adsorption capacity was also examined. The adsorption values for metal ions' intake followed the order Hg(II) > Cu(II) > Pb(II). The affinity of these polymers towards Hg(II) ions was so high that the total mercury level in the liquid decreased from 20 ppm to below 10 ppb after 2 h of treatment. Polymers can be regenerated by washing with a solution of hydrochloric acid (6N) and 10% by weight of an aqueous solution of thiourea. © 1994 John Wiley & Sons, Inc.     

Preconcentration and selective metal ion separation using chelating micelles

Chelating aggregates consisting of Triton X100 host micelles and hydrophobic derivatives of PAN have been examined as suitable candidates for preconcentration and selective separation of transition metal ions through micellar-enhanced ultrafiltration. The effective accumulation in the surfactant-rich retentate of nickel(II), copper(II), cobalt(II), manganese(II) and zinc(II), present at trace levels in aqueous samples, has been achieved by operating at pH ca. 6 with a ligand having a binding constant to the host micelles higher than 2000 l./mol. The efficient separation of micelle-bound metal chelates from unreactive ions has been assessed, together with the feasibility of selective enrichment and purification of the investigated metal ions present in mixtures through a multistage process.     

Competitive transport of toxic metal ions by polymer inclusion membranes

The paper gives a short overview of application of polymer inclusion membranes (PIMs) for separation and removal of metal ions. Investigation of the selective removal of toxic metal ions, i.e. Cr(VI), Cd(II), Zn(II) from acidic chloride aqueous solutions, as well as trace radionuclides, i.e., ¹³⁷Cs, ⁹⁰Sr and ⁶⁰Co from wastewaters using transport across polymer inclusion membranes was studied. The carriers, i.e., tri-n-octylamine for anionic metal species, as well as dibenzo-21-crown-7, tertbutyl-dibenzo-21-crown-7, and dinonylnaphtalenesulfonic acid for metal cations were incorporated into polymer inclusion membranes composed of cellulose triacetate as a support and o-nitrophenyl pentyl ether as a plasticizer. Selective transport of chromium(VI) over zinc(II) and cadmium(II) chloride complexes through PIMs was observed. Competitive transport of trace radionuclide ions, i.e., ¹³⁷Cs, ⁹⁰Sr, and ⁶⁰Co from NaNO₃ aqueous solutions across polymer inclusion membranes containing a mixture of dinonylnaphtalenesulfonic acid, and dibenzo-21-crown-7 as the carrier provide the selectivity order Cs(I)>Sr(II)>Co(II).     

Influence of the matrix on the complexation of metal ions by chelating ion exchangers

Summary Chelating ion exchangers show distribution coefficients that are considerably lower than those expected from complexation equilibria with the corresponding free ligands in solution. Furthermore, dependence of distribution coefficients on the concentration of exchanging ions in solution is observed. Both effects are due to the influence of the surrounding matrix on the anchor groups. The distribution coefficients of Fe³⁺, Ni²⁺, Cu²⁺, Pb²⁺ and UO ₂₊ ² on two cellulose exchangers carrying different anchor groups are investigated as function of the concentration in solution. In case of the anchor group of high flexibility a strong increase of the distribution coefficients with decreasing concentration in solution is measured. This is explained by the fact that the anchor groups located at the surface are less affected by interactions with the matrix, with the result of higher distribution coefficients. The explanation is in agreement with the sorption isotherm.

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Einfluß der Matrix auf die Komplexierung von Metallionen durch chelatbildende Ionenaustauscher

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Dedicated to Prof. Dr. G. Tölg on the occasion of this 60th birthday