Chelating resin containing s-bonded dithizonefor the separation of copper(II), nickel(II) and zinc(II)

Analytical and physicochemical properties of a crosslinked poly (vinyl pyridine) based resin containing dithizone were examined. The resin was further used for the preconcentration of copper, nickel and zinc at batch and column level. Various conditions such as pH, equilibration time, temperature were optimised for the maximum loading of copper, nickel and zinc. The loading capacities of the resin for copper, nickel and zinc were observed to be 0.51, 0.59 and 0.65 mmol g⁻¹ of dry resin respectively. Elution of loaded copper, nickel and zinc from the resin was done by using 0.1 M HCl, 0.1 M H₂SO₄ and 0.1 M HNO₃ respectively. Separation of copper, nickel and zinc in binary and ternary mixtures was achieved without any cross contamination.     

Cation-exchange separation of metals in dimethyl sulphoxide-aqueous hydrochloric acid media

The behaviour of bismuth, cadmium, copper, lead, silver, tin and zinc on a cation-exchange resin in a solvent system consisting of dimethyl sulphoxide, hydrochloric acid and water was studied. The distribution coefficients of these metal ions between liquid and resin were determined as functions of the concentration of dimethyl sulphoxide and of hydrochloric acid. On the basis of the distribution coefficients found, predictions were made as to the possibilities of separating these metals from mixtures. Such separations were confirmed experimentally for bismuth from lead, bismuth from copper, zinc from lead, lead from cadmium, silver from copper, silver from lead, lead from cadmium from zinc, bismuth from lead from zinc, and bismuth from zinc from copper.     

Use of a nitrate-form anion exchange resin for the determination of traces of gold in copper and cadmium by neutron activation analysis

A method is described for the determination of traces of gold in copper and cadmium by neutron activation analysis, using anion exchange resin as a preconcentration agent: gold was separated from large amount of copper or cadmium with Cl-form Dowex 1X8 AG, 100–200 mesh, resin. To reduce the interfering activities, the resin was irradiated in NO ₃ ⁻ -form and washed with dilute hydrochloric acid after irradiation.¹⁹⁸Au in the resin was then counted with a Ge(Li) or NaI(Tl) detector. The chemical yields were more than 99%. The concentration factors of gold for copper and cadmium samples were 1.1×10⁸ and 2.7×10⁶, respectively. The analytical results of gold in 99.99% copper and 99.999% cadmium were 65 and 0.15 ppb, respectively. The blank was 0.05 ng Au per 200 mg of wet resin.     

Adsorption of metal ions on crosslinked poly(4-vinylpyridine) resins prepared with a metal ion as template

Poly(4-vinylpyridine) (PVP) was crosslinked with 1,4-dibromobutane with a metal ion as template. The adsorption behavior of copper, cobalt, zinc, and cadmium ions on the obtained resin (DBQP) was studied. The DBQP resin prepared with a metal ion as template preferentially adsorbed the metal ion used as template. The stability constant of the copper complex of DBQP was largest for the DBQP resin prepared with a copper ion as template, which was due to its large entropy change for the complexation.     

铜印迹螯合树脂对金属离子的吸附特性

研究了铜印迹螯合树脂与非印迹螯合树脂对金属离子的吸附性能，结果表明：铜印迹树脂对Cu^2 、Ni^2 、Zn^2 的吸附量比非印迹树脂有显著增大,两者对Cu^2 的吸附速率均较快，其表观吸附速率分别为0．044s^-1和0．040s^-1；印迹树脂对Cu^2 的吸附可用Langmuir或Freundlish等温式来描述；其动态吸附曲线与离子的起始浓度相关；用0．5mol／L HCl即可快速洗脱吸附的Cu^2 ，树脂具有较强的再生能力，可以重复使用。     

Speciation of protein-binding zinc and copper in human blood serum by chelating resin pre-treatment and inductively coupled plasma mass spectrometry

A method for the speciation of zinc and copper binding with proteins in human serum was explored by chelating resin (Chelex-100) pre-treatment and inductively coupled plasma mass spectrometry (ICP-MS). It was shown by a SEC (size-exclusion chromatography)-ICP-MS system that albumin-zinc and albumin-copper (loosely-bound species) could be selectively removed from serum by adsorption on the Chelex-100 resin after the chelating resin pre-treatment, while alpha 2-macroglobulin-zinc and ceruloplasmin-copper (firmly-bound species) remained in the serum. The zinc and copper bound with alpha 2-macroglobulin and ceruloplasmin, respectively, were then determined by ICP-MS after batch treatment of the serum samples with the Chelex-100 resin. In addition, the total concentrations of zinc and copper were also determined by ICP-MS after a 20-fold dilution with 0.1 M HNO3. The albumin-zinc and -copper were estimated as the differences between the concentrations of total and firmly-bound species. The present batch pre-treatment method was applied to the speciation analysis of zinc and copper binding with proteins in sera donated from 25 healthy volunteers as well as from a pregnant woman and a myelodysplastic syndrome patient. The observed concentrations of alpha 2-macroglobulin-zinc and ceruloplasmin-copper were in the ranges 109-202 ng ml-1 (12.4-31.3% of total zinc) and 513-880 ng ml-1 (90.6-99.7% of total copper), respectively. The present method is simple (only addition of the chelating resin and centrifugation is required) and reproducible (average RSD = 2% for alpha 2-macroglobulin-zinc and 1% for ceruloplasmin-copper in intra-assay measurements, and 5% for alpha 2-macroglobulin-zinc and 4% for ceruloplasmin-copper in inter-assay measurements), and there is less risk of contamination during separation.     

Application of dithiocarbamate resin-metal complexes as stationary phases in gas chromatography

A chelating resin with dithiocarbamate functional groups to which silica gel was used as a matrix and silanes were used with diamino functional groups as a spacer was synthesized. The structure and the conversion of functional groups of the resin were confirmed by IR spectra and elemental analysis. The influence of pH on the adsorption of the resin for metal ions was also examined. The resin under optimum pH conditions formed a 1:1 metal complex with copper ion. The affinity of metal ions toward the synthesized resin decreased in the order Hg(II) >; Cu(ll) >; Cd(II) >; Zn(II). The resin exhibited efficient complexation of transition metal cations. The cadmium, copper and zinc complexes were investigated for application as stationary phase for the gas chromatographic analysis of dialkyl sulphides. The material was packed in a 2.1 m × 3.2 mm I.D. spiral glass column. Factors affecting the retention and sample selectivity were also studied. A shorter retention time and sharp peaks were obtained when ammonia was introduced into the mobile phase. At an oven temperature of 100°C, a flow-rate of 60 ml min⁻¹ and use of a flame ionization detector, the analysis of dialkyl sulphides showed that the copper resin complex as the stationary phase gave the best results. The stationary phase was also used for the separation of dialkyl sulphide from a hydrocarbon mixture.     

Combination of chelating behaviour with molecular recognition as interaction for ligand exchange chromatography

A novel chelating resin was synthesized, composed of chemically bonded glycinocyclodextrin (S-CD-G) to which silica gel was added as matrix and silanes with amino groups as spacer. It showed efficient complexation with transition metal cations. In this report the copper and zinc resin complexes were investigated for application as stationary phases for the separation of substituted phenol isomers. The results revealed that the copper resin complex has a high potential for this application.     

Preparation and analytical properties of a chelating resin containing phenylalanine groups

A polystyrene-based macroreticular resin containing phenylalanine groups has been prepared and its analytical properties have been investigated and compared with Dowex A-1. The phenylalanine resin shows high selectivity for mercury(II) and copper(II) in the pH region 2-3. The sorption behaviour of copper has been examined in detail, with the intention of using the resin analytically. The important characteristics of the resin are fast equilibration, high selectivity and small volume change between its hydrogen form and metal forms. These enable it to be applied for the rapid concentration of trace amounts of copper in the presence of large amounts of diverse metals. It may be used for the determination of copper in sea-water and the separation of copper/cobalt and copper/nickel.     

Development of physico-chemical speciation procedures to investigate the toxicity of copper,lead, cadmium and zinc towards aquatic biota

A range of model compounds was studied to test the effect of complexing agents on the adsorption of copper, lead, cadmium and zinc by Chelex-100 resin, oxine porous glass, thiol porous glass and thiol resin, from seawater and distilled water. The thiol materials, while showing behaviour similar to Chelex-100 resin and oxine porous glass for zinc, cadmium and lead, retained copper much more strongly. Methods for measuring lipid-soluble metal complexes in waters were also studied. Bio-Rad SM2 resin was the most suitable extractant, although a citrate buffer of pH 5.7 was needed to prevent the co-adsorption of free metal ions. Seawater and various fresh waters were analyzed for trace metal speciation by using Chelex-100 resin, thiol resin and anodic stripping voltammetry to determine labile metal. Bio-Rad SM2 resin and hexane—butanol extraction were used for the estimation of lipid-soluble metal. The polluted water samples had higher fractions of labile and organic-soluble metal, but it was concluded that some of the waters contained unidentified ligands which caused speciation behaviour different from that of the synthetic solutions with model ligands. The factors involved in the choice of speciation procedures for the measurement of the toxic fraction of a metal in a water sample are discussed in detail.     

Synthesis and properties of a new chelating resin containing the oxime group

A macroreticular polystyrene-based chelating resin with oxime and diethylamino functional groups has been synthesized. The resin is stable in acid and alkaline solutions; no decrease in nitrogen content or capacity for sorption of copper(II) is observed when it is exposed to 3M hydrochloric acid and 1M sodium hydroxide for 7 days. The resin has higher selectivity for copper(II) than for other metal ions tested and the time required for 50% uptake of copper(II) is 15 min. The highest capacity for copper(II) is 2.0 mmole/g at pH 6.0. In a column operation, quantitative recovery of copper(II) is achieved by elution with 1M hydrochloric acid, and the resin can be used repeatedly.     

Dialysis-Chelex method for determination of exchangeable copper in human plasma

A method based on dialysis in the presence of histidine, and subsequent copper adsorption and preconcentration using Chelex-100 resin, has been developed for selective extraction of exchangeable copper from blood plasma. The method was verified by comparative analysis using two different instrumental techniques, ICP–MS and AAS. The results obtained were in excellent agreement. Accurate quantification of the exchangeable copper and the firmly bound copper was achieved. The method was further validated by analysis of a lyophilised human serum certified reference material.     

咪唑盐聚合物与环氧树脂复合的研究

用红外光谱和X射线光电子能谱研究了咪唑与金属铜的反应,证明反应生成了咪唑铜盐聚合物,此聚合物能在铜表面形成极薄的保护层,并能引发环氧树脂开环聚合固化,用DSC对咪唑铜盐聚合物引发苯基缩水甘油醚的动力学进行了初步研究,同时测定了界面复合的剪切强度。     

Preconcentration of trace chalcophile elements by a zincon--loaded resin and its application to neutron activation analysis (author's transl)]

A chelating agent-loaded resin consisting of an anion exchange resin and zincon which has widely been employed as a specific reagent for zinc(II) and copper(II) in spectrophotometry was prepared. The adsorption behavior of some chalcophile elements was studied in detail, with respect to pH, flow rate and exchange capacity. From the results, it was confirmed that the zincon-loaded resin reacts selectively with copper(II), zinc(II), mercury(II) and lead(II) at lower pH region, and the above reaction is stoichiometric as in the case of the reaction of zincon with metal ions in aqueous solution. Furthermore, the zincon-loaded resin was applied to the selective concentration of trace amounts of chalcophile elements in natural water samples prior to neutron activation analysis. Water samples taken from the Watarase River were filtered and the pH of each filtrate was adjusted to ca. 5.5. After preconcentration was made by the column method (zincon-loaded resin: 2 x 10-4 mol/g resin, 1.0 g, 7 mm phi x 35 mm), the resin in the column was washed and dried in a desiccator. The standard material was also prepared according to the above mentioned scheme. The sample and the standard materials packed in polyethylene vials were irradiated for 40 min by a neutron flux of 5 x 10(13 n.cm-2.sec-1 in the JRR-4 of the Japan Atomic Energy Research Institute. After cooling the materials, activity measurements were made. The results were 53 ppb for copper, 0.25 ppb for mercury.     

Speciation of copper in fresh waters

The cations and readily dissociable complexes of copper are separated from copper adsorbed on inorganic and organic particulate species in river and pond waters by selective sorption on a strong-acid cation-exchange resin, AG 50W-X12, and a chelating resin, Chelex-100, for atomic absorption spectrometry. The sorption behaviour after the pH change and removal of carbon dioxide suggests that the dominant low-molecular-weight copper species in river waters are neutral CuCO⁰₃ and Cu²⁺ ions.     

Development of One-Step Derivatization and Preconcentration Technique Using Weak Anion-Exchange Resin Modified with Sodium Diethyldithiocarbamate for Determination of Trace Amount of Copper(II) in Water

A new method was developed using weak anion exchange resin modified with sodium diethyldithiocarbamate (DDTC) for the derivatization and preconcentration of copper(II) in water prior to spectrophotometric determination. Several conditions affecting the extraction efficiency were investigated. Under the optimum conditions, an enrichment factor of 50 was achieved. The reaction mechanism of copper(II) and DDTC on the resin and binding experiment was studied. The detection limit is 0.6 μ g L^?1. The relative standard deviations of intra- and inter-day ranging from 2.1 to 3.6% and from 1.3 to 4.0% were obtained, respectively, and the recoveries were in the range of 95.3–99.6%.     

Separation of lead-203 from cyclotron-bombarded thallium targets by ion-exchange chromatography

A simple method is presented for the separation of lead-203 from copper-backed thallium cyclotron targets. The procedure involves cation-exchange chromatography in hydrochloric acid and hydrochloric acid-acetone mixtures. Further purification involves anion-exchange chromatography in nitric acid-hydrobromic acid mixtures. A cation-exchange column containing 3.0 g of resin can handle as much as 15 g of thallium and 160 mg of copper. An anion-exchange column containing 3.0 g of resin can separate lead from up to 200 mg of thallium and 10 mg of copper. Separations are extremely sharp and less than 0.1 mug of thallium and less than 0.1 mug of copper remain in the lead-203 fraction.     

Copper resinate: preparation, characterisation and study of degradation

This paper describes a method for the synthesis of Copper Resinate, which disappeared from artists' palettes in the eighteenth century. This was carried out by interpreting ancient recipes following a scientific approach. Its characterisation using Fourier Transform-Infrared Spectrometry and Gas Chromatography-Mass Spectrometry demonstrated that it is a mixture containing copper and oxidised abietic acids, mainly dehydroabietic and 7-oxo-dehydroabietic acids, formed during the preparation of the pigment and the curing of the paint layer. The composition of copper resinate paint layers, artificially aged by U.V. irradiation at 365 nm (UV), heating (T), and exposed to atmospheric pollutants (NOX) in a climatic chamber, was investigated. The combination of irradiation and temperature produced a change in colour along with a significant increase in the recovered amount of 7-oxo-dehydroabietic acid. The identification of copper resinate in a sample from an old painting should be related to the presence of the following resin compounds which are stable in the ageing process: dehydroabietic and 7-oxo-dehydroabietic acid pimaradienic acids. Photo-oxidation of the resin acids co-ordinated with copper seem to be the most probable decay mechanism responsible for the colour change in the pigment.     

Continuous sonoassisted digestion coupled to flow injection minicolumn separation for the determination of total and labile Cu and Fe in fresh waters by flame atomic absorption spectrometry

An automatic on-line system is developed for the trace determination of copper and iron species in fresh waters by flame atomic absorption spectrometry using only 5 and 2?mL of sample, for copper and iron determination, respectively. This system, which includes a home-made minicolumn of commercially available resin containing aminomethylphosphonic acid functional groups (Chelite P), comprises two operational modes. The first, used for the determination of the dissolved labile fraction (free copper and iron ions and their weak complexes) is based on the elution of this fraction from a minicolumn containing the chelating resin loaded in-situ with the sample. The second mode is used for the determination of total trace copper and iron concentrations. This last mode is based on the retention/preconcentration of total metals on the Chelite P resin after on-line sonoassisted digestion of water samples acidified with nitric acid (0.5?mol?L^?1 final concentration) to break down metal organic complexes present in fresh waters as river waters. The figures of merit for copper and iron determination in both fractions are given and the obtained values are discussed. The analytical method was characterized and the limit of detection and limit of quantification for the two metals were 0.5 and 1.6?µg?L^?1 for Cu and 2.3 and 6.1?µg?L^?1 for Fe, respectively. The repeatability, expressed as relative standard deviation, was in the range 1.0–2.1%. The speciation scheme was applied to the analysis of river surface water samples collected in Galicia (Northwest, Spain).     

Selective metal sorption on cross-linked poly(vinylpyridine) resins

The sorption behaviour of several metal ions on five kinds of poly(4- or 2-vinylpyridine) resins, cross-linked with divinylbenzene, and with different surface properties, are examined. All the resins proposed sorb some metal ions effectively in a similar manner by anion-exchange, while the sorption of metal ions by complex formation with the pyridine moiety is strongly affected by the surface properties of the resins. A macroreticular poly(4-vinylpyridine) resin shows high affinity for copper and nickel ions in acetate buffer. Sodium chloride and/or methanol added to the working solutions influence the sorption capacities for metal ions. This resin was applied to the separation of copper/cobalt and nickel/cobalt and the concentration of copper from sea-water by a column operation.