A new selective and high affinity polymeric complexing agent for transition metal ions

Summary The synthesis and characteristics of a new chelating glycinohydroxamate-containing polymer resin is described. The functionality of the polymer is 1.76 mmolg^–1. The hydrogen capacity, water regain and adsorption capacities for iron(III), cadmium(II), cobalt(II), copper(II), nickel(II) and zinc(II) were measured at various pH values; uptake of the metal ions increased with pH and was quantitative above pH 3 for most of the metal ions. All cations studied showed high exchange rates towards the resin. The half saturation times for iron(III), cadmium(II), copper(II) and zinc(II) were all less than 1 min. The coordination behaviour of the resin was studied with the help of e.p.r., i.r., u.v. and potentiometry. The pK _a of the resin is 10.70 and the log value of the stability constants for iron(III), copper(II), lead(II), zinc(II), cobalt(II), manganese(II), cadmium(II) and nickel(II) were measured as 21.81, 19.50, 19.20, 18.59, 18.51, 18.46, 18.37 and 18.36, respectively, at 25 ° C and I = 0.2M KCl.     

Study on Determination of Six Transition Metal Ions in Biological Samples by SPE and RP‐HPLC

This paper reports the utilization of solid phase extraction and the reversed‐phase high‐performance liquid chromatography (RP‐HPLC) for the determination of six transition metal ions (iron, cobalt, nickel, copper, zinc and manganese) in biological samples. The samples were digested by microwave digestion. The iron, cobalt, nickel, copper, zinc and manganese ions in the digested samples can react with 2‐(2‐quinolinylazo)‐5‐diethylaminophenol (QADEAP) to form colored chelates in pH 4.0 acetic acid‐sodium acetic buffer solutions and cetyl trimethylammonium bromide (CTMAB) medium. These chelates were enriched by solid phase extraction with C₁₈ cartridge. Then the chelates were separated on a Waters Nova‐Pak‐C₁₈ column (3.9 × 150 mm, 5 μm) by gradient elution with methanol (containing 0.5% of acetic acid and 0.1% of CTMAB) and 0.05 mol/L pH 4.0 acetic acid‐sodium acetic buffer solution (containing 0.1% of CTMAB) as mobile phase at a flow rate of 0.5 mL/min. The detection limits of iron, cobalt, nickel, copper, zinc and manganese are 3 ng/L, 4 ng/L, 2 ng/L, 4 ng/L, 8 ng/L, 10 ng/L, respectively. This method was applied to the determination of iron, cobalt, nickel, copper, zinc and manganese in biological samples with good results.     

Potentiometric study of complexation between taurine and metal ions

The protolytic and complexation properties of taurine are studied by a potentiometric method. The dissociation constants of 2-aminoethanesulfonic acid functional groups and the stability constants of taurine complexes with copper(II), cobalt(II), nickel(II), zinc(II), manganese(II), cadmium(II), silver(I), magnesium(II), calcium(II), strontium(II), and barium(II) ions are calculated.     

Synthesis, characterization and analytical application of a hydroxamic acid resin

A chelating ion-exchange resin with hydroxamic acid functional groups was synthesized from styrene-maleic acid co-polymer cross-linked with divinylbenzene. A resin prepared from equimolar amounts of styrene and maleic anhydride with 0.75 mole% divinylbenzene gives the best sorption characteristics. The selectivity of the resin for metal ions is copper(II) > cobalt(II) > zinc(II) > nickel(II) > manganese(II) > chromium(III) > iron(III) > vanadium(V). Copper(II), chromium(III) and iron(III) in chromium plating baths can be separated by use of the resin and determined spectrophotometrically.     

Determination of transition metal ions in tobacco as their 2-(2-quinolinylazo)-5-dimethylaminophenol derivatives using reversed-phase liquid chromatography with UV-VIS detection

This paper reports the utilization of solid-phase extraction and the reversed-phase high-performance liquid chromatography for the determination of six important transition metal ions: iron, cobalt, nickel, copper, zinc and manganese in tobacco with 2-(2-quinolinylazo)-5-dimethylaminophenol (QADMAP) as chelating reagent. Iron, cobalt, nickel, copper, zinc and manganese ions react with QADMAP to form colored chelates in the medium of acetic acid-sodium acetate buffer solution (pH 4.0). These chelates can be enriched by solid-phase extraction with Waters Sep-Pak-C18 cartridge, and eluted the retained chelates from cartridge with tetrahydrofuran. The chelates were separated on a Waters Nova-Pak-C18 column (150x3.9 mm, 5 microm) by gradient elution with methanol (containing 0.5% of acetic acid) and 0.05 mol/l pH 4.0 acetic acid-sodium acetate buffer solution as mobile phase at a flow-rate of 0.5 ml/min. The detection limits of iron, cobalt, nickel, copper, zinc and manganese are 10, 12, 8, 13, 17 and 22 ng/l, respectively. This method had been applied to the determination of iron, cobalt, nickel, copper, zinc and manganese in tobacco with good results.     

Synthesis and properties of new chelating resin with a spacer containing alpha-nitroso-beta-naphthol as the functional group

A new chelating ion-exchange resin with a spacer CH₂-NH-C₆H₄- based on a microreticular chloromethylated styrene-divinylbenzene copolymer containing α-nitroso-β-naphthol as a functional group has been synthesized. The sorption characteristics for manganese(II), iron(III), cobalt(II), nickel(II), copper(II), and zinc(II) have been investigated over the pH range 1.0–7.0. The resin is highly stable in acidic and alkaline medium. Iron(III) and cobalt(II); copper(II) and iron(III) are separated very effectively in a column operation by stepwise elution.     

8-Quinolinol-5-sulfonic acid-loaded resin as a preconcentrating agent in the neutron activation analysis of the chalcophile elements (author's transl)]

A chelating agent-loaded resin consisting of 8-quinolinol-5-sulfonic acid and an anion-exchange resin (HOx-resin) was prepared in order to concentrate trace chalcophile elements in natural water samples selectively before neutron activation analysis. The exchange capacity of the Diaion SA No. 100 for the reagent (1.8 meq . g-1 resin) corresponds approximately to that for chloride ion (1.83 meq . g-1 resin), indicating that 8-quinolinol-5-sulfonic acid is adsorbed quantitatively on the exchange site of the resin through the sulfonate anion in the reagent. The basic conditions for the adsorption of the metal ions on the resin were investigated by employing the column method. The nitrate concentration and the pH of the sample solution affect the adsorption behavior of metal ions. Several solutions containing metal ions with varying pH or varying nitrate concentration were applied to the resin column (35 mm x 7 mm phi) with a flow rate of 2.0 cm3 . min-1. As a result, the optimum conditions for the quantitative adsorption of copper(II), zinc(II), cadmium(II), cobalt(II), nickel(II) and manganese(II) were as follows: NO3- less than 0.01 mol . dm-3 pH greater than 4.6. Furthermore, the feasibility of the above conditions as well as quantitative adsorption of the chalcophile elements was confirmed through the neutron activation analysis of the synthesized metal solutions.     

Thermal decomposition of some divalent metal selenates

Thermogravimetry, differential thermal analysis and differential thermogravimetry have been used to study the decomposition of hydrated selenates of manganese(II), cobalt, nickel, copper(II), zinc and cadmium. Based on the results obtained, mechanisms of decomposition have been proposed. The decomposition temperatures of non-hydrates show a gradual increase from manganese(II) selenate to zinc selenate and then a sudden drop for cadmium selenate.     

The determination of some toxic metals in human liver as a guide to normal levels in New Zealand. Part I. Determination of Bi, Cd, Cr, Co, Cu, Pb, Mn, Ni, Ag, T1 and Zn.

Procedures are described for the determination of bismuth, cadmium, chromium, cobalt, copper, lead, manganese, nickel, silver, thallium and zinc in post-mortem liver samples by atomic absorption spectrometry. The technique involves a simple HCl/HNO₃ digestion at 100 ±20 °C, gives good recoveries and appears to be applicable to other tissues, and blood. Results of analyses of post-mortem material from eleven subjects with no known exposure to toxic metals, are presented. They are comparable with overseas findings and show no excessive levels.     

The use of dithizone extraction and atomic absorption spectrometry for the determination of cadmium,zinc, copper,nickel and cobalt in rocks and sediments

A method is presented for the determination of cadmium, zinc, copper, nickel and cobalt in sediments. The sediments are digested with hydrofluoric, sulphuric and perchloric acids. The metals are extracted into dithizone. Cadmium and zinc are back-extracted into dilute hydrochloric acid, but the other metals are determined in a solution prepared after the destruction of the organic extract. The method has been applied to USGS rock reference samples and to estuarine sediments.     

The determination of metals at ppb levels by thin-film x-ray fluorescence spectrometry after coprecipitation with a molybdenum carrier complex

A method is described for the determination of iron, cobalt, nickel, copper, zinc, cadmium and lead in water at μg 1^-1 levels, in which the metals are coprecipitated with a molybdenum—pyrrolidinedithiocarbamate carrier complex. The precipitate is collected as a thin film on a membrane filter (0.4-μm pore-size) and analysed directly by x-ray fluorescence spectrometry. Detection limits, for 100-ml water samples and counting times of 200 s per element, are 1 μg metal l^-1 or lower. Total dissolved metal concentrations are obtained without boiling or u.v. irradiation of the water sample. The method is applicable to river and estuarine waters and is not affected by dissolved organic matter.     

Crystal Structure of 2-pyridine-2-yl-3(pyridine-2-carboxylideneamino)quinazolin-4(3H)-one and its Ligating Diversity Towards Transition Metal(II) Ions

The synthesis of a new ligand 2-pyridine-2-yl-3(pyridine-2-carboxylideneamino)-quinazolin-4(3H)-one (PPCAQ) is described together with its manganese(II), cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) complexes. The single crystal X-ray diffraction studies of the ligand reveal the presence of two crystallographically independent molecules in asymmetric unit cell, which exhibit N…N attractive interaction. The PPCAQ and its metal complexes were characterized by analytical, spectroscopic (i.r., n.m.r and u.v.–vis), magnetic moment, conductance and thermal studies. The i.r. spectral studies reveal the ligational diversity of the PPCAQ towards different metal ions as NNN donor in cobalt(II), copper(II), zinc(II) and cadmium(II) complexes and as ONN donor in manganese(II) and nickel(II) complexes. The antimicrobial activity of all the compounds was tested; copper(II), zinc(II) and cadmium(II) complexes show enhanced antibacterial activity compared to the free ligand.     

The use of Metomega Chrome Blue BBL as a metal indicator and its application for the determination of calcium and magnesium in serum

Summary Metomega Chrome Blue BBL was used as a metal indicator for the detection and titration of calcium, magnesium, manganese, nickel and manganese. A displacement reaction was described for the titration of cadmium using Mn-EDTA. A stepwise titration was conducted for the direct titration of both calcium and magnesium in blood serum.Fenugreek mucilage was used as a media for increasing the sensitivity limits of detection of barium, cadmium, cerous, calcium, copper, cobalt, magnesium, manganese, nickel, lead and zinc.     

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).     

ICP-AES法测定红土镍矿中镍、钙、钛、锰、铜、钴、铬、锌与磷的含量

建立了ICP-AES法测定红土镍矿中Ni;Ca;Ti;Mn;Cu;Co;Cr;Zn和P含量的方法。样品用HCl、HNO3溶解,加入HF和HClO4,加热至HClO4烟冒尽,用HCl溶解盐类,过滤,采用ICP-AES法同时测定滤液中Ni、Ca、Mn、Cu、Co、Zn、P;残渣经灼烧、挥硅、K2S2O7熔融、HCl浸取,所得溶液与滤液合并,测定溶液中Cr和Ti含量。方法检出限:P为0.022μg/mL,其它元素在0.0032～0.0085μg/mL之间,方法的精密度(n=7)在1.4%～2.9%之间。分析结果与分光光度法、XRF法和AAS法分析结果的相对误差:Ni、Cu、Co、Cr小于5%,Ti和Mn小于10%,Zn小于15%,Ca和P小于19%。     

A spectral study of transition-metal complexes on a chelating ion-exchange resin containing aminophosphonic acid groups

The coordination mode of a commercial chelating ion-exchange resin, ES 467, containing aminomethylphosphonic acid groups anchored on a macroporous styrenedivinylbenzene copolymer, with several metal ions, such as chromium(III), cobalt(II), nickel(II), copper(II) and zinc(II) has been studied with the aid of IR, ligand field and ESR spectra. The chelating group of ES 467, aminomethylphosphonic acid, appears to bind different metal ions mainly through oxygen atoms of the phosphonic acid group, though, in the case of those species containing low-loading of metal ions, the secondary amine nitrogen atom also appears to take part in coordination. Most of the metal ions studied seem to be present as six-coordinated species in the polymeric matrix, whereas cobalt(II) species show electronic spectra which are consistent with the presence of both four-coordinated (tetrahedral) and six-coordinated (octahedral) structures of these species. The distribution coefficients for cobalt(II), nickel(II), copper(II) and zinc(II) have been determined and it appears that the resin ES 467 binds copper(II) ions selectively. An attempt has been made to find a possible relationship between the selectivity of the chelating resin and the stereochemistry of the adsorbed metal ions.     

云南富源某地区土壤8种有效态元素的测定

一种DTPA土壤测试被成功开发并应用到云南富源某地区,以识别土壤中的有效锌、铁、锰、铜、铅、钴、镍和镉的含量,用于指导该地区的土壤施肥情况以获得作物的最大产量。提取剂由0.005molL-1DTPA(二乙烯三胺五乙酸)、0.1 molL-1三乙醇胺和0.001molL-1CaCl, pH为7.3。土壤测试包括用20ml的提取剂震荡10g风干土壤2小时,过滤渗滤液,用电感耦合等离子体发射光谱法测定滤液中的锌、铁、锰、铜、铅、钴、镍和镉。根据作物对锌、铁和锰等有效态的反应,土壤测试使用标准化的土壤准备、研磨和提取程序。提取剂在pH值7.30时得到缓冲,选用能有效地提取8种微量元素金属DTPA作为螯合剂。通过大量实验确定最佳的震荡时间是2h,最佳的水土比是2：1。通过实验,方法线性相关系数R＞0.99,国家一级标准物质的准确度、精密度和检出限满足云南富源地区土壤检测要求,确定了该的确的土壤检测方法,并通过加标回收实验,回收率在90%～110%之间。该方法绿色环保,简单快捷,准确度高,适合该地区土壤有效态的分析。     

Ion-selective chalcogenide electrodes for a number of cations

Ion-selective chalcogenide disc electrodes have been developed which are responsive to cations such as silver, lead, chromium(III), nickel, cobalt(II), cadmium, zinc, copper(II) and manganese(II) ions. Each was prepared by using the corresponding metal chalcogenide with silver sulphide. An electrode was assembled with both a compacted and a sintered disc. The sintered electrodes were more sensitive and stable than the compacted ones. Response to silver ion was 59.5 mV pAg , to lead, nickel, cadmium, zinc and copper(II) 29.5 mV pM and to chromium(III) 20 mV pM . Cobalt(II) and manganese(II) electrodes had a non-Nernstian response of 25 mV pM . Both selenides and tellurides can be used for potentiometric determination, but the manganese(II) electrode serves as an analytical tool only when the disc consists of manganese(II) telluride and silver sulphide.     

正常妊娠与妊高征患者血清中8种必需微量元素水平的研究

７８例正常妊娠妇女和４０例妊高征患者血清中铁、锌、铜、锰、硒、铬、钴和镍的含量与健康未孕妇女比较，正常妊娠妇女和妊高征患者均是铜和锰的含量升高，铁、锌、硒、铬、钴和镍含量降低；妊高征患者与正常妊娠妇女比较，则是铁、铜和锰的含量升高，锌、硒、铬、钴和镍的含量降低。     

Syntheses,Characterization and Anti-inflammatory Activity of a Benzamide Derivative and its Metal Chelates

N-Phenylbenzamide-2,2′-dicarboxylic acid (PBDA) and its copper(II), nickel(II), cobalt (II), zinc(II) and manganese(II) chelates have been synthesized and characterized by their physical measurements, infrared and electronic spectra and magnetic moment data. In an acute anti-inflammatory test, the cobalt chelate was most active (31.1% inhibition) followed by the zinc and copper chelates, whereas the copper chelate (22.3% inhibition) was most active in an adjuvant arthritis test. Again the cobalt chelate was most active in the cotton-wad granuloma test. Gastric irritancy was markedly reduced after chelation by copper, followed in order by zinc, cobalt, manganese and nickel chelates. © 1997 John Wiley & Sons, Ltd.