Study on the Determination of Cobalt,Nickel, Copper,Zinc and Vanadium in Environmental Samples by a Rapid High‐Performance Liquid Chromatography

A new method for the simultaneous determination of five transition metal ions in water and food by rapid high‐performance liquid chromatography was developed. The cobalt, nickel, copper, zinc and vanadium ions were pre‐column derivatized with 2‐(2‐quinolinylazo)‐4‐methyl‐1,3‐dihydroxidebenzene (QAMDHB) to form colored chelates, then the Co‐QAMDHB, Ni‐QAMDHB, Cu‐QAMDHB, Zn‐QAMDHB and V‐QAMDHB chelates were enriched by solid phase extraction with a C18 cartridge. The enrichment factor of 50 was achieved by eluting the retained chelates from the cartridge with tetrahydrofuran (THF). These chelates were separated on a ZORBAX Stable Bound rapid analysis column (4.6 × 50 mm, 1.8 um) with 68% methanol (containing 0.1% of acetic acid and 0.1% of CTMAB) as mobile phase at a flow rate of 2.0 mL/min and detected with a photodiode array detector from 450?600 nm. The Co‐QAMDHB, Ni‐QAMDHB, Cu‐QAMDHB, Zn‐QAMDHB and V‐QAMDHB chelates were separated completely within 2.0 min. The detection limits of cobalt, nickel, copper, zinc and vanadium are 2 ng/L, 1.5 ng/L, 2 ng/L, 3 ng/L, and 3 ng/L, respectively, in the original samples. This method was applied to the determination of the five transition metal ions in water and food samples with good results.     

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.     

Simultaneous Determination of Tin,Nickel, Lead,Cadmium and Mercury in Tobacco and Tobacco Additives by Microwave Digestion and RP‐HPLC Followed by On‐Line Column Enrichment

A new method for the simultaneous determination of five heavy metal ions, tin, nickel, lead, cadmium and mercury ions as metal‐tetra‐(2‐aminophenyl)‐porphyrin (T₂APP) chelates was developed using reversed‐phase high performance liquid chromatography (RP‐HPLC) equipped with a photodiode array detector and combined with an on‐line enrichment technique. The tin, nickel, lead, cadmium and mercury ions were pre‐column derivatized with T₂APP to form color chelates. The Sn‐T₂APP, Ni‐T₂APP, Hg‐T₂APP, Cd‐T₂‐APP and Pb‐T₂APP chelates can be absorbed onto the front of the enrichment column when they are injected into the injector and sent to the enrichment column [Waters Xterra? RP₁₈(5μ, 3.9 × 20 mm)] with a buffer solution of 0.05 mol/L pyrrolidine‐acetic acid (pH = 10.0) as mobile phase. After the enrichment had finished, by switching the six‐port switching valves, the retained chelates were back‐flushed by mobile phase and traveling towards the analytical column. These chelates separation on the analytical column [Waters Xterra? RP₁₈ (5μ, 3.9 × 150 mm)] was satisfactory by gradient elution with methanol (containing 0.05 mol/L pyrrolidine‐acetic acid buffer salt, pH = 10.0) and acetone (containing 0.05 mol/L pyrrolidine‐acetic acid buffer salt, pH = 10.0) as mobile phase. The linearity range is 0.01?120 μg/L for each metal ion. The detection limits (S/N = 3) of tin, nickel, lead, cadmium and mercury are 4.0 ng/L, 3.5 ng/L, 2.5 ng/L, 3.0 ng/L and 3.0 ng/L, respectively. This method was applied to the determination of tin, nickel, lead, cadmium and mercury ions in tobacco and tobacco additives with good results.     

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.     

4－（2－氨基噻唑）－间苯二酚为柱前衍化剂液相色谱／电化学检测Fe、Co、Ni

４－（２－氨基噻唑）－间苯二酚为柱前衍化剂液相色谱／电化学检测Ｆｅ、Ｃｏ、Ｎｉ格日勒，李惠梅，李南强，汪尔康（中国科学院长春应用化学研究所电分析化学开放实验室，北京大学化学系，长春，１３００２２）关键词液相色谱，Ｆｅ，Ｃｏ，Ｎｉ，４－（２－氨基噻唑）...     

Study on the Determination of Heavy-Metal Ions in Tobacco and Tobacco Additives by Microwave Digestion and HPLC with PAD Detection

A new method for the simultaneous determination of heavy-metal ions in tobacco and tobacco additive by microwave digestion and reversed-phase high-performance liquid chromatography (RP-HPLC) was developed. The tobacco and tobacco additive samples were digested by microwave digestion. The lead, cadmium, mercury, nickel, copper, and tin ions in the digested samples were precolumn derivated with tetra-(4-aminophenyl)-porphyrin (T₄-APP) to form color chelates; the Hg-T₄-APP, Cd-T₄-APP, Pb-T₄-APP, Ni-T₄-APP, Cu-T₄-APP, and Sn-T₄-APP chelates were then enriched by solid-phase extraction with C₁₈ disks and the retained chelates were eluted from the disks using tetrahydrofuran (THF). The chelates were separated on a Waters Xterra RP₁₈ column by gradient using methanol (containing 0.05 mol/L pyrrolidine-acetic acid buffer salt, pH 10.0) and acetone (containing 0.05 mol/L pyrrolidine-acetic acid buffer salt, pH 10.0) as a mobile phase at a flow rate of 0.5 mL/min and detected with a photodiode array detector in the range 350–600 nm. The detection limits of lead, cadmium, mercury, nickel, copper, and tin were 5, 4, 2.5, 5, 8, and 4 ng/L, respectively, in the original samples. The method was applied to the determination of lead, cadmium, mercury, nickel, copper, and tin in tobacco and tobacco additive with good results.__________From Zhurnal Analiticheskoi Khimii, Vol. 60, No. 5, 2005, pp. 542–548.Original English Text Copyright © 2005 by Yang, Li, Shi, Wang.This article was submitted by the authors in English.     

The separation by thin-layer chromatography of trace metals as their tetraphenylporphyrin chelates.

The tetraphenylporphyrin chelates of iron, cobalt, manganese, nickel, zinc, copper, rhodium lead, cadmium and mercury were prepared and their chromatographic behaviour investigated using four different adsorbents and eleven different solvent systems. Mixtures of lead, cadmium and mercury chelates exhibited isographic behaviour in all conditions; mixtures of the other metal chelates were adequately resolved on silica (MN Polygram Sil SHR) by the solvent system light petroleum (b.p. 80-100 degrees)-toluene-acetic acid-water (66:33:85:15, v/v, upper phase). The intense colours of the chelates permit their visual detection at levels of about 10(-10) moles; using the integrated ion-current mass spectrometric procedure, as little as 10(-14) moles of metal could be detected and assessed.     

Thermogravimetric study of some divalent metal chelate polymers of dithiooxamide

The thermal properties of polymeric chelates of dithiooxamide with divalent copper, cobalt, zinc and nickel have been investigated. The order of thermal stability is Ni>Co～Zn>Cu, which is the same as that observed for previously studied naphthazarin and rhodizonic acid chelates. The procedural decomposition temperatures indicate that the dithiooxamide chelates, which are not aromatic, are about as stable as the aromatic naphthazarin and rhodizonic acid chelates. Several unsuccessful attempts were made to prepare beryllium and manganese (II) chelates.     

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。     

Ion paired chromatography of iron (II,III), nickel (II) and copper (II) as their 4,7-Diphenyl-1,10-phenanthroline chelates

A reversed phase ion-paired chromatographic method that can be used to determine trace amounts of iron (II,III), nickel (II) and copper (II) was developed and applied to the determination of iron (II) and iron (III) levels in natural water. The separation of these metal ions as their 4,7-diphenyl-1,10-phenanthroline (bathophenanthroline) chelates on an Inertsil ODS column was investigated by using acetonitrile-water (80/20, v/v) containing 0.06 M perchloric acid as mobile phase and diode array spectrophotometric detection at 250-650 nm. Chromatographic parameters such as composition of mobile phase and concentration of perchloric acid in mobile phase were optimized. The calibration graphs of iron (II), nickel (II) and copper (II) ions were linear (r > 0.991) in the concentration range 0-0.5, 0-2.0 and 0-4.0 mug ml(-1), respectively. The detection limit of iron (II), nickel (II) and copper (II) were 2.67, 5.42 and 18.2 ng ml(-1) with relative standard deviation (n = 5) of 3.11, 5.81 and 7.16% at a concentration level of 10 ng ml(-1) for iron (II) and nickel (II) and 25 ng ml(-1) for copper (II), respectively. The proposed method was applied to the determination of iron(II) and iron(III) in tap water and sea water samples without any interference from other common metal ions.     

Microdetermination of Mn, Fe, Co, Ni, Cu, Zn, Ag, Cd, Hg, Pb, Bi and U in inorganic and organometallic compounds with morpholinium morpholine-N-dithiocarboxylate

The chelates of morpholinium morpholine-N-dithiocarboxylate with manganese(II), iron(II), iron(III), cobalt(II), nickel, copper(II), zinc, silver, cadmium, mercury(II), lead, bismuth and uranium(VI) have been prepared and their compositions elucidated. Simple, accurate and relatively rapid procedures for the gravimetric and titrimetric microdetermination of these metals in inorganic and organometallic compounds are presented.     

Simultaneous Determination of Palladium and Platinum by On‐Line Enrichment Followed by Rapid Column High Performance Liquid Chromatography

In this paper, a new method for the simultaneous determination of palladium and platinum ions was developed using a rapid column high performance liquid chromatograph equipped with an on‐line enrichment technique. The palladium and platinum ions were pre‐column derivatized with 5‐(p‐aminobenzylidene)‐thiorhodanine (ABTR) to form colored chelates. The Pd‐ABTR, Pt‐ABTR chelates can be absorbed onto the front of an enrichment column when they were injected into the injector and sent to the enrichment column [ZORBAX Stable Bound, 4.6 × 10 mm, 1.8 μm] with a buffer solution of 0.05 mol/L sodium acetate‐acetic acid buffer solution (pH 3.5) as mobile phase. After the enrichment had finished, by switching the six‐ports switching valve, the retained chelates were back‐flushed by mobile phase and traveled towards the analytical column. These chelates separation on the analytical column [ZORBAX Stable Bound, 4.6 × 50 mm, 1.8 μm] was satisfactory with 65% methanol (containing 0.05 mol/L of pH 3.5 sodium acetate‐acetic acid buffer salt and 0.01 mol/L of tritonX‐100) as mobile phase. The palladium and platinum were separated completely within 2 min. The detection limits (S/N = 3) of palladium and platinum are 1.4 ng/L and 1.6 ng/L, respectively. This method was applied to the determination of palladium and platinum in water and urine samples with good results.     

偏最小二乘分光光度法同时测定痕量铁、锰、铜、锌、钴和镍

痕量Fe^3 ,Mn^2 ,Cu^2 ,Zn^2 ,Co^2 ,Ni^2 与2－（5－溴－2－吡啶偶氮）－5－二乙氨基苯酚（5－Br-PADAP)和溴化十六烷基三甲基铵（CTMAB）在PH8．3时发生高灵敏显色反应，所形成的三元胶束络合的吸收光谱严重重叠，采用偏最小二乘法（PLS）辅助分光光度法测定了合成试样及饲料中上述6种痕量组分，结果表明，PLS法是化学计量学中一种可适用于基体较复杂的实际试样中痕量组分分光度同时测定的多元计算方法。     

Simultaneous Determination of Palladium,Platinum and Rhodium by On‐Line Column Enrichment and a Rapid Column High Performance Liquid Chromatography with 2‐Carboxyl‐1‐Naphthalthiorhodamine as Precolumn Derivatization Reagent

Abstract

In this paper, 2‐carboxyl‐1‐naphthalthiorhodamine (CNTR) was synthesized, and a new method for the simultaneous determination of palladium, platinum, and rhodium ions as metal‐CNTR chelates was developed using rapid column high performance liquid chromatography combined with on‐line enrichment. The palladium, platinum, and rhodium ions were precolumn derivatized with CNTR to form colored chelates. The Pb‐CNTR, Pt‐CNTR, and Rh‐CNTR chelates could be absorbed onto the front of the enrichment column when they were injected into the injector and sent to the enrichment column (ZORBAX Stable Bound, 4.6×10 mm, 1.8 µm) with a buffer solution of 0.05 mol/L sodium acetate–acetic acid buffer solution (pH 3.5) as mobile phase. After enrichment, and by switching the six ports switching valve, the retained chelates were back‐flushed by mobile phase and traveling towards the analytical column. The separation of these chelates on the analytical column (ZORBAX Stable Bound, 4.6×50 mm, 1.8 µm) was satisfactory with 54% methanol (v/v) in 0.05 mol/L sodium acetate buffer (pH 3.5) containing 1 g/L Triton X‐100 as mobile phase. Palladium, platinum, and rhodium were separated completely within 2 min. The detection limits (S/N=3) of palladium, platinum, and rhodium are 1.4 ng/L, 1.2 ng/L, and 1.8 ng/L, respectively. This method was applied to the determination of palladium, platinum, and rhodium in water, urine, and soil samples with good results.     

过敏性哮喘患者血清中10种必需微量元素水平的研究

３４例过敏性哮喘患者血清中铁，锌、铜，锰硒铬，钴镍，钡，钼的含量水平与对照组比较，揭示：（１）铁，铜，铬的含量升高；（２）硒，镍，钴、钒的钼的含量降低；（３）锌和锰的含量差异无显著性，Ｐ〉０．０５。     

116例冠心病患者血清中10种必需微量元素水平的研究

１１６例冠心病患者血清中１０种必需微量元素的含量与正常值比较，具有如下特点：（１）铁，锌、铬，镍含量升高；２硒钴，钒，钼含量降低；（３）铜和锰差异无显著性。     

肿瘤患者放疗前后血清八种微量元素含量的研究

对临床、病理、放射线或CT检查确诊的82名癌肿患者，在放疗前后和对42名健康人进行了微量元素铁、锌、铜、锰、硒，铬、钴、镍的分析。研究结果显示：1．癌肿患者血清铜、镍、锰、铬、钴的含量比健康人高，而血清锌、铁、硒的含量却比健康人低；2．血清Cu／Zn、Cr／Zn、Co／Zn、Ni／Zn的比值癌肿患者均比健康人高，而Fe、Zn、Se／Zn的比值却相反。因此，可根据血清铜升高、血清锌降低，血清铜／锌比值升高的特点。用于癌肿的早期诊断；3．癌肿患者放疔后血清铁、锌含量进一步下降，铜、锰、铬的含量也出现降低，唯有硒的含量有所上升。因此，放疗时应注意补充铁、锌、铜元素。     

Biligand metal chelates of 1,10-phenanthroline and several salicyclic acid derivatives in solution

Summary Mixed ligand complexes of copper(II), zinc(II), nickel(II) and cobalt(II) ions involving 1,10-phenanthroline (phen) as primary and 3,5-dinitrosalicylic acid (dnsa), 5-nitrosalicylic acid (nsa), 5-chlorosalicylic acid (csa) and 3,5-dibromosalicylic acid (dbsa) as secondary ligands in solution have been investigated potentiometrically [25°, µ = 0.1 M [NaClO₄], medium 50% v: v aqueous ethanol]. The stability order of mixed ligand complexes with respect to the metal ions obeys the natural order: cobalt(II) < nickel(II) < copper(II) > zinc(II). The stabilities of the heterometal chelates have been compared with the corresponding homometal chelates of the secondary ligands and have been interpreted in terms of metal-ligand effects and coulombic interactions between various ligand anion species present.     

Organic complexation and total dissolved trace metal analysis in estuarine waters: comparison of solvent-extraction graphite furnace atomic absorption spectrometric and chelating resin flow injection inductively coupled plasma-mass spectrometric analysis

The measured concentrations of cadmium, cobalt, copper, nickel, lead, zinc, and manganese in acidified (pH<2) estuarine water samples analyzed for total dissolved trace metal concentrations using on-line chelating resin column partitioning with inductively coupled plasma-mass spectrometry (CRCP-ICP-MS) were compared to those analyzed by graphite furnace atomic absorption spectrometry (GFAAS) after liquid-liquid extraction using a combination of 1-pyrrolidinedithiocarbamate/diethyldithiocarbamate (PDC/DDC). Although there was good agreement between the two sets of analyses for cadmium, lead, manganese, and zinc concentrations, those of cobalt, copper, and nickel determined by CRCP-ICP-MS were found to be 10-20% lower than those determined by solvent-extraction GFAAS. The different yields were positively correlated (R>0.961, simple linear regression) to the dissolved organic carbon (DOC) concentration of the samples. Good agreement between the two methods for cobalt and copper was achieved after ultraviolet (UV) digestion of the acidified samples. Samples collected from the South Bay of the San Francisco Estuary with high DOC showed the greatest difference for cobalt, copper, and nickel which is tentatively attributed to complexation with humic material for copper and cobalt and strong synthetic chelating agents such as ethylenediaminetetraacetic acid (EDTA) for nickel. This is consistent with previous studies on copper, nickel and cobalt complexation in this region. We recommend UV digestion of acidified estuarine samples prior to multi-element analysis by chelating resin flow injection ICP-MS methods.     

The mass spectrometry of metal chelates--II. Oxinates of common metals

The mass spectra of the oxinates of zinc, iron(III), manganese(II), nickel, cobalt, aluminium, copper and magnesium have been measured. Concentrations of several of these chelates have been related to the integrated ion currents recorded at a significant m/e value during evaporation of the sample in the source of an A.E.I. M.S.9 mass spectrometer. The structural significance of some of the mass spectra is discussed.