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）...     

Synthesis of narrowly size-distributed metal salt/poly(HEMA) hybrid particles in inverse miniemulsion: versatility and mechanism

Hybrid particles containing different hydrophilic metal salts such as tetrafluoroborates of iron(II), cobalt(II), nickel(II), copper(II), and zinc(II), and nitrates of cobalt(II), nickel(II), copper(II), zinc(II), and iron(III), and cobalt(II) chloride were synthesized via inverse miniemulsion polymerization of 2-hydroxyethyl methacrylate (HEMA). All salts delivered narrowly size-distributed hybrid particles with the exception of iron(III), where only the nitrate salt could be successfully employed. The size and size distribution of the hybrid particles were characterized by dynamic light scattering (DLS) and transmission electron microscopy (TEM). The particle morphology and the distribution of salt in the dried particles were observed by TEM. The influences of the type of metal salts and salt content on the particle size distribution were extensively investigated.     

Surface modification of spherical nickel hydroxide for nickel electrodes

Electroless cobalt plating on spherical nickel hydroxide is tested in order to improve the conductivity of Ni(OH)₂ and the capacity of the electrode. The factors affecting the process of electroless cobalt plating are cobalt solution, temperature and pH, etc. The effects have been examined and the optimum process parameters have been obtained. The nickel hydroxide electrode which is made by nickel hydroxide deposited cobalt has excellent performance, the results showing that electroless cobalt plating on the surface of spherical nickel hydroxide particles is an effective method for modifying electrodes.     

The determination of nickel with dimethylglyoxime in the presence of iron and cobalt

A method for the determination of nickel in the presence of both ferric iron and cobalt is presented. The nickel is precipitated directly with dimethylglyoxime, without the prior reduction of the iron. The interference of the iron and cobalt is eliminated by the addition of N,N-dihydroxyethylglycine, which chelates the iron and prevents the formation of the iron-cobalt-dimethylglyoxime contaminant.     

Spectrophotometric estimation of cobalt(II) with nitrilotriacetic acid

A convenient and efficient method for the estimation of cobalt(II) ions in the presence of other metal ions is described. Interference of metal ions such as iron(II), iron(III), nickel(II), manganese(II), and copper(II) have been investigated. Only iron(III) ions seriously affect this determination. Copper(II) and nickel(II) ions do not interfere if present in a molar-ratio less than 1:2 in the cobalt(II) ion solution. Cobalt(II)-nickel(II) and cobalt(II)-copper(II) binary mixtures can be efficiently analyzed at selective wavelengths.     

Contributions to the basic problems of complexometry—X: Determination of nickel and cobalt in the presence of iron, copper and some other metals

A complexometric determination of nickel and cobalt in the same solution has been devised. It is based on the determination of the sum of nickel and cobalt by back-titration of added excess EDTA in a strongly alkaline medium with calcium chloride using Fluorexon (Calcein) as indicator. After oxidation of cobalt with hydrogen peroxide to form the cobalt^III- EDTA complex and screening of nickel by potassium cyanide, the liberated EDTA corresponding to the amount of nickel present is titrated with further calcium chloride. High concentrations of iron and aluminium are screened with triethanolamine. Copper and other heavy metals are screened with thioglycollic acid.     

Extraction with long-chain amines-V Colorimetric determination of cobalt with nitroso-R salt

The colorimetric determination of cobalt with nitroso-R salt (NRS) has been modified and improved by the introduction of extraction of the Co-NRS chelate into a chloroform solution of trioctylmethylammonium chloride. Ammonium phosphate, fluoride and mainly citrate were used for masking iron, nickel, copper and calcium, which under the described conditions do not interfere even in 2000-fold excess. The method is very sensitive and permits determination of about 1 mug of cobalt per ml of the extractant.     

Colloid and nanodimensional catalysts in organic synthesis: II. The hydrogenation of alkenes with hydrogen at atmospheric pressure

Colloid particles of metals of varying valence are found to be relatively cheap and easily prepared catalyst permitting the the hydrogenation under mild conditions. Procedure of reduction of unsaturated compounds with gaseous hydrogen at atmospheric pressure and low temperaturehas been developed. Colloid solutions of metals from the series iron, nickel, cobalt, chromium, manganese or their mixtures were prepared in situ directly in the reaction mixture. Selective the hydrogenation of multiple carbon-carbon bonds without the reduction of a series of functional groups was observed.     

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.     

The chromatographic properties of transition metal complexes of pyridine-2-aldehyde-2-quinolylhydrazone

A scheme has been devised whereby PAQH complexes of iron, nickel, copper and cobalt can be separated chromatographically and determined semiquantitatively in presence of up to tenfold excesses of interfering metal ions. The visual detection limits for iron, nickel and copper were found to be 0.01 μg and for cobalt 0.007 μg per spot. Interesting relationships were observed between R_F values, decomposition temperatures and position of the absorption maxima of the adsorbed complexes.     

沉积钴镀层的粘接式氢氧化镍电极电化学性能研究

研究了在碱性可充电电池正极活性物质－球型氢氧化镍粒子表面化学镀钴后氢氧化镍电极的性能。通过比较充放电曲线和循环伏安试验结果,讨论了电极的放电容量、活性物质利用率和Ｎｉ（ＯＨ）２／ＭｉＯＯＨ氧化还原可逆性。实验还发现镀钴后的氢氧化镍电极有更好的充放电性能和优良的电极特性。测定了化学镀钴前后氢氧化镍电极的交流阻抗,表明镀钴后氢氧化镍的基体之间的有较低接触电阻。此外,本文还对钴镀层改进氢氧化镍性能的机理     

Picolinaldehyde 4-phenyl-3-thiosemicarbazone as a spectrophotometric reagent for the selective determination of small amounts of cobalt in the presence of iron

The characteristics and analytical applications of picolinaldehyde 4-phenyl-3-thiosemicarbazone are described. This compound gives coloured reactions with cobalt(II), iron(II) and (III), nickel(II), copper(II), palladium(II) and other ions, that are much more sensitive than those with picolinaldehyde thiosemicarbazone. The 1:2 yellow cobalt(II) complex has been used for the spectrophotometric determination of cobalt in the presence of iron, and applied to steel analysis.     

Anion-exchange separation of iron,cobalt and nickel

From 90% acetone-10% 6 M hydrochloric acid medium, cobalt and nickel are strongly adsorbed on the anion-exchange resin Dowex I-X8; iron is not adsorbed and can thus be separated from cobalt and nickel. Cobalt and nickel are then separated by elution with 70% acetone-30% 2 M hydrochloric acid; nickel is eluted before cobalt. The method can be applied to the determination of nickel and cobalt in materials with high iron content such as steels ; compleximetric titrations are used for the final step.     

Extraction and spectrophotometric determination of cobalt with dithizone

Cobalt(II) in acetate-tartrate buffer (pH 6.0-7.3) is extracted quantitatively as cobalt(III) dithizonate with excess of dithizone in CCl(4). The molar absorptivity in the CCl(4) phase is 4.6 x 10(4) 1.mole(-1).cm(-1) at the absorption maximum 550 nm. The calibration graph is linear for 1-10 mug of cobalt in 10 ml of CCl(4) when excess of dithizone is removed by back-extraction with 0.01M aqueous ammonia. Most interferences can be overcome by (a) initial extraction with dithizone at pH 1.3, (b) selective back-extraction into hydrochloric acid (pH 1 to 2), (c) oxidation of iron and tin to iron(III) and tin(IV) and addition of fluoride to complex the former, and (d) selective reaction of nickel dithizonate with 1,10-phenanthroline in the CCl(4) phase followed by back-extraction of nickel into 0.1M acid. The method has been applied to determination of cobalt in a copper-nickel-zinc alloy and a nimonic alloy.     

铁、钴、镍在汞中扩散系数的测定

用恒电位球形汞齐电极伏安法可测定金属在汞中的扩散系数^[1,2].本文报导了用这个方法测定的铁、钴、镍在汞中的扩散系数值.     

Quantum chemical modeling of reaction mechanism for 2-oxoglutarate dependent enzymes: effect of substitution of iron by nickel and cobalt

Enzymatic hydroxylation reactions carried out by 2-oxoglutarate (2OG) dependent iron-containing oxygenases were recently implicated in oxygen sensing. In addition to oxygen depletion, two metals, cobalt and nickel, are capable of inducing hypoxic stress in cells by inhibiting oxygenase activity. Two possible scenarios have been proposed for the explanation of the hypoxic effects of cobalt and nickel: oxidation of enzyme-bound iron following cobalt or nickel exposure, and substitution of iron by cobalt or nickel. Here, by using density functional theory calculations, we modeled the reaction route from the reaction components to the high-spin metal-oxide intermediate in the activation of oxygen molecule by 2OG-dependent enzymes for three metal ions Fe(II), Ni(II), and Co(II) in the active site. An initial molecular model was constructed based on the crystal structure of iron-containing asparaginyl hydroxylase (FIH-1). Nickel- and cobalt-containing enzymes were modeled by a consequent replacement of the iron in the active center. The energy profiles connecting stationary points on the potential surfaces were computed by using the intrinsic reaction coordinate (IRC) technique from the located transition states. The results of calculations show that the substitution of iron by nickel or cobalt modifies the reaction energy profile; however, qualitatively, the reaction mechanism remains essentially the same. Thus, we would postulate that if the iron ion in the active site were substitutable by nickel and/or cobalt ions enzyme activity would be considerably altered due to high activation barriers.     

Extraction chromatography with macroreticular polymer beads impregnated with monothiodibenzoylmethane solution

Extraction chromatography using macroreticular ethylstyrene-divinylbenzene beads impregnated with monothiodibenzoylmethane (SBB) solution has been investigated. Of the solvents used as the stationary phase, heptan-1-ol showed the highest rate of metal extraction, and loading with 0.5 ml of the solvent per g of resin was found to be the optimum. A column packed with such loaded beads can be used for the separation of nickel(II), iron(III) and cobalt(II).     

Solid phase extraction preconcentration of cobalt and nickel with 5,7-dichloroquinone-8-ol embedded styrene-ethylene glycol dimethacrylate polymer particles and determination by flame atomic absorption spectrometry (FAAS)

This article explores the synthesis of styrene-divinyl benzene (DVB)/ethylene glycol dimethacrylate (EGDMA) polymers embedded with quinoline-8-ol (Q) or its dihalo derivatives by thermal means in the presence and absence of 4-vinyl pyridine (VP). The above-synthesized polymers were found to enrich cobalt and nickel present in admixtures. Of these, 5,7-dichloroquinoline-8-ol (DCQ) embedded styrene-EGDMA polymer particles enrich cobalt and nickel quantitatively from dilute aqueous solutions within 5 min of preconcentration time. Styrene-EGDMA, DCQ embedded styrene-EGDMA particles obtained by bulk polymerization and cobalt/nickel bonded polymers were characterized by FTIR, thermogravimetric analysis (TGA), elemental analysis and surface area studies. The use of these polymer particles obtained by bulk polymerization for the solid phase extractive preconcentration of cobalt and nickel was investigated in detail and explores the possibility of employing this procedure for the analysis of cobalt and nickel in soil and sediment samples using a simple, low cost and readily available flame atomic absorption spectrometric instrument was explored.     

The determination of copper by complexometric titration with ethylenediaminetetraacetic acid

A method has been developed for the determination of cupric copper by complexometric titration with ethylen.ediaminetctraacetic acid. The titrations were followed potentiometrically, and were effected at pH 5–6 in the presence of an ammonium acetate buffer. Interfering metals such as ferric iron, aluminium, cadmium, zinc, manganese, nickel, cobalt and lead must be removed by a preliminary separation.     

Synthesis of certain pyridinyl and diazinyl hydrazones containing one or more ferroin groups, and their chromogenic reactions with iron, copper, cobalt and nickel

Fifteen new hydrazones with one or more ferroin groups were prepared, and their chelation and chromogenic properties with iron(II), copper(I), cobalt(II) and nickel(II) were investigated. Improved sensitivity in the spectrophotometric determination of cobalt, copper, and nickel is provided by several of the new compounds. Several others are capable of forming unusually stable and interesting binuclear iron(II) complexes.