(Series Editor) Transform Techniques in Chemistry,P.R. Griffiths,D. Hercules (Eds.), in: Modern Analytical Chemistry Series,Plenum, New York,NY (1978), 385 pp. $47.40

Concentration potentials in zinc sulphate, copper sulphate, nickel sulphate and cobalt sulphate solutions across liquid membranes based on myristates and laurates of zinc, copper, nickel and cobalt and caprate and caprylate of copper have been studied in concentration cells in which the liquid membrane separates the two solutions of the same electrolyte. The behaviour of the cell with heavy metal soap liquid ion-exchange membranes becomes more and more nernstian as the number of carbon atoms in the hydrocarbon chain of the fatty acid soap increases. Concentration potential values with copper, zinc, nickel or cobalt soap follow the order of their insolubility in water. The failure to record the theoretical potentials as calculated by Nernst's equation has been explained by considering the transport of water across organic phase by hydrated ions and the dissolution of heavy metal soaps in aqueous solutions. Liquid membranes based on heavy metal myristate soaps when used in concentration cells could measure the activities of zinc, copper, nickel and cobalt ions in the concentration range of 10^?4–10^?1M.     

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.     

Continuous spectrophotometric determination of copper, nickel and zinc in copper-base alloys by flow-injection analysis

Flow-injection methods have been developed for the determination of copper, nickel and zinc in copper-base alloys, including several types of brasses, deoxidized copper, beryllium copper and German silver. The system for copper and nickel involves the measurement of the absorbance of the copper(II) and nickel(II) aquo-complexes at 805 and 410 nm, respectively, after simple dissolution of the sample in a nitric acid-phosphoric acid mixture. The system needs no further reagents and the sample solutions can be analysed at rates of up to 280 /hr for copper (or nickel in German silver) without any carry-over. The system for zinc consists of automatic dilution of the injected sample with a thiosulphate-acetate buffer solution and the subsequent measurement of the absorbance of the zinc-Xylenol Orange complex at 568 nm. This system permits analysis rates of up to 90/hr for zinc solutions, with no carry-over. The procedures have been applied to standard copper-base alloys. The results agreed satisfactorily with the certified values. The precision ranges are 0.2-0.7% for copper and nickel and 0.5-0.8% for zinc.     

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。     

Chronopotentiometric and controlled-potential electrolytic studies of the formation of intermetallic compounds in copper-zinc,platinum-zinc,and other amalgams

The behaviors of amalgams containing: copper and zinc; platinum and zinc; platinum and cadmium; silver and zinc; silver and cadmium; cadmium and copper; cadmium, copper and platinum; and silver, nickel and zinc were investigated by controlled-potential electrolysis and chronopotentiometry. Copper-zinc amalgams contain the compound CuZn, for which the solubility product at 25°C is equal to (3.8±0.6)×10^?6M², and also a soluble but sparingly dissociated compound that is richer in zinc. Platinum-zinc amalgams contain PtZn₂, PtZn₃ and PtZn₄ in metastable equilibrium. Gold-cadmium amalgams contain the compound AuCd, whose solubility product at 25°C is equal to (1.7±0.1)×10^?5M². Compound formation could not be detected in silver-zinc, silver-cadmium, cadmium-copper, platinum-copper or cadmium-copper-platinum amalgams, but there was an uncertain indication that silver-nickel-zinc amalgams might contain the first ternary intermetallic compound found in amalgams.     

Minimization of Cu and Ni interferences in the determination of Sb by hydride generation atomic absorption spectrometry: the use of picolinic acid as masking agent and the influence of l-cysteine

The minimization of copper and nickel interference on the determination of antimony by hydride generation atomic absorption spectrometry using picolinic acid and l-cysteine as masking agents was studied. Concentrations up to 4000 and 1000 mg l⁻¹ of nickel and copper respectively were found to be tolerable in the presence of picolinic acid. The simultaneous presence of both transition metals could be tolerated by using a mixture of picolinic acid and l-cysteine. In the analysis of a nickel oxide certified reference material good agreement between the recommended and found values was verified. A detection limit (3 s, n=10) of 0.1 μg Sb g⁻¹ in the original sample was estimated.     

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.     

100例鼻咽癌患者与健康人头发中微量元素含量的比较

用原子吸收和火焰光谱分析法检测鼻咽癌患者100例，并以本地区100例健康人及同期我院内科住院非肿瘤患者150例为对照组，进行头发锌、铜、铁，钙，镍等的含量进行测定，结果发现鼻咽癌患者头发中钙及镍的含量比对照组明显升高，而头发中锌、铜的含量明显降低。     

Investigation of bis(carboxymethyl)dithiocarbamate complexes by the extraction method

The extraction of copper, lead, cadmium, nickel and zinc dithizonates was investigated in the presence of ammonium bis(carboxy-methyl)dithiocarbamate. For all metals studied, except zinc, masking of extraction was observed, depending on the amount of the dithio-carbamate in the aqueous phase. From the shift of the pH(1 2 ) values for dithizonate extraction, the stability constants beta(2) for the metal complexes with bis(carboxymethyl)dithiocarbamate were calculated. The logarithms of the constants are 21.46, 15.45,11.24 and 7.93 for the copper, lead, cadmium and nickel complexes respectively.     

The X-ray fluorescence determination of Cd, Ni, and Zn electrodeposited from aqueous solutions

The concentrations of cadmium, nickel, and zinc in standard solutions were determined by energy-dispersive X-ray fluorescence analysis of deposits prepared by flow electrolysis on graphite cloth electrodes. Reduction of the metal species in solution was complete only if cadmium or zinc was the major constituent (80 or 90 mole%, respectively). Deposits of cadmium and zinc, and cadmium-rich Cd---Ni, Cd---Zn, and Cd---Ni---Zn deposits were analysed. For pure metals the detected X-ray intensity displayed a power-law relationship, Rn^p, for up to 10⁻⁴ moles. The enhancement effect of the cadmium on the nickel and zinc signals, and the absorption and enhancement effects between nickel and zinc, were corrected empirically. The absorption of cadmium X-rays by nickel and zinc was insignificant. Deposits of pure copper on heavier electrodes displayed similar fluorescent intensities.     

Metal — organic interactions in sea water: an ecosystem experiment

A model plankton ecosystem was used to study the interactions of trace metals and organic compounds over a 10-day period during a phytoplankton bloom. Six bags of 1200–1 capacity were filled with coastal sea water. Three bags were spiked with copper (78, 157 and 314 nM) and one with copper (4.57 μM) plus nitrilotriacetic acid (10 μM). Samples were analysed for total dissolved copper, zinc, iron, nickel and manganese. The copper complexing capacity, determined by a method based on competition with Chelex-100 resin, was found to be essentially the same (35 nM) in all bags and independent of time. Organically bound complexes of copper (18% of the total), zinc (7%), nickel (4%) and iron (2%) were isolated by adsorption on Sep-Pak cartridges. The metal—organic complexes, were analysed on a liquid chromatograph interfaced to a multichannel atomic fluorescence detector. Organic complexes of zinc, iron and nickel were formed even in the presence of a large excess of copper. The organic and metal—organic compounds isolated by Sep-Pak cartridges became more polar as the bloom progressed.     

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。     

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.     

Detection and separation of metal ions on paper impregnated with 4-hydroxybenzthiazole

Zinc, magnesium and cadmium ions in the presence of ammonia, form intense blue chelates on paper impregnated, with 4-hydroxybenzthiazole, 0.25 microgram, 1.0 microgram and 0.1 microgram respectively, of these metal ions can be detected by means of this test. Several cations interfere.Alumunium can be separated from zinc, cadmium, copper, nickel and cobalt on paper impregnated with 4-hydroxybenzthiazole, which acts as a chromatographic column.     

Metal chelates of phosphonate-containing ligands: VII. Analytical applications of 1-hydroxyethane-1,1-diphosphonic acid

The polarographic behavior of copper, lead, antimony, and zinc ions in the presence of the title ligand, HEDP, is discussed. In highly alkaline solutions, the reversible wave of copper splits into two components, reversible and irreversible, the first of which is attributed to the reduction of the free cupric ions and the second wave was assigned to the reduction of the copper phosphonate species. The polarograms of zinc and antimony showed the presence of a single irreversible wave. In the case of lead, a quasi-reversible wave is observed. Cobalt and nickel forms inactive phosphonate chelates as inferred from the suppression of the wave heights with increasing of both the concentration of the ligand and the pH of the medium. In the presence of sufficiently excess HEDP buffered to pH 11.8, mixtures of the six elements showed the presence of four reasonably separated waves at half-wave potential values ?0.51, ?0.83, ?1.17, and ?1.55 V vs SCE corresponding to the reductions of copper, lead, antimony, and zinc complexes, respectively. The possibility of the individual and simultaneous analysis of these elements in their ternary mixtures with cobalt and nickel is discussed.     

Ion flotation of zinc using ethylhexadecyldimethylammonium bromide

Zinc ions react with the surfactant ethylhexadecyldimethylammonium bromide (EHDABr) to form a surface active sublate which can be removed from aqueous chloride solutions by ion flotation. A typical ion flotation procedure involves passing air through a 235-ml solution containing 5 ppm Zn²⁺, 2.0 M HCl, and 2.5 × 10^?3M EHDABr at a flow rate of 40 ml/min for 150 min. The procedure is simple and rapid. Cadmium, copper, lead, and nickel ions cause reductions of zinc flotation efficiencies of less than 2.5% under the experimental conditions.     

Polarized spectroscopy and hybrid materials of chiral Schiff base Ni(II), Cu(II), Zn(II) complexes with included or separated azo-groups

Chiral Schiff base complexes containing azo-groups, bis(N-R-1-naphtylethyl-4-phenyldiazenylsalicydenaminato) nickel(II), copper(II), and zinc(II) complexes affording a distorted square planar trans-[MN₂O₂] coordination geometry were prepared newly. Organic/inorganic hybrid materials in polymethylmethacrylate (PMMA) cast films of them (a containing type) or the analogous chiral Schiff base complexes, bis(N-R-1-phenylethyl-3,5-dichlorosalicydenaminato) nickel(II), copper(II), and zinc(II), and azobenzene (AZ) (a separated type) were assembled for comparison of polarized UV light induced molecular arrangement caused by Weigert effect. Investigation of parameters for optical anisotropy of metal complexes as well as AZ suggested that the degree of increasing optical anisotropy of the containing type is higher than that of the separated type based on π-π^∗ (of which characteristic band appeared around 380 nm), n-π^∗, and d-d bands of polarized absorption electronic spectra. Rigid nickel(II) or zinc(II) complexes are easy to increase optical anisotropy than flexible copper(II) complexes for both types.     

Thermodynamics of ion association XXV. Transition metal complexes of proline and hydroxyproline

Calorimetric and potentiometric measurements have been made at 25°C of the formation of the mono- and bis-hydroxyproline complexes of cobalt(II), nickel(II), copper(II) and zinc(II) and the proline complexes of copper(II) and nickel(II). The data have been used to calculate ΔG, ΔH and ΔS values for both protonation and metal complexation and these are discussed in terms of the nature of the metal—ligand binding.     

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。     

Copper(II) complexation and extraction with 2-ethylhexanoic acid <Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dialkylhydrazides

2-Ethylhexanoic acid N′,N′-dibutylhydrazide (DBH) and N′,N′-diheptylhydrazide (DHH) were synthesized. The existence regions of copper (II), zinc(II), nickel(II), and cobalt(II) complexes formed upon extraction with DBH in kerosene were studied. The neutral complex ML₂ extracted over a wide pH range (from pH ～ 6 to \(c_{NH_3 } \) ～ 4 mol/L) is formed only by copper(II), while zinc(II), nickel(II), and cobalt(II) react with DBH to yield precipitates that float at pH 7–9, 9–10.5, and 9.5–11, respectively. On the basis of IR spectra, elemental analysis, and properties, a structure was suggested for the CuL₂ complex with DBH. The DBH and DHH complexes with copper(II) are readily stripped with H₂SO₄ and H₂SO₄ + CuSO₄ solutions. The capacity of a 1.5 mol/L DHH in kerosene with respect to copper(II) is 26 g/L.