硫酸铵-锌试剂-Tween 80体系萃取分离铜(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)、镉(Ⅱ)、锰(Ⅱ)

研究了(H4)2SO4-Zincon(锌试剂)-Tween 80体系萃取分离金属离子Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)的行为.试验表明,Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)在pH 6～9范围内,与Zincon形成的螯合物可被Tween 80相完全萃取,而Zn(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)基本不被萃取,进而实现了Cu(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)与Zn(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)混合离子的定量萃取分离.     

用聚乙二醇-硫酸铵-铬黑T体系从铁(Ⅲ)、钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)中萃取分离镉的研究

本文研究了聚乙二醇(PEG)-(NH_4)_2SO_(4-)铬黑T(EBT)体系对Fe(Ⅲ)、CO(Ⅱ)Ni(Ⅱ)、Cu(Ⅱ)、Cd(Ⅱ)的非有机溶剂萃取行为.结果表明,在pH7~11的 NH_3·H_2O-NH_4Cl缓冲溶液中,Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)可被聚乙二醇(PEG)相萃取,而Cd(Ⅱ)基本上不被萃取,从而获得了Cd(Ⅱ)与Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)混合离子的定量分离.     

聚乙二醇-硫酸铵-二甲酚橙体系萃取分离钯

研究了萃取剂二甲酚橙与Pd(Ⅱ)离子的螯合物在聚合物-硫酸铵-水体系中两相间的分配行为。在pH1．0～6．0条件下，Pd(Ⅱ)几乎被二甲酚橙完全萃取到PEG相中，而Fe(Ⅱ)、Co(Ⅱ)、Zn(Ⅱ)萃取率随pH变化显著，Mn(Ⅱ)、Cd(Ⅱ)基本不被萃取。在HClO4介质pH1．0～2．0条件下，实现了Pd(Ⅱ)与Fe(Ⅱ)、Co(Ⅱ)、Zn(Ⅱ)、Mn(Ⅱ)、Cd(Ⅱ)的定量萃取分离。     

Synthesis and Characterization of the cis-Dicyanoiron(Ⅱ) Building Block and Its Interactions with Selected Metal Ions

In this work, a cis-dicyanoiron(Ⅱ) building block, cis-Fe~(Ⅱ)(bpy)_2(CN)_2(1, bpy = 2,2?-bipyridine), has been prepared and fully characterized by IR, electronic absorption spectra, elemental analysis, cyclic voltammetry and single-crystal X-ray diffraction analysis. The interactions of complex 1 with selected metal ions, such as Cu(Ⅱ), Fe(Ⅲ), Pb(Ⅱ), Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ), were investigated employing electronic absorption spectroscopy. The electronic absorption spectroscopy indicates Cu(Ⅱ), Fe(Ⅲ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Zn(Ⅱ) and Ni(Ⅱ) ions steadily coordinate with 1 via cyanide, respectively. Fluorescent emission intensity of 1 increased upon the addition of Zn(Ⅱ) ion, quenched by adding ions Cu(Ⅱ), Fe(Ⅲ) and Pb(Ⅱ), and it was almost unchanged when adding the Fe(Ⅱ), Cr(Ⅲ), Cd(Ⅱ), Co(Ⅱ), Ni(Ⅱ) and Mn(Ⅱ) ions.     

混酸体系中31种金属离子的浮选行为

在总浓度为0.17～3.4N的HCl-HNO_3(〔HCl〕:〔HNO_3〕=2.4:1)体系中,以(18～60)×10~(-5)M的CPC为捕集剂,对(2.755～28.69)×10~(-5)M的31种金属离子进行了浮选,表明Ir(Ⅳ)、Pt(Ⅳ)、Ge(Ⅳ)、Sn(Ⅳ)、Bi(Ⅲ)、Au(Ⅲ)、T1(Ⅱ)、Pd(Ⅱ)、Sn(Ⅱ)可浮选95％以上,而Cr(Ⅵ)、Ti (Ⅳ)、Zr(Ⅳ)、Ga(Ⅲ)、In(Ⅲ)、Fe(Ⅲ)、Sb(Ⅲ)、Al(Ⅲ)、Mn(Ⅱ)、Fe(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ)、Pb(Ⅱ)浮选率低于20％或几乎不浮选,Ru(Ⅱ)、Rh(Ⅱ)、Ir(Ⅱ)、Hg(Ⅱ)、Ag(Ⅰ)、TI(Ⅰ)部分被浮选。与HCl体系的浮选结果进行了比较,发现贵金属的浮选率和选择性在HCl-HNO_3体系中更好。进行了Au(Ⅲ)、Pt(Ⅳ)、Pd(Ⅱ)与Zn(Ⅱ)、Cd(Ⅱ)、Hg(Ⅱ)、Sb (Ⅲ)的分离试验,结果令人满意。     

薄层色谱法测定痕量的镍(Ⅱ)、铜(Ⅱ)、镉(Ⅱ)、钴(Ⅱ)、锌(Ⅱ)的研究

在pH值为9.5～9.9的氨-氯化铵的缓冲溶液中,镍(Ⅱ)、铜(Ⅱ)、镉(Ⅱ)、钴(Ⅱ)、锌(Ⅱ)形成氨合络合物,而银(Ⅰ)、铋(Ⅲ)、铁(Ⅲ)、铁(Ⅱ)、汞(Ⅱ)、汞(Ⅰ)、锰(Ⅱ)、铅(Ⅱ)、锡(Ⅳ)、锡(Ⅱ)、钒(Ⅴ)、铝(Ⅲ)、钛(Ⅳ)等生成各种形式的沉淀。用甲醇-乙醇-氯化铵-氨-水体系(pH9.0～9.1),在硅胶H薄层板上,可以实现镍(Ⅱ)、铜(Ⅱ)、镉(Ⅱ)、钴(Ⅱ)、锌(Ⅱ)的分离。双硫腙显色后,用CS-930双波长薄层扫描仪测定含量。线性范围:锌0.01～0.20微克,铜0.01～0.25微克,镍、镉、钴0.01～0.30微克。     

用Tween 80-硫酸铵-1-(2-吡啶偶氮)-2-萘酚-磺酸体系萃取分离钯(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)、镉(Ⅱ)、锰(Ⅱ)和铝(Ⅲ)

研究了Tween 80水溶液在(NH4)2SO4存在下,水溶性螯合剂1-(2-吡啶偶氮)-2-萘酚-磺酸与金属离子螯合物在该体系中两相间的分配行为.结果表明,Pd(Ⅱ)、Co(Ⅱ)在pH 2.0～3.5缓冲溶液中可被Tween相完全萃取,而Zn(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)、Al(Ⅲ)基本上不被萃取.在不同pH条件下实现了Pd(Ⅱ)、Co(Ⅱ)、Ni(Ⅱ)、Zn(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)、Al(Ⅲ)混合离子的定量萃取分离.     

用2-(5-溴-吡啶偶氮)-5-二乙氨基苯酚改性硅胶富集,分离痕量金属离子的研究

本文用分批平衡法研究了几种常见过渡金属离子在2—(5—溴—吡啶偶氮)—5—二乙氨基苯酚改性硅胶(5—Br-PADAP-SG)上的吸附行为。5-Br-PADAP-SG对Cu(Ⅱ)、Zn(Ⅱ)、Ni(Ⅱ)、Cd(Ⅱ)、Co(Ⅱ)、Fe(Ⅱ)的最大吸附量分别是17.7、24.0、15.8、16.4、10.2、13.8μmol/g。pH 5.8,经5—Br—PADAP—SG柱富集后,用0.4mol/L HClO_4溶液洗脱,可进行Cu(Ⅱ)、Ni(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)、Fe(Ⅲ)的全分析,在pH3,Cu(Ⅱ)、Ni(Ⅱ)与Cd(Ⅱ)、Mn(Ⅱ)可完全分离。用原子吸收分光光度法测定水样中金属离子下限可达ppb级。     

新型络合吸附剂的研究(Ⅳ)──铜(Ⅱ)、镍(Ⅱ)模板高分子多乙烯多胺吸附剂的记忆性

研究了铜(Ⅱ)、镍(Ⅱ)离子模板高分子多乙烯多胺络合吸附剂的动态吸附金属离子的行为。5个周期的动态吸附结果表明,合成的铜(Ⅱ)、镍(Ⅱ)模板吸附剂分别对铜(Ⅱ)和镍(Ⅱ)金属离子具有稳定的吸附能力,其动态饱和吸附量达4.357mmolCu(Ⅱ)/g[铜(Ⅱ)模板吸附剂]、3.153mmolNi(Ⅱ)/g[镍(Ⅱ)模板吸附剂];相对误差分别为±1.5%和±2.2%.     

桑色素及其配合物与DNA作用的比较

采用光度法、粘度法和电化学方法考察了桑色素及其配合物和DNA的作用.并对桑色素合铜(Ⅱ)、桑色素合锌(Ⅱ)、桑色素合钴(Ⅱ)、桑色素与DNA作用的方式进行了比较.Cu(Ⅱ), Zn(Ⅱ), Co(Ⅱ)桑色素配合物与DNA作用时的荧光光谱性质类似,不同于配体.钴(Ⅱ)配合物的电化学行为与铜(Ⅱ)配合物相似,不同于锌(Ⅱ)配合物.三种配合物的存在,都可引起DNA的粘度增加.但钴(Ⅱ)配合物对EB-DNA复合物的荧光光谱影响很小,而铜(Ⅱ)、锌(Ⅱ)配合物对EB-DNA复合物的荧光光谱影响较大.实验结果表明,与DNA之间的作用,钴(Ⅱ)配合物弱于铜(Ⅱ)、锌(Ⅱ)配合物.这可能是钴(Ⅱ)配合物的抗肿瘤活性低于与DNA嵌入结合的铜(Ⅱ)、锌(Ⅱ)配合物的原因之一.     

Discrete Rh(III)/Fe(II) and Rh(III)/Fe(II)/Co(III) cyanide-bridged mixed valence compounds

The heterotrinuclear complexes trans- and cis-[{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) are unprecedented examples of mixed valence complexes based on ferrocyanide bearing three different metal centers. These complexes have been assembled in a stepwise manner from their {trans-III-L(14S)Co(III)}, {cis-VI-L(15)Rh(III)}, and {Fe(II)(CN)(6)} building blocks. The preparative procedure follows that found for other known discrete assemblies of mixed valence dinuclear Cr(III)/Fe(II) and polynuclear Co(III)/Fe(II) complexes of the same family. A simple slow substitution process of [Fe(II)(CN)(6)](4-) on inert cis-VI-[Rh(III)L(15)(OH)](2+) leads to the preparation of the new dinuclear mixed valence complex [{cis-VI-L(15)Rh(III)(μ-NC)}Fe(II)(CN)(5)](-) with a redox reactivity that parallels that found for dinuclear complexes from the same family. The combination of this dinuclear precursor with mononuclear trans-III-[Co(III)L(14S)Cl](2+) enables a redox-assisted substitution on the transient {L(14S)Co(II)} unit to form [{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+). The structure of the final cis-[{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) complex has been established via X-ray diffraction and fully agrees with its solution spectroscopy and electrochemistry data. The new species [{cis-VI-L(15)Rh(III)(μ-NC)}{trans-III-L(14S)Co(III)(μ-NC)}Fe(II)(CN)(4)](2+) and [{cis-VI-L(15)Rh(III)(μ-NC)}Fe(II)(CN)(5)](-) show the expected electronic spectra and electrochemical features typical of Class II mixed valence complexes. Interestingly, in the trinuclear complex, these features appear to be a simple addition of those for the Rh(III)/Fe(II) and Co(III)/Fe(II) moieties, despite the vast differences existent in the electronic spectra and electrochemical properties of the two isolated units.     

Water-activity and double-layer effects on the Fe(II)/Fe(Hg) reaction

The title subject is studied by electrode-kinetic measurements in acetate buffered potassium chloride and magnesium sulphate solutions of varied concentration at 25°C, using literature data for activity and double-layer properties. The results indicate that the Fe(II)/Fe(Hg) reaction occurs by an essentially symmetric (α near 1/2) ferrous-ion transfer (n=2), that this transfer is second order in water-activity dependence, and that it exhibits a smaller than classically expected double-layer effect. No specific interaction appears for any of the ions of the supporting salts. An e.c. reaction scheme is proposed for the Fe(Hg)/Fe(II) electrode in non-complexing aqueous solution.     

Concatenation of two molecular switches via a Fe(II)/Fe(III) couple

[reaction: see text] Modulation of the fluorescein fluorescence in the presence of spiropyran and ferric ion by light was observed. Such fluorescence modulation was due to the low oxidation potential of complex MC.Fe(2+), which made the electron transfer from MC.Fe(2+) to Flu(+)()(*)() thermodynamically favorable. As a result, the communication between two molecular switches based on fluorescein and spiropyan, respectively, was realized via the reversible Fe(III)/Fe(II) redox couple. The communicating behavior corresponds well to the function of an INHIBIT logic gate.     

Some quantum chemical aspects on outer-sphere electron-transfer reactions: the U(V)/Fe(III)-U(VI)/Fe(II) system

The activation energy and rate constant of U(V)-Fe(III) to U(VI)-Fe(II) outer-sphere electron-transfer reaction was studied using Marcus model. Experimental values were used for Gibbs energy change of the reaction, and energy surfaces were calculated by quantum chemical methods. The calculated rate constant was in reasonable accord with experimental value.     

Titration curves in complexometric titrations with the redox system Fe(III)/Fe(II)

Potentiometric titrations of metal ions with EDTA have been carried out with a platinum or graphite electrode and the Fe(III)/Fe(II) redox system. In the absence of oxygen and for pH < 2 the titration curves may be described by an equation similar to that given previously for titrations with silver and mercury electrodes. Titration curves for bismuth and indium, which are more strongly complexed than iron, are asymmetrical and useful for analytical purposes. When the titrated ions are complexed less strongly than iron(III) ions the kinetics of metal complexation have a pronounced effect. The titration curves of thorium and copper, which react more rapidly than iron, are analytically useful. The curves recorded rapidly after titrant additions have a better end-point break than those which correspond to thermodynamic equilibrium. When a metal, e.g., nickel, is weakly bound by EDTA, and reacts more slowly than iron, a very small end-point break or none at all is observed.     

Influence of freezing of aqueous samples on the Fe(II)/Fe(III) equilibrium

The influence of freezing of aqueous samples on the Fe(II)/Fe(III) equilibrium has been investigated by ion chromatography. No change has been observed in the pH-range 2–5, irrespective of the freezing temperature.     

对乙酰氨基酚在Fe（Ⅲ）／草酸盐体系中的光降解

药品和个人护理用品(Pharmaceuticals and Personal Care Products,简称PPCPs)作为潜在环境污染物,在近几年成为新的环境热点问题[1,2].对乙酰氨基酚(APAP)作为一种典型的药品和个人护理用品被用作阿司匹林的替代物,主要起到减轻疼痛的作用.     

Ethylene Oligomerization by (dppe)MCl_2 [M = Fe(II), Co(II),Ni(II)] Complexes/EAO

Transition-metal-catalyzed oligomerzation of ethylene is an important process to provide a-olefins in the C6~C20 range. In recent years, the catalytic behavior of late transition metal complexes containing bi- and tri-dentate ligands for oligomerization of ethylene to a-olefins has attracted much attention. When oligomerization of ethylene catalyzed by nickel diimine and Fe(II), Co(II) 2,6-bis(imino)pyridine catalysts, the oligomers with high average molecular weight were obtained1-5. Eth…     

Electrochemical characterization of the redox couple of Fe(III)/Fe(II) mediated by grafted polymer electrode

A new grafted polymer electrode (GPE) (polystyrene as polymer) was grafted with acrylonitrile as a monomer using gamma irradiation to produce a new grafted polymer. The redox process of K₃Fe(CN)₆ during cyclic voltammetry was studied by the new GPE. The ratio of Ipc/Ipa >1 of GPE to GCE Ipc/Ipa = 1.7, indicating that this electrode is a reversible electrode and can be used in conductivity studies by voltammetric analysis. The physical properties of the new electrode GP have good hardness, insolubility, and stability at different high temperatures and at different pH. Also, the sensitivity under conditions of cyclic voltammetry is significantly dependent on pH, electrolyte, and scan rate. At different scan rates, two oxidation peaks and two reduction peaks of Fe(III) were observed in a reversible process: Fe(III) Fe(II), and Fe(II) Fe(0). Interestingly, the redox reaction of Fe(III) solution using GPE remained constant even after 15 cycles. It is therefore evident that the GPE possesses some degree of stability. The potential use of the grafted polymer as a useful electrode material is therefore clearly evident.     

Synthesis,characterization and evaluation of heterobimetallic Fe(II)/Rh(I) and Fe(II)/Ru(II) complexes as catalyst precursors for hydroformylation of 1-octene

Abstract

Two new ferrocenyl iminopyridyl ligands, L1 and L2, have been synthesized and characterized using spectroscopic and analytical techniques. Both ligands were used to prepare new Rh(I) and Ru(II) ferrocenyl complexes 1–4. The structures of the complexes were confirmed using ¹H and ¹³C nuclear magnetic resonance spectroscopy, high resolution electrospray ionization mass spectrometry, and infrared spectroscopy. The complexes were tested as catalysts in the hydroformylation of 1-octene. Rh ferrocenyl complexes 1 and 4 produced aldehydes under mild conditions while the Ru-ferrocenyl complexes 2 and 3 required higher temperature and pressure for effective hydroformylation to occur. The catalysts display excellent aldehyde chemoselectivity with varying regeoselectivity depending on temperature and pressure conditions employed. At high temperatures, the Rh ferrocenyl precatalysts favor formation of branched aldehydes due to increased isomerization at high temperatures. The Ru ferrocenyl precatalysts displayed less hydroformylation activity; however, the complexes show good chemoselectivity for aldehydes with no hydrogenation products formed.