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。     

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.     

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（NH4）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pH6～9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。     

柱后反应高效离子交换色谱法测定Cu(Ⅱ)、Zn(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)、Fe(Ⅱ)

目前,在无机离子交换色谱中,多使用电化学检测系统,今年我国也研制成了库仑检测器。我们应用了高效离子交换柱,实现了某些离子的分离;并选用了适当的螯合剂与流出组分进行了柱后螯合显色反应;用一般高效液相色谱仪常备的分光光度检测器,实现了某些无机离子的检测。这种方法既增强了检测某些离子的选择性,也提高了检测灵敏度。实践表明,用Partisil-10 SCX键合相离子交换柱进行分离,用水溶性二乙醇胺二硫代甲酸螯合剂为柱后反应试剂,检测波长为405毫微米,测得Cu(Ⅱ)、Zn(Ⅱ)、Ni(Ⅱ)、Co(Ⅱ)、Fe(Ⅱ)的检出限量为毫微克级。实验液相色谱仪Perkin-Elmer Series 3型,配有LC-65T紫外-可见分光光度检     

茶叶、银杏叶中铅(Ⅱ)、镉(Ⅱ)、铜(Ⅱ)的测定

1　引　　言四 (4 磺酸苯基 )卟啉 (ＴＰＰＳ4)在最佳条件下可与Ｐｂ 、Ｃｄ 、Ｃｕ 形成稳定的络合物。但由于卟啉可与多种金属离子反应 ,因此 ,要将此络合物体系用于成分复杂的天然植物分析 ,则必须解决干扰问题。本文利用简便、易操作、不需使用大量有毒有机试剂及具有选择性吸附的巯基棉富集分离方法 ,实现了样品中干扰离子的分离以及痕量Ｐｂ 、Ｃｄ 、Ｃｕ 的富集和相互分离。此体系应用于茶叶、银杏叶中Ｐｂ 、Ｃｄ 、Ｃｕ 的测定 ,获得良好结果。2　实验部分2 .1　仪器和试剂　ＵＶ 2 4 0型紫外可见分光光度计 (日本岛津公司 …     

四元淋洗液的离子色谱法同时分离和测定铁(Ⅲ)、铁(Ⅱ)、铜(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)、钴(Ⅱ)和铅(Ⅱ)

本文叙述了一种四元淋洗液同时分离和测定七种金属离子的色谱条件。探讨了各离子的保留行为与淋洗液pH值和络合剂浓度间的变化规律。方法用于镀铬槽液中金属杂质分析,相对标准偏差小于2.0％,相对误差不超过3.5％。     

pH电位法研究水杨醛缩氨基硫脲与铜(Ⅱ)、锌(Ⅱ)、镍(Ⅱ)、钴(Ⅱ)、锰(Ⅱ)及镉(Ⅱ)的相互作用

水杨醛缩氨基硫脲对青霉菌、黄萎病菌、枯萎病菌及黑曲霉菌等真菌有显著的抑制活性。Thimmaiah等认为缩氨基硫脲的抗真菌活性来自对真菌代谢过程所需金属离子的螫合作用。为了进一步了解具有生物活性的水杨醛缩氨基硫脲在溶液中与常见金属离子的作用本质。我们在半微量恒温滴定池上用pH电位法研究了该物质与铜(Ⅱ)、锌(Ⅱ)、镍(Ⅱ)、钴(Ⅱ)、锰(Ⅱ)及镉(Ⅱ)等二价金属离子的配位作用。     

用聚乙二醇-硫酸铵-铝试剂体系萃取分离铁(Ⅲ)、铝(Ⅲ)、铜(Ⅱ)、钴(Ⅱ)、镉(Ⅱ)、锰(Ⅱ)、镍(Ⅱ)

研究了在聚乙二醇-硫酸铵-铝试剂体系中Fe（Ⅲ）、Al（Ⅲ）、Cu（Ⅱ）、Co（Ⅱ）、Cd（Ⅱ）、Mn（Ⅱ）、Ni（Ⅱ）的萃取分离行为．结果表明，在pH 5．0～6．5HAc-NaAc 缓冲溶液中，Fe（Ⅲ）、Al（Ⅲ）可被 PEG相几乎完全萃取，而 Cu（Ⅱ）、Co（Ⅱ）、Cd（Ⅱ）、Mn（Ⅱ）基本上不被萃取，从而实现了 Fe（Ⅲ）与 Cu（Ⅱ）、Co（Ⅱ）、Cd（Ⅱ）、Mn（Ⅱ）及Al（Ⅲ）与 Fe（Ⅲ）、Co（Ⅱ）、Cu（Ⅱ）混合离子的定量萃取分离。井研究了不同类型的表面活性剂对PEG相萃取行为的影响。     

Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)、Cu(Ⅱ)和Zn(Ⅱ)含硫Schiff碱配合物的合成

合成了5种含硫Schiff碱,8种相应的金属配合物。并对合成的配体和配合物进行了元素分析,红外光谱分析。对有代表性的化合物还进行了¹HNMR和质谱分析。确定了可能的分子结构式。     

邻苯二酚-3,6-二甲撑亚氨基二乙酸的酸离解平衡及其与碱土金属、锰(Ⅱ)、镉(Ⅱ)、锌(Ⅱ)、钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)、铁(Ⅱ)、钍(Ⅳ)及铀酰离子配合物稳定性的研究

本文报道用 pH 滴定法测得25.0±0.1℃时0.1mol·dm~(-3)KNO_3水溶液中邻苯二酚-3,6-二甲撑亚氨基二乙酸(CBMIDA,H_6L)的六级酸解离常数及 CBMIDA 的镁(Ⅱ)、钙(Ⅱ)、锶(Ⅱ)、钡(Ⅱ)、镍(Ⅱ)、锌(Ⅱ)、钴(Ⅱ)、镉(Ⅱ)、锰(Ⅱ)、铜(Ⅱ)、铁(Ⅲ)、钍(Ⅳ)和铀酰离子的配合物稳定常数 K_(MH_2L)~M、K_(MHL)~M、K_(ML)~M、K_(M_2L)~M 及配合物的质子化常数 K_(MH_2L)~H 和 K_(MHL)~H.讨论了 CBMIDA 的逐级酸离解的动态平衡机理以及金属离子与 CBMIDA 形成的各种配合物的配位形式.     

草酸根桥联的不对称双核铜(Ⅱ)和铜(Ⅱ)-锌(Ⅱ)配合物的合成与磁性

本文合成了一组新的不对称的双核配合物,[Cu_2(C_2O_4)_2terp]和〔Cu Zn(C_2O_4)_2terp〕(图1),terp表示联三吡啶。配合物〔Cu_2(C_2O_4)2terp〕的变温磁化率已测,其数值已用最小二乘法与Bleaney-Bowers方程拟合,求得交换积分J=-47.20cm~(-1)。文中还用Kahn理论解释了这种较弱的反铁磁自旋交换作用。     

酚氧桥联的不对称双铜(Ⅱ)和铜(Ⅱ)-锌(Ⅱ)配合物的合成和磁性

本文合成了一组新的不对称双核配合物「Cu(samen)Cu(terp)」和「Cu(samen)Zn(terp)」,samen~4和terp分别表示N N’-乙二水杨酰胺胺根阴离子和2.2′:6′2″-联三吡啶。配合物「Cu(samen)Cu(terp)」的变温磁化率已测,其数值用最小二乘法与Bleancy-Bowers方程拟合,求得交换积分J=-0.538cm~(-1),表明配合物中铜离子间有极弱的反铁磁自旋交换作用。     

SYNTHESIS AND STRUCTURES OF DICHLOROTETRAKIS-(PHENYLTHIOUREA) CADMIUM(II) AND CATENA-BIS(THIOCYANATE) BIS(PHENYLTHIOUREA)CADMIUM(II)

Abstract

Two new cadmium(II) complexes with phenylthiourea (PTU), namely Cd(PTU)₄Cl₂ (1) and [Cd₂(NCS)₂(μ₂-SCN)₂(PTU)₂(μ₂-PTU)₂] _n (2), have been prepared and characterized structurally by X-ray diffaction. Complex 1 crystallizes in the monoclinic space group C2/c, with a = 27.057(13), b = 8.108(3), c = 16.751(8) Å, β = 114.46°, V = 3345(3) ų, Z = 4. Complex 2 crystallizes in the triclinic space group P-1, with a = 9.336(3), b = 14.686(5), c = 16.911(5) Å, α = 71.36(2), β = 84.31(2), γ = 72.470(10)°, V = 2095.0(12) ų Z = 4. The structural analysis shows that each metal atom in both the mononuclear complex 1 and polynuclear complex 2 is octahedrally coordinated by four sulfur atoms and two chloro ligands or two nitrogen atoms from the thiocyanate groups, respectively. The PTU ligand can serve as either a monodentate ligand or a μ₂-bridging ligand upon coordination to a metal atom.     

镉(Ⅱ)与牛血清白蛋白的相互作用及pH、钙(Ⅱ)、锌(Ⅱ)和表面活性剂的影响

本文用恢复电位法、荧光分光光度法及粘度法研究了镉(Ⅱ)与牛血清白蛋白(BSA)的配位平衡和pH的影响。结果表明BSA有两类镉结合部位(2个强结合和10个弱结合部位)。Cd—BSA配位反应受pH影响,在近中性pH范围Cd(Ⅱ)与BSA结合未接近饱和时,以CURFIT程序对结合曲线拟合发现,每摩尔BSA平均结合Cd(Ⅱ)摩尔数的对数值与游离镉浓度的对数间成线性关系,进一步用Marguardt法处理得到Cd(Ⅱ)与BSA结合平衡方程式:N =K[Cd²⁺]^m,K和m均为pH函数。构象研究表明H⁺和Cd(Ⅱ)的结合都能引起BSA构象改变。用凝胶色谱法测定了Zn(Ⅱ)、Ca(Ⅱ)、吐温—80和十二烷基硫酸钠(SDS)对Cd—BSA结合的影响。Z_n(Ⅱ)可以竞争Cd(Ⅱ)在BSA上结合部位使Cd(Ⅱ)活动化。SDS能够有效抑制Cd(Ⅱ)与BSA结合,这种作用可能与SDS引起BSA构象改变有关。     

THE SYNTHESES AND PROPERTIES OF COBALT(II), NICKEL(II) AND COPPER(II) COMPLEXES WITH SOME 1,4-BENZODIAZEPINES

Abstract

The preparation and characterization of some cobalt(II), nickel(II) and copper(II) complexes with 7-chloro-2-methylamino-5-phenyl-3H-1, 4-benzodiazepin-4-oxide and 1, 3-dihydro-7-nitro-5-phenyl-2H-1, 4-benzodiazepin-2-one are reported. The complexes have been studied by means of magnetic susceptibility measurements, infrared and far infrared spectra, electronic spectra and conductivity measurements. Assignments for the metal-ligand and metal-halide bands have also been made. The evidence suggests that the cobalt(II) and nickel(II) complexes have a pseudotetrahedral symmetry, whereas the copper(II) complexes are octahedral.     

香草醛异烟酰腙与钴、镍、铜、锌和镉配合物的合成和性质研究

本文合成了香草醛异烟酰腙(H_2L~Ⅰ)和邻香草醛异烟酰腙(H_2L~Ⅱ)与钴(Ⅱ)、镍(Ⅱ)、铜(Ⅱ)、锌(Ⅱ)和镉(Ⅱ)的九个新配合物:M(HL~Ⅰ)_2·nH_2O[M(Ⅱ)=Co、Ni、Cu、Zn和Cd,n=0,2]和M(HL~Ⅱ)_2·nH_2O[M(Ⅱ)=Co、Ni、Cu和Zn,n=0-3]。采用元素分析、红外光谱、电子光谱、电导、磁化率、X-射线粉末衍射和热分析研究了两系列配合物的组成和性质。     

STRUCTURES OF PYRIDINE CARBOXYLATE COMPLEXES OF COBALT(II) AND COPPER(II)

Abstract

The syntheses and crystal structures of [Co(nic)₂(H₂O)₄] (1). [Co(iso)₂(H₂O)₄] (2). [Cu(nic)₂(H₂O)₄] (3), and [Cu(iso)₂(H₂O)₄] (4) (nic = nicotinate; iso = isonicotinate) are reported. Complex 1 crystallizes in monoclinic, space group C2/m with cell parameters a =14.150(4). b = 6.883(2)., c = 8.497(2) Å, β= 118.28(2)° and Z = 2. The other crystals. 2. 3. and 4. are all triclinic, Pī; a = 9.777(3), b = 6.348(4), c = 6.888(3)Å, a= 113.10(6)., β= 110.55(3). γ = 97.61(5)°, and Z=l for 2; a = 7.0281(4), b = 7.7176(6), c = 8.6978(7)Å, a = 68.103(7), β = 68.526(5), γ = 62.550(6)°, and Z=1 for 3; a = 9.1807(4), b = 6.3334(3), c = 6.8871(3)Å, a= 108.213(4), β = 99.433(4), γ= 105.190(4)°, and Z= 1 for 4. The arrangements around the metal ions are trans-octahedra with two pyridyl nitrogens and two aqua oxygens in the equatorial positions and two aqua oxygens in the axial positions, although the Cu(II) complexes show a larger Jahn-Teller distortion.     

REPARATION AND CHARACTERIZATION OF NEW SUPROFEN COMPLEXES OF Fe(III), Co(II) AND Ni(II)

Abstract

The preparation and properties of new complexes containing the biometals Fe(III), Co(II) and Ni(II) coordinated to the anti-inflammatory drug Suprofen are reported. The elemental analyses, together with the magnetic and thermal behavior and electronic, IR and Raman spectra, indicated the following stoichiometries for the latter two complexes: [M(Sup)₂(H₂O)₄]. For the Fe(III) complex, the generation of a dinuclear species may be proposed on the basis of ⁵⁷Fe Mössbauer measurements.     

SYNTHESIS OF 1,2-DIHYDROXYIMINO-l-PHENYL-3,7-DIAZA-9,10-O-BENZALOCTANE AND ITS COMPLEXES WITH Co(II), Cu(II) AND Ni(II)

Abstract

A novel dioxime, 1,2 dihydroxyimino-3,7-diaza-9,10-O-benzaloctane (LH₂) was prepared by reaction of l,2-0-benzylidene-4-aza-7-aminoheptane and anti-phenylchloroglyoxime in absolute ethanol. Mononuclear complexes with a metal-ligand ratio of 1:2 were prepared with Co(II), Cu(II) and Ni(II). To elucidate the structures of the ligand and complexes, elemental analyses, IR, ¹H NMR and ¹³C NMR spectral data and magnetic susceptibility measurements have been examined.     

AQUEOUS EQUILIBRIA OF COPPER(II)- AND NICKEL(II)-POLYGLYCINE COMPLEXES

Abstract

Magnetic susceptibility measurements, new potentiometric data, optical spectra, and a new statistical method of calculation are combined in the formulation of an equilibrium scheme defining the dilute solution interactions of nickel(II) and copper(II) ions with diglycine, triglycine, and tetraglycine as a function of pH. At low pH appreciable concentrations of a previously unreported complex, MHL²⁺ (HL =polyglycine ligands) are shown to be present in all nickel(II)-polyglycine systems and in the copper(II)-triglycine system. This new protonated species is assigned a structure in which the metal ion is coordinated to the terminal carboxylate and to the adjacent peptide carbonyl oxygen with the proton residing on the terminal amino group. As the pH is raised in the 1:1 systems, MH_?1L, MH_?2L^? and MH_{_3}L^2- are formed in succession depending on the number of peptide linkages in the ligands, HL. The concentration of the monodeprotonated intermediate species NiH_?1L never exceeds 10% of the total metal ion concentration in the triglycine case and is always less than 0.5% when tetraglycine is the ligand. The dideprotonated intermediate NiH_?2L- reaches a maximum of 38% of the total metal concentration in the 1:1 Ni-tetraglycine system. An explanation is presented for this negative deviation from the predictions based on statistical grounds. Complete species distribution diagrams which include the new protonated complexes are presented and are employed to explain the differences in the interactions of copper(II) and nickel(II) ions with polyglycine ligands. Probable coordinate bonding sites suggested for the complexes formed in solution are inferred on the basis of stoichiometry, relative stabilities, and available microscopic information.