笼形聚偕氨肟树脂的研究：酸处理树脂的吸附性能

笼形聚偕氨肟树脂（ＣＡＯ）经盐酸处理垢，伯胺基转变成胺盐。酸处理笼形聚偕氨肟树脂（ＡＣＡＯ）对Ｍｇ＾２＋，Ｃａ＾２＋，Ｂａ＾２＋，Ｍｎ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋离子不吸附；对Ｚｎ＾２＋，Ｃｄ＾２＋，Ｃｕ＾２＋，Ｐｂ＾２＋离子的吸附效率在２０％以下，但对Ｈｇ＾２＋离子的吸附效率则高达７１．２％；对一些金属络阴离子的吸附效率顺序是Ｆｅ（ＣＮ）＾２－６＞Ｃｒ２Ｏ＾２－７＞ＭｏＯ＾２－４＞ＰｔＣｌ＾２     

PTFE—乙醚柱反相萃取层析连续分离和测定镓（Ⅲ）铟（Ⅲ）的研究

研究了在抗坏血酸存在下的６ｍｏｌ／Ｌ ＨＢｒ介质作流动相，以ＰＴＦＥ（聚四氟乙烯）负载的乙醚作固定相，反相萃取层析使微量Ｇａ（Ⅲ），Ｉｎ（Ⅲ）与Ｆｅ＾３＋、Ｔｌ＾３＋、Ｍｏ＾６＋、Ａｕ＾３＋、Ｔｉ＾４＋、Ｂｉ＾３＋、Ａｌ＾３＋、Ｍｇ＾２＋、Ｃａ＾２＋、Ｎｉ＾２＋、Ｃｏ＾２＋、Ｃｄ＾２＋、Ｚｎ＾２＋、Ｐｂ＾２＋、Ｃｕ＾２＋等多种离子分离。留于柱上的铟、镓分别用ＨＣｌ（４ｍｏｌ／Ｌ）－Ｈ２Ｏ２（３％）     

丙醇—溴化十六烷基三甲胺—硫酸铵—水体系萃取分离汞（Ⅱ）

研究了丙醇－溴化十六烷基三甲胺９ＣＴＭＡＢ）－（ＮＨ４）２ＳＯ４－水体系萃取分离泵的行为及与常见离子分离条件。试验表明：调节ｐＨ１．０或３．０,能使Ｈｇ从Ｆｅ＾３＋,Ｃｏ＾２＋,Ｎｉ＾２＋ｍ,Ｚｎ＾２＋,Ｍｎ＾２＋,Ｃｕ＾２＋,Ａｌ６３＋等离子混合液中分离出来。     

低压离子色谱仪的原理及应用

本介绍了一种新型的离子色谱仪，它可以在１．９６－２．９４×１０＾５Ｐａ（约２８－４３Ｐｓｉ）的低压下，分析Ｃｕ＾２＾＋，Ｚｎ＾２＾＋，Ｎｉ＾２＾＋，Ｃｏ＾２＾＋，Ｆｅ（Ⅲ），Ｃｄ＾２＾＋，Ｍｎ＾２＾＋，Ｆｅ＾２＾＋，Ａｌ（Ⅲ），Ｚｒ（Ⅲ），Ｃｒ（Ⅲ），Ｃｒ（Ⅵ）等金属阳离子。中介绍了该仪器的原理及应用。     

活性碳纤维ZnO—SACF氧化还原机理的研究

本文借助于ＩＲ，ＴＧ和ＸＰＳ，研究了ＺｎＯ－ＳＡＣＦ制备过程中及其吸附Ａｇ＾＋和Ａｕ＾３＋前后的化学结构变化。实验结果表明：从ＳＡＣＦ到ＺｎＯ－ＳＡＣＦ，纤维表面上的Ｏ／Ｃ原子比和含氧基团如Ｃ＝Ｏ和ＣＯＯ都有所减少；ＺｎＯ－ＳＡＣＦ上还原性功能基团主要是－Ｃ－ＯＨ，当ＺｎＯ－ＳＡＣＦ吸附Ａｇ＾＋后，－Ｃ－ＯＨ被氧化为－Ｃ＝Ｏ，而当其吸附Ａｕ＾３＋后，－Ｃ－ＰＨ被氧化为－Ｃ＝Ｏ和－（Ｏ＝Ｃ）－ＯＨ，     

2—氨基苯并噻唑萃取铑及铑,铱分离的研究

本文研究用２－氨基苯并噻唑（简写ＡＢＴ）溶剂萃取铑的最佳条件，在ＫＩ存在下于ｐＨ１～３，加热６０ｍｉｎ，所形成的络合物能定量地被己烷萃取，贱金属离子如Ｆｅ＾３＋，Ａｌ＾３＋，Ｃｕ＾２＋，Ｃｄ＾２＋，Ｃｏ＾２＋，Ｎｉ＾２＋，Ｚｎ＾２＋，Ｍｎ＾２＋，Ｃａ＾２＋，Ｍｇ＾２＋及铂族离子Ｐｔ（Ⅳ），Ｉｒ（Ⅳ）不被萃取，Ｐｄ＾２＋，可在未加入ＫＩ之前预先萃取分离，斜率测得萃合物组成为ＲｈＩ３（ＡＢＴ），红外光     

PAN—聚氨酯泡沫塑料富集ICP—AES同时测定天然水中铜锌镉锰…

研究了１－（２－吡啶偶氮）－２－萘酚（ＰＡＮ）在聚氨酯泡沫塑料上的吸附特征，对Ｃｕ＾２＾＋，Ｚｎ＾２＾＋，Ｃｄ＾２＾＋，Ｍｎ＾２＾＋，Ｆｅ＾２＾＋，Ｃｏ＾２＾＋和Ｐｂ＾２＾＋７种离子的吸附性能，以及富集体积，流速，基体元素的影响。建立了ＰＡＮ－聚氨酯泡塑料富集ＩＣＰ－ＡＥＳ同时测定天然水样中上述７种元素的分析方法，获得满意结果。     

联氨在d—过渡金属配合物的MTP（о—NO2）TBP修饰石墨电…

研究了Ｎ２Ｈ４在间－四（邻－硝基苯基）四苯并卟啉铁（Ⅲ）、钴（Ⅱ）、锌（Ⅱ）和镍（Ⅱ）配合物［ＭＴＰ（о－ＮＯ２）ＴＢＰ，简称ＭＴＢＰ］修饰石墨电极上的催化电氧化反应，测得该系列金属四苯并卟啉的催化活性的顺序为Ｃｏ（Ⅱ）ＴＢＰ＞ＣｌＦｅ（Ⅲ）ＴＢＰ＞Ｎｉ（Ⅱ）ＴＢＰ＞Ｚｎ（Ⅱ）ＴＢＰ≈石墨，考察了Ｃｏ（Ⅱ）ＴＢＰ和ＣｌＦｅ（Ⅲ）ＴＢＰ催化联氨电氧化反应的动力学过程。结果表明，ＯＨ＾－和Ｎ２Ｈ４在Ｃ     

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…

本研究了聚乙二醇（ＰＥＧ）－（ＮＨ４）２ＳＯ４－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ＮＨ３·ＨＮＨＣｌ缓冲溶液中，Ｆｅ（Ⅲ）、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（Ⅲ）、Ｃｏ（Ⅱ）、Ｎｉ（Ⅱ）、Ｃｕ（Ⅱ）混合离子的定量分离。     

碘量法测定冶金物料中铁

系统地研究了Ｆｅ＾３＋与Ｉ＾－定量反应的条件，共存离子的干扰及消除方法，在ＨＣｌ和ＫＩ存在下，Ｆｅ＾３＋与Ｉ＾－定量反应，Ｃｕ＾２＋，ＡｓＯ４＾３－，ＶＯ２＾＋，等定量干扰，使用ＮａＦ或Ｈ３ＰＯ４制备参比液可抵消干扰。可不经分离直接测定大部分冶金物料中的高含量铁。     

卟啉化合物电化学性质研究 Ⅰ.5,10,15,20-四-(4-乙酰氧基苯)卟吩及其Cu、Zn、Fe、Co、Ni配合物的合成及循环伏安研究

本文报道了5,10,15,20-四-(4-乙酰氧基苯)卟吩[T(4AOP)P]及其Cu、Zn、Fe、Co、Ni配合物的合成及其在CH_2Cl_2-0.1mol/1 TBAP体系中的循环伏安(CV)研究结果.CV实验表明:Cu~(2+)、Zn~(2+)、Ni~(2+)离子以稳定的+2价存在于T(4AOP)P中,电子转移反应在卟啉环上进行,而Fe~(3+)、Co~(2+)离子在氧化还原过程中发生价态变化。实验发现:不同金属卟啉在卟啉环上氧化还原顺序及其非均相电子转移反应速率常数与环上π电子云密度成规律性变化.     

Studies on the reaction products of bis(2-furanthiocarboxyhydrazidato)m(II) with pyridine-2- and -4-carboxaldehydes

Condensation of bis(2-furanthiocarboxyhydradatometal(II), M(fth)₂; [M (II) = Mn, Fe, Co, Ni, Cu and Zn] with pyridine-2- and -4-carboxaldehydes gave complexes of the formula M(pfth)₂ [pfth? = pyridine-2-carboxaldehyde-2-furanthiocarboxyhydrazonato], Ni(Ifth)₂, Zn(Ifth)₂, Cu(Ifth) and Co(Ifth)₃, (Ifth? = pyridine-4-carboxaldehyde-2-furanthiocarboxyhydrazonato). The magnetic and electronic spectral studies coupled with photoacoustic or Mössbauer spectra suggested octahedral geometry for the M(II) complexes with low-spin states for Co(Ifth)₃ and Fe(pfth)₂. IR and ¹H NMR spectral studies of diamagnetic complexes suggested bonding through “azomethine” nitrogen and “thiolo” sulphur. IR spectra also showed the involvement of pyridine ring nitrogen in coordination in all the complexes except Cu(Itfh), Co(Ifth)₃, and Zn(Ifth)₂. Some of the compounds possessed antimicrobial activity.     

Raman spectroscopic studies on surface coordination mechanism of benzotriazole and triphenylphosphine with metals

The complexes of benzotriazole (BTAH) with Ag, Cu, Fe, Zn and Ni were prepared respectively in the non-aqueous solution by the direct electrochemical synthesis and characterized by microanalysis and normal Raman spectroscopy. The influence of the neutral ligand of triphenylphosphine (pph₃) on the coordination process was deduced by the normal Raman spectroscopy and electrochemistry. The metals were classified into two categories. For the first type, such as Cu and Ag, CuBTA and AgBTA were obtained in the solution without pph₃. The introduction of pph₃ led to its participation in the coordination processes of BTAH with Cu or Ag and appeared in the final complex. Fe, Zn and Ni belonged to the second type, there was no influence on the coordination of BTAH with Zn, Ni and Fe, i.e., the final complexes were Fe(BTA)₂, Zn(BTA)₂ and Ni(BTA)₂, respectively, in the solution with/without pph₃. The electrochemical results revealed that the BTAH can inhibit the corrosion of all the above metals, and the introduction of pph₃ resulted in the decrease of inhibition efficiency to Cu surface, while no influence was observed on the Ni surface. The different role of pph₃ was explained in terms of hard/soft acids and bases rule and coordination mechanism was proposed.     

Raman spectroscopic studies on surface coordination mechanism of benzotriazole and triphenylphosphine with metals

The complexes of benzotriazole (BTAH) with Ag, Cu, Fe, Zn and Ni were prepared respectively in the non-aqueous solution by the direct electrochemical synthesis and characterized by microanalysis and normal Raman spectroscopy. The influence of the neutral ligand of triphenylphosphine (pph₃) on the coordination process was deduced by the normal Raman spectroscopy and electrochemistry. The metals were classified into two categories. For the first type, such as Cu and Ag, CuBTA and AgBTA were obtained in the solution without pph₃. The introduction of pph₃ led to its participation in the coordination processes of BTAH with Cu or Ag and appeared in the final complex. Fe, Zn and Ni belonged to the second type, there was no influence on the coordination of BTAH with Zn, Ni and Fe, i.e., the final complexes were Fe(BTA)₂, Zn(BTA)₂ and Ni(BTA)₂, respectively, in the solution with/without pph₃. The electrochemical results revealed that the BTAH can inhibit the corrosion of all the above metals, and the introduction of pph₃ resulted in the decrease of inhibition efficiency to Cu surface, while no influence was observed on the Ni surface. The different role of pph₃ was explained in terms of hard/soft acids and bases rule and coordination mechanism was proposed.     

Synthesis, characterization and electrochemical investigation of a novel vic-dioxime ligand and its some transition metal complexes

4-(Chloroacetyl)diphenyl ether was synthesized from chloroacetyl chloride and diphenyl ether in the presence of AlCl₃ as catalyst in a Friedel-Crafts reaction. Then, its keto oxime and dioxime derivatives were prepared. 4-phenoxy-(N-4-chlorophenylamino)phenylglyoxime (H₂L) was synthesized from 4-(phenoxy)chlorophenylglyoxime and 4-chloroaniline. Ni(II), Co(II) and Cu(II) complexes of H₂L were obtained. The mononuclear Ni(II), Co(II) and Cu(II) complexes of H₂L have a metal–ligand ratio of 1:2 and the ligand coordinates through the two N atoms, as do most of the vic-dioximes. The structure of the ligand was identified by FT-IR, ¹H NMR, ¹³C NMR, ¹³C NMR (APT) spectroscopy and elemental analysis data. The structures of the complexes were characterized on the basis of FT-IR, ICP-AES, UV-Vis, elemental analysis, magnetic susceptibility measurements, and cyclic voltammetry. The electrochemical measurements were obtained by using cyclic voltammetry in DMF solution at room temperature. The electrochemical behaviors of H₂L and its complexes showed that the redox process of H₂L has one irreversible oxidation wave, whereas the redox processes of the complexes have both oxidation and reduction waves with metal centered.     

Structure of (5656)macrotetracyclic chelates in the ternary systems M(II)-ethanedithioamide-acetone (M = Mn, Fe, Co, Ni, Cu, Zn) according to DFT calculations

The thermodynamic and geometric parameters of M(II) macrotetracyclic chelates (M = Mn, Fe, Co, Ni, Cu, and Zn) with the (NNNN) coordination of the donor ligand sites, formed by the complexation reactions of corresponding M(II) compounds, ethanedithioamide H₂N-C(=S)-C(=S)-NH₂, and acetone H₃C-C(=O)-CH₃ in gelatin-immobilized matrix implants have been calculated by the OPBE/TZVP density functional theory method with the use of the Gaussian 09 program package. The bond lengths and bond and torsion angles in these complexes have been reported. It has been shown that despite the fact that the MN₄ chelate core in them is almost planar, the five- and six-membered chelate rings are pronouncedly non-coplanar. In the Mn(II), Fe(II), Co(II), and Ni(II) complexes, these chelate rings are pairwise identical, whereas in the Cu(II) and Zn(II) complexes, they are noticeably different.     

Synthesis,Spectroscopic and Magnetic Studies on Metal Complexes of 5-Methyl-3-(2-Hydroxyphenyl)Pyrazole

A tridentate ONN donor ligand, 5-methyl-3-(2-hydroxyphenyl)pyrazole; H₂L, was synthesized by reaction of 2-(3-ketobutanoyl)phenol with hydrazine hydrate. The ligand was characterized by IR, ¹H NMR and mass spectra. ¹H NMR spectra indicated the presence of the phenolic OH group and the imine NH group of the heterocyclic moiety. Different types of mononuclear metal complexes of the following formulae [(HL)₂M][sdot]xH₂O (M=VO, Co, Ni, Cu, Zn and Cd), [(HL)₂M(H₂O)₂] (M=Mn and UO₂) and [(HL)LFe(H₂O)₂] were obtained. The Fe(III) complex, [(HL)LFe(H₂O)₂] undergoes solvatochromism. Elemental analyses, IR, electronic and ESR spectra as well as thermal, conductivity and magnetic susceptibility measurements were used to elucidate the structures of the newly prepared metal complexes. A square-pyramidal geometry is suggested for the VO(IV) complex, square-planar for the Cu(II), Co(II) and Ni(II) complexes, octahedral for the Fe(III) and Mn(II) complexes and tetrahedral for the Zn(II) and Cd(II) complexes, while the UO₂(VI) complex is eight-coordinate. Transmetallation of the UO₂(VI) ion in its mononuclear complex by Fe(III), Ni(II) or Cu(II) ions occurred and mononuclear Fe(III), Ni(II) and Cu(II) complexes were obtained. IR spectra of the products did not have the characteristic UO₂ absorption band and the electronic spectra showed absorption bands similar to those obtained for the corresponding mononuclear complexes. Also, transmetallation of the Ni(II) ion in its mononuclear complex by Fe(III) has occurred. The antifungal activity of the ligand and the mononuclear complexes were investigated.     

Magnetic and spectral studies on N-(thiophene-2-carboxamido)salicylaldimine complexes of some bivalent 3d metal ions

Metal(II) complexes of N-(thiophene-2-carboxamido)salicylaldimine (H₂TCS) of types M(H₂TCS)₂Cl₂ [M = Ni, Cu and Zn], M(HTCS)Cl [M = Co, Ni and Cu], M(HTCS)₂ [M = Mn, Fe, Co, Ni, Cu and Zn], M(TCS)·xH₂O [M = Mn, Co and Ni, x = 2; M = Cu, x = 0], Ni(TCS)py₂ and Cu(TCS)py have been prepared. Elemental analyses, molar conductance, magnetic moment, electronic, IR and ESR spectral studies have been used to characterize these complexes. The different modes of chelation of the ligand and the stereochemistry of the complexes are discussed.     

Synthesis, Characterization, and Electrochemical Properties of a Novel Macrocylic Ligand and its Transition Metal Complexes

 2,3-Dibromo-6,7,13,14,15,16,22,23-octahydro-14,15-bis-(hydroxyimino)-tribenzo [e,k,q][1,4,7,10,13,16]tetraoxadiazacyclohexadecine (LH₄) was prepared by condensation of 1,2-bis-(2′-aminophenoxyethoxy)-4,5-dibromobenzene with cyanogen-di-N-oxide. Mono-, di-, and trinuclear transition metal complexes of this ligand ((LH₃)₂Ni, (LH₃)₂Zn, (LH₃)₂Co, (LH₃)₂Cu, (LH₃)₂Fe, (LH₃)₂(UO₂)₂(OH)₂, (LH)₂Cu₃, (LH)₂Co₃) were synthesized under basic conditions. The electrochemical properties of the mono- and dinuclear complexes were studied by cyclic voltammetry in DMSO solution containing TBAP. The results showed that all redox processes are based on the metal center and the oxime ligands stabilize the Ni(III), Fe(III), Co(III), and Cu(III) species formed during oxidation. The Fe(II) and U(VI)O₂ complexes displayed a different behaviour: a reduction peak with the corresponding anodic signal during the reverse scan was observed. The oxime moiety also stabilizes U(V)O₂ which forms during the reduction process of the uranyl complex. Cu(II) was adsorbed on the electrode surface upon scanning cathodically.     

Geometric parameters and energies of molecular structures of macrocyclic metal chelates in the ternary 3<Emphasis Type="Italic">d</Emphasis> M(II) ion-ethanedithioamide-ethanedial systems according to quantum-chemical DFT B3LYP calculations

The thermodynamic and geometric parameters of isomeric macrotricyclic Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II) complexes with the (NSSN) coordination of the ligand donor centers formed in the reaction of corresponding hexacyanoferrates(II) with ethanedithioamide H₂N-C(=S)-C(=S)-NH₂ and ethanedial HC(=O)-CH(=O) in gelatin-immobilized matrix implants have been calculated by the hybrid B3LYP density functional theory method with the use of the 6–31G(d) basis set and the Gaussian 03 program package. The bond lengths and bond and torsion angles in these complexes have been reported, and it has been stated that the Mn(II), Co(II), and Cu(II) complexes are nearly planar, the Fe(II) and Ni(II) complexes are slightly nonplanar, while the Zn(II) complex exhibits a rather considerable deviation from coplanarity. The additional five-membered chelate ring resulting from template cross-linking is almost planar in all cases.