IAP-4S螯合物和离子对反相高效液相色谱测定铁、钴和镍

借有机分析试剂螯合物和高效液相色谱测定金属离子,最常用的有机分析试剂有:二硫代氨基甲酸盐、8-羟基喹啉、4-(2-吡啶偶氮)-间苯二酚和其它高灵敏的偶氮染料。咪唑偶氮类显色剂是一类新合成的高灵敏有机分析试剂.2-(2-咪唑偶氮)-苯酚就是其中的一种.它难溶于水,但将其磺化后得到2-(2-咪唑偶氮)-苯酚-4-磺酸(IAP-4S)及其金属螯合物均溶于水.本文首先探讨了它与Fe~(2+)、Co~(2+)和Ni~(2+)生成螯合物及其离子对反相HPLC分离的各种条件,并提出了同时测定铁、钴和镍的新方法.     

聚丙烯酸双(乙氧羰基)甲酯及其螯合物的合成和磁性能的检测

以溴代丙二酸二乙酯、丙烯酸钠为原料合成了聚丙烯酸双(乙氧羰基)甲酯(PEOCMA),并制备了其相应的与稀土金属Gd3+、Nd3+以及过渡金属Ni2+的高分子螯合物.利用FTIR、1H-NMR、GPC对聚合物和高分子螯合物的结构进行了表征,通过电感耦合等离子质谱仪(ICP)测得了高分子螯合物中的金属含量,借助多功能材料物理特性测试系统(PPMS,physical property measurement system)测定螯合物的磁性能.结果表明这些高分子螯合物具有较高的磁饱和强度,在低温下呈现出一定的铁磁相互作用,且为软磁性材料.     

N-二茂铁甲酰基-芳基羟胺及其铜(Ⅱ)螯合物的合成与表征

二茂铁甲酰羟胺衍生物分子中含有N-羟基和α-羰基,可与过渡金属形成螯合物.我们试图将该类螯合物用作复合固体推进剂的燃速调节剂,为此,研究了该类化合物的合成方法及其性质,并使它们与铜(Ⅱ)螯合制成铜螯合物.     

稀土—5—Br—PADAP螯合物的高效液相色谱分离与测定

以配合物形式分离金属离子已有报道.胡之德等研究了In、Pt、Pd等金属与5-Br-PADAP螯合物的色谱行为,在硅胶柱上成功地分离了这几种金属元素.林长山等应用反相高效液相色谱法,分离了Fe(Ⅲ)、Co(Ⅱ)和V(Ⅱ)3种金属的5-Br-PADAP螯合物,并做了定量的研究.本文应用高效液相色谱法研究了镧系-5-Br-PADAP螯合物色谱行为,探讨了相关因素对分离和测定的影响,讨论了螯合物的保留值与稀土元素原子半径的关系.     

金属螯合物催化环氧E-51/酸酐体系的催化活性及固化过程

Uri等曾对水杨酸铬系列金属螯合物催化环氧树脂与羧酸之间的固化反应进行了研究,但对呋喃甲酸铬系列金属整合物催化环氧树脂与酸酐之间的固化反应的研究,尚未见报道。我们在首次合成呋喃甲酸铬系列催化剂的基础上,对其催化环氧树脂/酸酐体系的催化活性、固化过程进行了研究,并与水杨酸系列金属螯合物及由不同金属元素配位中心、不同配位体组成的其它类型金属螯合物催化E-51/MTHPA体系的催化活性进行了比较;对不同配     

一种偶氮染料金属螯合物薄膜的光学特性研究

偶氮染料是一类广泛应用的纺织用有机染料^[1],近年来随着光电子技术的发展,偶氮染料作为非线性光学材料^[2]和光信息记录介质^[3]引起人们极大的兴趣.偶氮染料具有对光吸收大,容易制备,在有机溶剂中具有较高的溶解度而适用于湿法涂布等优点,可以作为可录光盘(CD-R)的记录介质.     

表面增强拉曼光谱在偶氮染料检测中的研究进展

简述了偶氮染料的检测现状,对偶氮染料研究中表面增强拉曼光谱检测方法进行了综述。介绍了表面增强拉曼光谱用金属溶胶、金属电极、金属薄膜3种增强基底在偶氮染料检测中的方向,并对其在偶氮染料检测中的研究前景进行了展望。表面增强拉曼光谱法是一种新型光谱分析技术,具有操作简单、快速、灵敏度高等优势,为偶氮染料的检测开辟了新道路。     

含双噻唑高分子及其螯合物的制备和磁性能研究进展

设计和合成有机及高分子磁性材料是当前国内外十分关注的课题,本课题组在先前研究的基础上,以电子理论和磁性理论为指导,从分子设计出发,合成出含双噻唑新型芳杂环聚合物及其过渡金属离子或稀土离子螯合物,测定了它们的磁性能,研究高分子结构、螯合物组成与磁性能的关系,探索产生磁性的机理.发现本研究体系的高分子螯合物具有顺磁居里温度(Tp)高,剩余磁场(Mr)少,矫顽力(Hc)低,是一类很好的软磁性材料,呈现出有一定特色的磁性能.本文综述了含双噻唑高分子过渡金属螯合物、稀土金属螯合物、纳米碳管接枝高分子及其螯合物的制备和磁性能研究,以及典型螯合物的非常规磁性现象的发现和机理探索研究.     

酰胺衍生寡聚DTPA钆配合物的合成、表征及弛豫性能

以寡聚二乙撑三胺-N,N′-二(乙酰苯胺)-N,N′,N″-三乙酸([H₃L]_n)为配体, 与GdCl₃在二甲基甲酰胺-水混合溶剂中组装得到了寡聚金属螯合物. 采用傅里叶变换红外光谱(FTIR)、元素分析、核磁共振氢谱(¹H NMR)和热重及差热分析(TG-DTA)确定了寡聚金属螯合物的组成单元为[GdL(H₂O)]·4H₂O, 即寡聚配体的每个链节与1个金属离子配位. 采用反转恢复法测试了寡聚金属螯合物和小分子配合物Gd-DTPA(DTPA为二乙撑三胺五乙酸)的纵向弛豫时间T₁, 该寡聚金属螯合物体外弛豫率为8.526 mmol·L^-1·s^-1, 与配合物Gd-DTPA的弛豫率(4.370 mmol·L^-1·s^-1) 相比, 弛豫性能明显提高.     

傅立叶变换离子回旋共振质谱用于金属加工助剂中的成分分析

金属加工助剂是金属加工生产过程中必不可少的化工产品,其组成复杂,易形成螯合物干扰成分分析。该文利用傅立叶变换离子回旋共振质谱(Fourier transform ion cyclotron resonance mass spectrometry,FT-ICR MS)技术的高分辨性能,结合电感耦合等离子体质谱(ICP-MS)、红外光谱(IR)和核磁共振谱(NMR)对一种含未知成分的金属加工助剂进行成分分析。结果表明,该金属加工助剂中含有柠檬酸钠、乙二胺四乙酸(EDTA)与金属铋螯合物。该方法简便、准确,适用于含有金属螯合物的金属加工助剂成分的快速鉴定。     

Thermo-XRD-analysis and peptization study of the adsorption of alizarinate by Co-, Ni-, and Cu-montmorillonite

The adsorption of the monovalent anionic dye alizarinate onto Co-, Ni- and Cu-montmorillonite was carried out by adding the dye into aqueous clay suspensions. During the loading of the clay suspension by alizarinate, only some of the added organic anion is adsorbed by the clay forming d-coordination chelate complexes on the clay surface. Maximum adsorption of Co-, Ni- and Cu-clay were 13, 13 and 25 mmol dye per 100 g clay. Since the capacity of the clay for these transition metal cations is 38 mmol per 100 g clay, these saturations indicate that only part of the transition metal cations form positively charged d-coordination chelate complexes with metal:ligand ratio of 1. The complex cations can be located inside the interlayer spaces or on the broken bonds surfaces. Thermo-XRD-analysis and peptization studies of the solids and the clay water systems respectively were used here to identify the sorption sites. The Co and Ni complexes were obtained on the broken bonds surfaces whereas the Cu complexes were obtained in the interlayer space. Co²⁺, Ni²⁺ and Cu²⁺ were extracted from the clay into suspensions containing excess alizarinate.     

Synthesis,characterization and in vitro antimicrobial and anti‐breast cancer activity studies of metal complexes of novel pentadentate azo dye ligand

A new azo dye with N3O2 donor set of atoms has been synthesized via coupling reaction of 2,6‐diaminopyridine with p‐methoxybenzaldehyde. The molecular and electronic structure of the azo dye ligand (L) was optimized theoretically and the quantum chemical parameters were calculated. Molecular docking was used to predict the binding between L and the receptors of breast cancer mutant 3hb5‐oxidoreductase, crystal structure of Escherichia coli (3 T88) and crystal structure of Staphylococcus aureus (3q8u). The newly synthesized L was used for complex formation with Cr(III), Mn(II), Fe(III), Co.(II), Ni(II), Cu(II), Zn(II) and Cd(II) ions. The nature of bonding and the stoichiometry of L and its mononuclear complexes were deduced from elemental analyses, spectroscopic, magnetic susceptibility, molar conductance, electron spin resonance and conductivity measurements, thermogravimetric analyses and powder X‐ray diffraction. Elemental analysis data show that the complexes have composition of ML type with an octahedral geometry for all the complexes. The activation thermodynamic parameters were calculated. The prepared azo dye and its metal complexes were tested against various Gram‐positive and Gram‐negative bacteria and a fungus. Most complexes exhibit antibacterial and antifungal activities against these organisms. Anticancer evaluation studies against standard breast cancer cell line were performed using various concentrations. The activity index was calculated. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis and characterization of metal complexes of azo dye based on 5‐nitro‐8‐hydroxyquinoline and their applications in dyeing polyester fabrics

New Mn(II), Ni(II), Co(II) and Cu(II) complexes of an azo dye ligand based on p ‐phenylenediamine with 5‐nitro‐8‐hydroxyquinoline were synthesized and characterized using elemental analysis, inductive coupled plasma analysis, molar conductance, powder X‐ray diffraction, thermogravimetric analysis, magnetic moment measurements, and infrared, ¹H NMR, electron ionization mass and UV–visible spectral studies. The spectral and analytical data reveal that the azo dye ligand acts as a monobasic bidentate ligand via deprotonated OH and nitrogen atom of the quinoline ring. The data support the formulation of all complexes with a 2:1 ligand‐to‐metal ratio, except the Mn(II) complex that has a mononuclear formula. All complexes have an octahedral structure. The molar conductance data reveal that all the metal complexes are non‐electrolytic in nature. From the X‐ray data, the average particle size of the ligand and its complexes is 0.32–0.64 nm. The colour fastness to light, washing, perspiration, sublimation and rubbing of the prepared ligand and its complexes on polyester fabrics and colorimetric properties were measured. The results reveal that the ligand and its complexes have a good to moderate affinity to polyester fibres.     

Polyelectrolyte complexes. V. Solid‐state properties of some polycation/azo dye complexes controlled by the dye structure

The solid‐state properties of some polycation/azo dye complexes according to the dye structure were studied in this work. One polycation contained about 95 mol % N,N‐dimethyl‐2‐hydroxypropyleneammonium chloride units in the backbone (PCA₅), and eight azo dyes, different in either the number of sulfonic groups or their distribution, were used as opposite components. The selected azo dyes were as Crystal Scarlet, Congo Red, Crocein Scarlet MOO, Ponceau SS, Amaranth, Ponceau S, Direct Blue 1, and Direct Red 80. Information on the compensation degree of the oppositely charges was obtained by the elemental analysis of the solid‐state polycation/dye complexes (the experimental contents of chlorine, nitrogen, and sulfur were compared with the calculated values). Differential scanning calorimetry was employed to probe the strength of the intermolecular interactions in the PCA₅/dye complexes. Wide‐angle X‐ray diffraction was used to assess the supramolecular order of the solid‐state complexes. The physical properties of the PCA₅/azo dye complexes (the complex stoichiometry, glass‐transition temperature, decomposition temperature, and degree of supramolecular order) were influenced mainly by the dye structure but also by the polycation concentration and the presence of NaCl. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 264–272, 2003     

The nature of the complexes of 2.2'-dihydroxyazo compounds

The metal complexes of Pontachrome Violet SW, a di-ortho-dihydroxyazo type dye, were studied in an attempt to deduce a reason for the unusual polarographic behavior such as gave rise to the Willard-Dean method for aluminum. Cis-trans isomers, anionic species and azo coordination to the central cation are ruled out. The most likely cause scems to be the rigidity of the complex with the result that the reduction of the complex occurs by a different mechanism then the reduction of the free dye.     

Synthesis and characterization of azo sulfaguanidine complexes and their application for corrosion inhibition of silicate glass

A new azo dye ligand of sulfaguanidine with 5‐nitro‐8‐hydroxyquinoline and its Mn(II), Ni(II), Co(II) and Cu(II) complexes were synthesized and characterized using elemental analysis, inductively coupled plasma, molar conductance, X‐ray powder diffraction, thermogravimetric analysis, magnetic moment measurements, and infrared, ¹H NMR, electron impact mass and UV–visible spectral studies. The spectral studies and analytical data revealed that the azo dye ligand acts as a monobasic bidentate ligand via deprotonated OH and nitrogen atom of the azo group. The data support the mononuclear formulation of all complexes, except Cu(II) complex that has a binuclear formulation with a 1:2 metal to ligand ratio. The complexes have tetrahedral structure except Ni(II) which has octahedral geometry. The molar conductance data reveal that all the metal complexes are non‐electrolytic in nature The average particle size of the ligand and its Mn(II), Ni(II), Co(II) and Cu(II) complexes is 0.12–0.91 nm. The effect of these compounds for improvement of chemical durability of silicate glass in 0.1 M HCl was studied. Window and soda‐lime silica glass were taken as samples for the durability experiments. The inhibition efficiency of the ligand and its complexes for corrosion of glass surfaces after dissolution experiments was evaluated quantitatively using the specific weight loss method and qualitatively using scanning electron microscopy. The inhibition efficiencies of the tested compounds follow the order Co(II) complex > Mn(II) complex > Ni(II) complex > H₃L > Cu(II) complex. The chemical durability improvement is 88.12–56.25% and 87.99–51.96% for window and soda‐lime silica glass, respectively. Copyright © 2016 John Wiley & Sons, Ltd.     

Synthesis of a New Azo Dye Sensor and its Chelation with Ag+

A new azo dye containing thiadiazoline ring was synthesized from the reaction of the diazobenzaldehyde with O‐aminothiophenol, which was characterized by NMR, IR spectroscopy and high resolution mass spectrometry. This dye compound can chelate Ag⁺ in CH₂Cl₂‐EtOH and then result in the variation of UV absorbances.     

Development of nanomaterial chemosensors for toxic metal ions sensing

Heavy metal ions are harmful to aquatic life and humans owing to their high toxicity and non‐biodegradability, so their removal from wastewater is an important task. Therefore, this work focuses on designing suitable, simple and economical nanosensors to detect and remove these metal ions with high selectivity and sensitivity. Based on this idea, different types of mesoporous materials such as hexagonal SBA‐15, cubic SBA‐16 and spherical MCM‐41, their chloro‐functionalized derivatives, as well as 4‐(4‐nitro‐phenylazo)‐naphthalen‐1‐ol (NPAN) azo dye have been synthesized, with the aim of designing some optical nanosensors for metal ions sensing applications. The mentioned azo dye has been anchored into the chloro‐functionalized mesoporous materials. The designed nanosensors were characterized using scanning and transmission electron microscopy as well as Fourier transform infrared and UV–visible spectral analysis, nitrogen adsorption–desorption isotherms, low‐angle X‐ray diffraction and thermogravimetric analyses. Their optical sensing to various toxic metal ions such as Cd (II), Hg (II), Mn (II), Fe (II), Zn (II) and Pb (II) at different values of pH (1.1, 4.9, 7 and 12) was investigated. The optimization of experimental conditions, including the effect of pH and metal ion concentration, was examined. The experimental results showed that the solution pH had a major impact on metal ion detection. The optical nanosensors respond well to the tested metal ions, as reflected by the enhancement in both absorption and emission spectra upon adding different concentrations of the metal salts and were fully reversible on adding ethylene diamine tetra acetic acid or citric acid to the formed complexes. High values of the binding constants for the designed nanosensors were observed at pHs 7 and 12, confirming the strong chelation of different metals to the nanosensor at these pHs. Also, high binding constants and sensitivity were observed for NPAN‐MCM‐41 as a nanosensor to detect the different metal ions. From the obtained results, we succeeded in transforming the harmful azo dye into an environmentally friendly form via designing of the optical nanosensors used to detect toxic metal ions in wastewater with high sensitivity.     

Nitroxoline Azo Dye Complexes as Effective Heterogeneous Catalysts for Color Removal and Degradation of Some Organic Textile Dyes

A new azo dye ligand of sulfadiazine with 5‐nitro‐8‐hydroxyquinoline (H₂L) and its Cu(II), Mn(II), Co(II), and Ni(II) complexes have been synthesized and characterized using CHN, ¹H NMR, EI‐mass, inductive coupled plasma, molar conductance, IR, thermogravimetric analysis, magnetic moment measurements, and UV–vis spectra. On the basis of spectral studies and analytical data, the azo dye acts as a monobasic bidentate ligand coordinating to the metal ions via deprotonated OH and azo nitrogen atom. The spectral data showed that the synthesized complexes have octahedral geometry. The application of the obtained chelates in the oxidative decomposition of three different textile dyes (i.e., AB92, AB40, and AB129) in the presence of H₂O₂ as an oxidant has been studied. The obtained results indicated that the reactivity of catalysts toward the decolorization of AB40 showed the following order: Cu complex > Ni complex > Co complex > Mn complex; the reactions obey the first‐order reaction mechanism, and the rate constants were determined.