邻苯二胺、邻氨基酚的电化学聚合及聚合的膜性质

邻苯二胺(ODB), 邻氨基酚(OAP)在酸性水溶液中易电聚合, 可形成致密的聚合膜。聚邻苯二胺(PODB)在PH<4时具有电活性, 其氧化还原反应与电变色效应对应。聚邻苯二胺,聚邻氨基酚(POAP)膜电极电位在pH=4～10范围对pH有Nernst响应, 电极系数分别为59mV/pH和57mV/pH。响应时间小于3分钟。PODB, POAP膜能与Ni~(2+), Co~(2+)过渡金属离子形成稳定的聚合络合膜。此膜在碱性介质中具有稳定的循环伏安行为, 膜中的金属离子可被H~+交换。PODB电极的—NH_2基可再修饰引入醌/氢醌功能团。     

8-羟基喹啉-2-醛缩芳香酰肼Ni(Ⅱ)配合物的合成及表征

合成并表征了8-羟基喹啉-2-醛缩苯甲酰肼、8-羟基喹啉-2-醛缩水杨酰肼以及8-羟基喹啉-2-醛缩对羟基苯甲酰肼Ni(Ⅱ)配合物,并利用黏度滴定、紫外光谱和荧光光谱法研究了它们与CT-DNA相互作用情况.结果表明,这些配合物均为良好的DNA插入试剂,它们与DNA的结合常数(Kb)分别为1.006× 105 M-1、9...     

分子内氢键——Ⅲ.2-(邻羟基苯基)喹啉及其类似物的结构和内氢键

本文通过紫外光谱、~1H核磁共振谱、质谱和HMO计算,研究了2-(邻羟基苯基)喹啉及其类似物的结构和内氢键,并估算出1-(邻羟基苯基)异喹啉的苯酚环和异喹啉环间的扭转角约70°,2-(邻羟基苯基)-8-甲氧基喹啉具三中心氢键性质。从内氢键强度与给予原子的电荷密度及内氢键稳定化能有近似的线性关系,说明2-(邻羟基苯基)喹啉的pK_a值特别高是由于它具有强的内氢键。8位氢的位阻对配合物的生成有重要影响。     

聚邻甲苯胺的合成及物理化学性质

聚苯胺的导电性和电化学特性已被广泛地研究。最近,对苯胺衍生物的聚合物也开始了研究,如聚邻甲氧基苯胺、聚邻苯二胺和聚邻氨基酚,其中聚邻甲氧基苯胺是一种可溶性的导电高分子材料。为了探讨苯胺聚合的机理和苯胺上不同基团对聚苯胺性质的影响,我们使用了十六种苯     

多巴胺在dsDNA/Ni2+/聚邻氨基酚修饰碳糊电极上的伏安行为

通过电化学聚合法在碳糊电极上共聚制备了聚邻氨基酚/Ni2+膜(Ni2+/P-OAP/CPE), 研究了膜的伏安特性, 并制成dsDNA修饰电极, 通过电化学和紫外光谱法进行表征. 将dsDNA/Ni2+/P-OAP/CPE电极应用于多巴胺的电催化氧化, 同时将该方法用于盐酸多巴胺针剂的测定, 亦获得了满意的结果.     

邻氨基酚电聚合膜的研究

在酸性溶液中, 邻氨基酚(OAP)可电聚合成均匀的活性聚邻氮基酚膜(POAP), 膜有致密结构和“张开”结构。POAP膜的主要结构形式为: 与Ni~(2+)络合后, 形成POAP—Ni~(2+)膜, 其主要结构形式为:     

8-羟基喹啉的高分子化及其Eu(Ⅲ)配合物的制备和表征

在合成含有8-羟基喹啉(8HOQ)配位基单体的基础上,将其与甲基丙烯酸甲酯(MMA)共聚得到含有8-羟基喹啉侧基的聚甲基丙烯酸甲酯(PMMA8q),实现了8-羟基喹啉的高分子化;通过PMMA8q和小分子协同配体与稀土离子Eu(Ⅲ)的配位反应,制备了两个稀土高分子发光配合物:Eu(PMMA8q)(8HOQ)2(H2O)3和Eu(PMMA8q)2(TTA)(H2O)3(TTA:噻吩甲酰三氟丙酮)。利用元素分析、红外光谱方法对各阶段产物进行了表征,用荧光光谱研究了两个稀土高分子配合物的荧光特性及发光机理。     

8-羟基喹啉基稀土络合物的近红外发光研究

以8-羟基喹啉(Q)作为配体,通过控制配位反应条件,制备了二配体(ErQ2),三配体(ErQ3)和四配体(ErQ4,NdQ4和YbQ4)的8-羟基喹啉基稀土络合物,并用元素分析、红外光谱、紫外-可见吸收光谱和荧光光谱对其结构和性能进行了研究。通过激发配体,络合物均发射稀土离子的特征近红外光;随着配体数目的增加,络合物的近红外发光效率和寿命均增加,非辐射衰减速率常数减少。研究结果表明,稀土离子的近红外发光是通过8-羟基喹啉敏化产生的,并且8-羟基喹啉对铒离子的敏化不如对钕离子和镱离子的有效。     

聚邻苯二胺/镍氢氧化物修饰电极的研究

采用循环伏安法(CV)在聚邻苯二胺修饰玻碳电极表面络合Ni2+,然后将其置于NaOH溶液中CV扫描成功制备了镍氢氧化物/聚邻苯二胺/玻碳修饰电极(Ni(OH)2/PoPD/GC).通过CV探讨了聚合和负载机理,电化学交流阻抗谱(EIS)表征了电极修饰过程中界面阻抗变化,扫描电镜表征了PoPD膜负载Ni(OH)2后的形态...     

聚N-[5-(8-羟基喹啉)甲基]苯胺/硅杂化材料的制备与性能

以8-羟基喹啉、甲醛和苯胺为原料,制备了5-[(苯胺基)甲基-8-羟基喹啉,并以此为单体,以过硫酸铵作为氧化剂,采用化学氧化聚合法,在酸性水溶液中合成了聚N-[5-(8-羟基喹啉)甲基]苯胺.通过正硅酸乙酯表面修饰聚N-[5-(8-羟基喹啉)甲基]苯胺获得了具有荧光特性的聚N-[-5-(8-羟基喹啉)甲基]苯胺/硅杂化材料.该杂化材料不仅在480 nm附近发出较强的荧光,而且在强酸和弱酸电解质溶液中均表现出了较好的氧化-还原可逆性.     

Surface layer-by-layer chemical deposition reaction for thin film formation of nano-sized metal 8-hydroxyquinolate complexes

The feasibility of a novel and simple layer-by-layer chemical deposition method for the preparation of nano-sized metal 8-hydroxyquinolate complexes has been investigated and reported. Uniform nanocrystalline films have been synthesized via dipping a substrate alternately in metal ion solution followed by ligand solution. The stoichiometry of the as-grown anhydrous Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) complex crystals were confirmed from the metal analysis and molar stoichiometric ratio of metal ion to 8-hydroxyquinoline. This was characterized as 1:2 for the Co(II), Ni(II), Cu(II) and Zn(II)–quinolate complexes. The Fe(III)–quinolate thin film was found to exhibit a 1:3 ratio. Electron impact-mass spectra (EI-MS) of all the synthesized thin film metal quinolate complexes were recorded and the results refer to the existence of the molecular ion peak at the corresponding m/z values. Confirmation of such stoichiometric 1:2 and 1:3 ratios were also evident from the (EI-MS) study. The deposited thin films were also subjected to analysis by a scanning electron microscope (SEM) and a particle size ?50 nm was detected. FT-IR and UV–Vis spectroscopy were further used to confirm the structure of the metal 8-hydroxyquinolate complexes. Thermal gravimetric analysis (TGA) was also used to follow up the possible thermal decomposition steps and to calculate the thermodynamic parameters of the nano-sized metal complexes.     

1,2,3,4-Tetrahydro-8-hydroxyquinoline-promoted copper-catalyzed coupling of nitrogen nucleophiles and aryl bromides

Based on the dramatic accelerating effect of 2-aminophenol, three ligands derived from 2-aminophenol were developed. Copper-catalyzed coupling reaction of nitrogen-containing nucleophiles with aryl bromides was efficiently carried out under mild conditions using 1,2,3,4-tetrahydro-8-hydroxyquinoline as a novel, simple, and versatile ligand.     

A novel potential oscillation in situ removal method: preparation of ion imprinted 8-HQ/PPy film for the selective separation of zinc ions

Journal of Solid State Electrochemistry - The zinc ion–imprinted 8-hydroxyquinoline/polypyrrole (8-HQ/PPy) composite film is successfully prepared by using the unipolar pulse...     

Analysis of metal ions in crude oil by reversed-phase high performance liquid chromatography using short column

In this study a rapid, simultaneous analysis of V, Ni, Fe and Cu in crude oil was achieved by high performance liquid chromatography using 10 cm length reversed-phase C18 column. Since the amount of metal ions is at a very low level, in this work, solvent extraction of metals by a ligand such as 8-hydroxyquinoline from acidic media was investigated with some modification to previous procedures. Average extraction recoveries were 99, 85, 94 and 96 for V, Ni, Fe and Cu, respectively. The proposed method was successfully applied to the crude oil which was obtained from Koshk area in southern Iran. Fast analysis of metal ion in reversed-phase short column was achieved with methanol/water (55/45, v/v) and the detection limits measured as three times the background noise were obtained. Also it was shown that if small amount of 8-hydroxyquinoline was added to the mobile phase, the peak height and the peak symmetry were improved. A typical chromatogram for the separation of the 8-hydroxyquinoline complexes of V (V), Ni (II), Fe (III) and Cu (II) in crude oil was obtained in less than 4 min.     

四氢叶酸辅酶模型的合成及甲基取代的一碳单元转移反应

本文报道了甲基取代的甲酸态的四氢叶酸辅酶模型--碘化1, 2-二甲基-3-对氯苯磺酰基咪唑啉的合成。研究了模型与单官能团亲核体(苯胺、对氯苯胺、对硝基苯胺)和双官能团亲核体(邻苯二胺、邻氨基酚、乙二胺)作用, 转移甲基取代的一碳单元的反应。     

Preparation and study of new poly-8-hydroxyquinoline chelators for an anti-Alzheimer strategy

Fourteen different ligands have been synthesized with two covalently linked 8-hydroxyquinoline motifs that favor metal complexation. These bis-chelators include different bridges at the C2 positions and different substituents to modulate their physicochemical properties. They can form metal complexes in a ratio of one ligand per metal ion with Cu II and Zn II, two metal ions involved in the formation of amyloid aggregates of the toxic Abeta-peptides in the Alzheimer disease. The apparent affinity of all bis-8-hydroxyquinoline ligands for Cu II and Zn II are similar with logK Cu II approximately 16 and logK Zn II approximately 13 and are 10,000 times more efficient than for the corresponding 8-hydroxyquinoline monomers. Their strong chelating capacities allow them to inhibit more efficiently than the corresponding monomers the precipitation of Abeta-peptides induced by Cu II and Zn II and also to inhibit the toxic formation of H2O2 due to copper complexes of Abeta. The best results were obtained with a one-atom linker between the two quinoline units. X-ray analyses of single-crystals of Cu II, Zn II or Ni II complexes of 2,2'-(2,2-propanediyl)-bis(8-hydroxyquinoline), including a one-atom linker, showed that all heteroatoms of the bis-8-hydroxyquinoline ligand chelate the same metal ion in a distorted square-planar geometry. The Cu II and Zn II complexes include a fifth axial ligand and are pentacoordinated.     

Poly(2,2′-(1,4-phenylenedivinylene) Bis-8-hydroxyquinaldine) Modified Glassy Carbon Electrode for the Simultaneous Determination of Paracetamol and p-Aminophenol

A novel assay is reported for the simultaneous determination of paracetamol and p-aminophenol using a poly(2,2′-(1,4-phenylenedivinylene)bis-8-hydroxyquinaldine) modified glassy carbon electrode. Poly(2,2′-(1,4-phenylenedivinylene)bis-8-hydroxyquinoline) modified electrodes were prepared by electrochemical polymerization. The electrode surface was characterized by scanning electron microscopy. The electrochemical behavior of the modified electrode was investigated by cyclic voltammetry, square wave voltammetry, and electrochemical impedance spectroscopy. The anodic peak potentials for paracetamol and p-aminophenol were at 580 and 337 millivolts, respectively, with a separation of 243 millivolts, adequate for their simultaneous determination. The results showed that the linear dynamic ranges for paracetamol and p-aminophenol were 0.5–200 micromolar and 3–150 micromolars, whereas the limits of detection were 0.075 and 0.45 micromolar, respectively. The novel poly(2,2′-(1,4-phenylenedivinylene)bis-8-hydroxyquinaldine) modified electrode provided excellent selectivity, sensitivity, and stability and was employed for the determination of paracetamol and p-aminophenol in pharmaceutical products and urine.     

一种新型有机多羧酸镍（Ⅱ）配合物的合成与结构

合成了一种新型有机多羧酸HOOCCH2OC6H4N（CH2COOH）2（H3L）,并用它与六水合硫酸镍在常温下反应得到配合物[Ni3（L）2（H2O）12]·6H2O（1）的单晶。经单晶结构测定,该配合物中含有两种不同配位环境的镍（Ⅱ）离子,一种镍（Ⅱ）离子与配体中氮原子上的两个亚甲基羧基配位,另一种与六个水分子配位．配体中与氧原子连接的亚甲基羧基没有配位。配合物（1）属三斜晶系,P-1空间群,晶胞参数为：a=0．7301（14）nm,b=1．0597（17）nm,c=1．3639（16）nm,α=97．14（8）°,β=91．26（6）°,γ=96．50（8）°,V=1．040（3）nm^3,Z=1．     

NH3/NH4Cl中镍(Ⅱ)-丁二肟体系在悬汞电极上电化学还原机理的研究

The behaviour of the Nickel(Ⅱ) ion in the presence of dimethyl-glyoxime (DMG) on the hanging mercury drop electrode in NH_3/NH_4Cl media was investigated with different electrochemical techniques. It was found that: (1) the reactant was Ni(Ⅱ) complex with DMG, Ni(Ⅱ)A_2, adsorbed on the electrode surface; (2) the intermediate was Ni(Ⅰ)A_2 and (3) the product was metal amalgam Ni(0)(Hg). Two electrons were transferred in the overall reaction and the transfer coefficient was 1.8 which was measured experimentally. From experimental results, it was obvious that the reaction orders with respect to Ni(Ⅱ), DMG and H~+ were 1,2, and 1, respectively. A new compound, X, was detected. The reaction scheme could be written as followsNi(Ⅱ)A_2+Hg<=>Ni(Ⅱ)A_2(ads)(Hg)Ni(Ⅱ)A_2(ads)(Hg)+e~-<=>Ni(Ⅰ)A_2(ads)(Hg)Ni(Ⅰ)A_2(ads)(Hg)+H~++e~-→Ni(0)(Hg)+HA(des)+A~-(des)→X+Hg     

5-(4′-烷氧基苯基)-8-羟基喹啉锌的合成及其偏振发光性能

本文通过在8-羟基喹啉的5位上引入含不同碳链长度的对烷氧基苯基,合成了一类5-(4′-烷氧基苯基)-8-羟基喹啉锌配合物(C6OphQ)2Zn、(C8OphQ)2Zn和(C12OphQ)2Zn。通过DSC和偏振显微镜等热力学仪器考察了它们的液晶性,发现长链的5-对烷氧基-苯基-8-羟基喹啉锌均具有液晶性。将它们在聚酰亚胺取向薄膜上进行排列,应用装备有偏振器的紫外分光光度计和荧光分光光度仪测定了薄膜偏振光性质。实验发现,这些具有液晶性质的发光配合物在聚酰亚胺取向薄膜上能够产生有序排列,表现出一定的吸收和发射二色比。其中配合物(C8OphQ)2Zn在332 nm处的最大吸收二色比是2.0,在500 nm处的发射二色比为2.4。