高分子化8-羟基喹啉金属配合物的合成研究进展

阐述了8-羟基喹啉金属配合物的发光原理,重点综述了8羟基喹啉金属配合物高分子化研究进展,总结归纳了合成高分子化8-羟基喹啉金属配合物的4种方法,概述了8羟基喹啉金属配合物的发光性能,同时对8-羟基喹啉聚合物发光材料的应用前景进行了展望。     

聚丙烯荧光材料制备及其3D打印测试

通过配位反应合成了三种荧光配合物:铕配合物[Eu(DBM)3phen],8-羟基喹啉铝配合物(AlQ3)和8-羟基喹啉锌配合物(ZnQ2),然后通过熔融共混的方式在聚丙烯(PP)材料中分别掺杂这三种荧光配合物,制得三种PP/荧光配合物复合材料,以提高PP发光性能.对这三种复合材料进行了一系列的荧光和力学性能测试.结果表...     

喹啉生物碱锌配合物的合成研究

以8-羟基喹啉、5-氯-8-羟基喹啉、5,7-二氯-8-羟基喹啉为原料,选择具有潜在药理活性的锌金属离子,采用溶剂热法合成了3种金属配合物,通过红外光谱、紫外-可见光谱仪等分析方法对其进行了结构表征.实验结果表明,喹啉和金属离子可以进行配位结合,实验结果为后续的抗肿瘤活性研究提供了数据参考.     

8-羟基喹啉类金属配合物电致发光材料研究进展

本文简述了8-羟基喹啉类金属配合物的发光原理、分子结构与发光性能的关系,综述了8-羟基喹啉类金属配合物发光材料的研究现状及研究进展并展望了其发展趋势和应用前景.     

双-8-羟基喹啉高分子配合物的合成与应用

用8-羟基喹啉在有相转移催化剂存在的碱性条件下,与氯仿作用合成5-甲酰基-8-羟基喹啉,然后将5-甲酰基-8-羟基喹啉分别与对苯二胺、联苯二胺,4,4＇-二氨基二苯砜反应,得到三种双-8-羟基喹啉-席夫碱配体,然后与金属离子配位,得到了一类新型的双-8-羟基喹啉-席夫碱-金属高分子配合物,再结合双-8-羟基喹啉-席夫碱配体与其它离子的显色反应,进行对比分析.利用红外光谱、紫外光谱对配体和配合物的结构进行表征,利用荧光光谱研究了高分子配合物的光致发光性能.     

镧三元配合物的合成及其抑菌活性

在常温下,以乙醇为溶剂,用肉桂酸、8-羟基喹啉和七水合氯化镧反应合成了镧的三元配合物,并对其进行络合滴定、摩尔电导率、元素分析、红外光谱、紫外光谱、热重-差热分析、氢谱等测试,推测其化学组成为LaL1(L2)2·H2O(其中,HL1为肉桂酸;HL2为8-羟基喹啉)。对其进行大肠杆菌、金黄色葡萄球菌、白色葡萄球菌、枯草芽孢杆菌和藤黄微球菌抑菌性能的测试,结果表明,镧离子、8-羟基喹啉和配合物均有抑菌活性。配合物抑菌效果明显优于其配体。     

喹啉氧钒配合物合成、表征及其降糖活性探讨

以硫酸氧钒、乙酰丙酮和8-羟基喹啉为原料合成了四种氧钒配合物,通过红外、核磁等手段表征和推测了配合物的结构。进而探讨了四种配合物对蛋白酪氨酸磷酸酶(PTP1B)的活性抑制能力,结果表明:与硫酸氧钒的抑制效率相比,草酸过氧钒(配合物2)、二乙酰丙酮氧钒(配合物4)和乙酰丙酮(8-羟基喹啉)氧钒(配合物5)对PTP1B有明显的抑制作用,其IC50值分别为12.6μmol/L、0.89μmol/L和0.74μmol/L;而二(8-羟基喹啉)氧钒(配合物6)几乎没有抑制作用,可能与其结构的空间位阻有关。     

8-羟基喹啉衍生物金属配合物的发光研究

通过Claisen重排反应合成了7-烯丙基-8-羟基喹啉配体,并且合成了金属离子Zn~(2+)、Cu~(2+)和Cd~(2+)的配合物。研究了配体及金属配合物的紫外吸收光谱、红外光谱以及光致发光现象。结果表明,配体与金属离子之间形成了稳定配合物,在紫外光激发下,Zn-配合物和Cd-配合物分别发出黄光和蓝-绿光,而Cu-配合物表现为配体的发光。     

2-(8-羟基喹啉-7-亚甲氨基)苯甲酸及其金属配合物的合成与表征

以8-羟基喹啉为原料,通过Reimer-Tiemann反应得到8-羟基喹啉-7-醛,然后与邻氨基苯甲酸缩合得到标题化合物及其金属配合物。通过IR、UV、1HNMR、元素分析、热失重分析等对其结构和性能进行表征,确定配合物分子组成为Zn2.5L·2H2O和Al2(L·1.5H2O)·H2O。测定了两种配合物的荧光性,其最大荧光发射波长(λmax)分别为493、497 nm,通过荧光滴定光谱求得标题配合物与Zn2+和Al3+两种离子的结合常数logβ分别为10.391、8.518。     

不同取代基对喹啉铂(Ⅱ)配合物发光材料光量子效率的影响

以2,4-二苯基喹啉及其衍生物为芳香配体,选用乙酰丙酮为辅助配体,合成铂(Ⅱ)配合物发光材料。通过改变喹啉基团上取代基团的种类,特别是引入树枝状的叔丁基咔唑结构,增加了空间位阻,合理调控了分子间距离,抑制了分子间相互作用,最终提高了铂(Ⅱ)配合物的光量子效率,使发光量子效率提高至0.15。     

Chelating polymers derived from polyvinyl alcohol and cellulose

Hydrophilic chelating polymers have been prepared by the reaction of organic compounds containing both a reactive halogen and a chelating function, with cellulose and, more especially, polyvinyl alcohol or their alkali metal derivatives. Suitable organic compounds used to illustrate the general reaction included: 5-chloromethyl-8-hydroxyquinoline, 5-chloro-8-hydroxyquinoline, ethyl γ-chloroacetoacetate and chloromethyl-kojic acid. Subsequent reaction of the kojic acid-polyvinyl alcohol polymer with diazotised o-arsanilic acid to give a polymer containing the azo-phenylarsonic acid group indicates further scope for these materials. Preliminary tests have shown that the polymers remove metal ions from aqueous solutions. Degradation occurred, however, when the polymers were regenerated with acids to elute adsorbed metal ions.     

Design and synthesis of near-IR luminescent mesoporous materials covalently linked with tris(8-hydroxyquinolinate)lanthanide(III) complexes

By using the bifunctional ligand, 8-hydroxyquinoline-functionalized organosilane (Q-Si), the new mesoporous material Q–MCM-41 covalently bonded with 8-hydroxyquinoline was synthesized. Through the ligand exchange reaction, the new near-infrared (NIR) luminescent mesoporous LnQ₃–MCM-41 (Ln = Er, Nd, Yb) materials were prepared by linking the lanthanide quinolinate complexes to the ordered mesoporous Q–MCM-41 material. The LnQ₃–MCM-41 materials were characterized by powder X-ray diffraction and N₂ adsorption/desorption, and they all show the characteristic mesoporous structure of MCM-41 with highly uniform pore size distributions. Fluorescence spectra of these LnQ₃–MCM-41 materials were recorded and the corresponding luminescence decay analyses were measured. After ligand-mediated excitation, all the emission spectra of the LnQ₃–MCM-41 materials show the characteristic NIR-luminescence of the corresponding lanthanide ions via the intramolecular energy transfer from the ligands to the lanthanide ions. The good luminescent performances enable these NIR-luminescent mesoporous materials to have potential applications in optical amplification (operating at 1.3 or 1.5 μm) and laser systems, etc.     

超声波照射合成双二苯基膦烷烃的研究

以锂片、三苯基膦、二氯代烷烃为主要原料,合成了Ph2P(CH2)nPPh2(n=1~6)系列双二苯基膦烷烃化合物。该类化合物是四电子供体,具有较强的电子给与能力,是较好的桥连和螯合配体,和许多金属离子能形成较稳定的配合物。结果表明,反应在高纯氮气保护下,采用超声波照射,反应温度控制在10℃以下,产品收率提高了30%,经元素分析、红外光谱和熔点测定等手段,证明产品的化学结构同理论吻合。     

氨荒酸盐的合成及配位性能

以CS2、NaOH和仲胺为原料,在无水乙醇中制得了3种N,N-二烃基氨荒酸盐R2NCS2Na.H2O[R2N=i-Pr2N、O(CH2CH2)2N、MeN(CH2CH2)2N],用元素分析、XRD、FTIR等对产物进行了表征,并探索了合成工艺条件,利用紫外分光光度法测定了氨荒酸盐与As3+、Sb3+、Bi3+的配位性能。结果表明,氨荒酸盐与金属离子能形成稳定的配合物,其配位能力的强弱顺序为BiI3.(i-Pr)2NCS2Na.H2OSbI3.(i-Pr)2NCS2Na.H2OAsI3.(i-Pr)2NCS2Na.H2O。实验确定的合成工艺条件为:n(仲胺)∶n(NaOH)∶n(CS2)=1.0∶1.5∶1.8,反应时间2h,产率分别为89.7%、91.2%和93.2%。     

胆红素金属配合物的合成与表征

本文报导了从猪胆中提取的胆红素与锰、钴、铜、锌的醋酸直力氯化亚锡、二氯二甲基锡等分别在不同条件下，在ＣＨＣｌ３或ＤＭＦ溶剂中合成的一系列金属配合物固体。对它们进行了元素分析、红外、紫外、差热、质谱等表征。着重讨论了它们的分子组成和配位结构。研究发现：胆红素对金属离子的配位表现出多样性，由于胆红素分子本身结构的异构化和金属离子性质的不同，它们的结构随金属离子不同而异，既可以形成１：１（摩尔比）的类卟     

高分子金属配合物发光材料的制备技术进展

高分子金属配合物发光材料是一类很有价值的功能材料,评述了有关它的各种合成方法。以金属离子与含配位基团的聚合物进行反应,容易在高聚物之间形成交联,难以获得发光强度高的高分子配合物;使金属离子与高分子配体和小分子配体同时作用,可以得到荧光强度比较理想的产物,但反应难以定量控制;以小分子金属配合物单体与某些单体之间进行共聚合反应,也可获得荧光强度较高的高分子配合物,但聚合反应的空间位阻较大;通过两端都含有配位基团的刚性链的有机小分子配体直接与金属离子配合形成高分子金属配合物;以小分子金属配合物单体进行均聚或者将小分子金属配合物接枝到高聚物上也可以形成高分子金属配合物。     

A Study of the Purification and Acid-Base Behavior of the Commercial Extractants KELEX 100 and LIX 26

Abstract

Several methods for the purification of the active components of the 8-hydroxyquinoline derivative commercial extractants KELEX 100 and LIX 26 have been studies. Among the different methods tried (washing with different solutions, formation of insoluble metal complexes, and column chromatography), the best performance was observed for column chromatography. The active components of KELEX 100 from Ashland (producer up to 1976) and from Sherex (producer from 1976) were characterized using IR, ¹H NMR, ¹³C NMR, and mass spectrometry as 7-(1′-vinyl-3′,3′,5′,5′-tetramethylhexyl)-8-hydroxyquinoline and 7-(1′-methyl-4′-ethyloctyl)-8-hydroxyquinoline, respectively. In the case of LIX 26, a TLC “pure” fraction was isolated and characterized as a 7-alkyl substituted (～ 14 carbon) derivative of 8-hydroxyquinoline that could not be fully resolved. A study of the acid–base properties of the active components of the extractants has also been carried out, and their acidity constants have been calculated by means of both graphical and numerical methods. Finally, several methods for the spectrophotometric determination of these compounds have been proposed.     

Fluorescence properties of ternary complexes of polymer-bond triphenylphosphine,triphenylarsine, triphenylstibine,and triphenylbismuthine,rare earth metal ions,and thenoyltrifluoroacetone

Rare earth metal ions containing polymer ternary complexes were synthesized and characterized. The functional polymers investigated were polymer-bond triphenylphosphine (PBDP), polymer-bond triphenylarsine (PBDAs), polymer-bond triphenylstibine (PBDSb), and polymer-bond triphenylbismuthine (PBDBi) as polymer ligands. Several substances, such as thenoyltrifluoroacetone (TTA), and 8-hydroxyquinoline (oxin), phenanthroline (phen) were used as low molecular weight ligands. The results show that TTA is the best low molecular weight ligand among them. The fluorescence properties of synthesized complexes were investigated; PBDAs is a better polymer ternary complex that possesses stronger fluorescence intensity coordinated with any low molecular weight ligand. The fluorescence lifetimes of Eu³⁺-containing polymer ternary complexes are between 0.350 and 0.469 MS. The reaction conditions of the formation and stability of rare earth metal ions–polymer–TTA ternary complexes are discussed. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 68: 1605–1611, 1998