FLUORESCENCE PROPERTIES OF METAL-COMPLEXES OF 8-HYDROXYQUINOLINE-5-SULFONIC ACID AND CHROMATOGRAPHIC APPLICATIONS

FLUORESCENCE PROPERTIES OF METAL-COMPLEXES OF 8-HYDROXYQUINOLINE-5-SULFONIC ACID AND CHROMATOGRAPHIC APPLICATIONS
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DOI:
10.1021/ac00131a019
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发表时间:
1987-02-15
影响因子:
7.4
通讯作者:
DASGUPTA, PK
DASGUPTA, PK
中科院分区:
化学1区
文献类型:
--
作者:
SOROKA, K;VITHANAGE, RS;DASGUPTA, PK

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研究了78种金属与8-羟基喹啉-5-硫酸(HQS)螯合物的荧光性质;其中42个发出荧光,许多发出强烈的荧光。由配体电离和羟基络合物形成决定的最优pH值在5到8之间。镉在纯水溶液中形成最具荧光性的复合物。在含有表面活性剂(十六烷基三甲基铵离子,HTA+)的介质中和在甲基甲酰胺溶剂中,许多金属的荧光增强。许多金属离子可以猝灭其他金属- hqs螯合物的荧光,其中铁(III)是迄今为止最有效的,并且这种猝灭在含有HTA+的介质中得到加强。荧光特性可以通过柱后反应器引入配体或将其掺入色谱系统的洗脱液中来利用。对Cd、Mg和Zn均可达到亚皮摩尔检出限。氧(8-羟基喹啉,HQ)及其衍生物在分析化学中占有独特的重要地位,可能仅次于EDTA及其类似物。事实上,很少有分析试剂值得专门研究它们的多卷本专著(1),并且氧及其衍生物在现代分析化学中的新应用正在不断发展(2,3)。我们特别感兴趣的是许多氧及其衍生物的金属配合物所表现出的强烈荧光,这些金属配合物本身除了在浓硫酸和高氯酸或无水氟醇中是无荧光的(4,5)。在一系列的论文中,Rogers及其同事(4,6 -8)和Stevens(9)对氧及其金属配合物的荧光或缺乏荧光以及取代基和溶剂介质对这种荧光的影响进行了极好的描述。
Seventy-eight metal species are examined for fluorescence properties of their chelates with 8-hydroxyqulnollne-5-suHonic acid (HQS); 42 of these fluoresce, many Intensely. The op-timum pH, determined by ligand Ionization vs. hydroxo com-plex formation, lies between 5 and 8. Cadmium forms the most fluorescent complex In a purely aqueous solution. Fluorescence Is enhanced for many metals In surfactant (hexadecyltrimethylammonium Ion, HTA+) containing media and In a watencHmethytformamfde solvent. A number of metal Ions quenchthe fluorescence of other metal-HQS chelates, Fe (III) being by far the most effective, and such quenching Is accentuated In media containing HTA+. The fluorescence properties can be exploited by Introducing the ligand through a postcolumn reactor or by Incorporating It In the eluent In a chromatographic system. Subpicomole detection limits are attainable for Cd, Mg, and Zn.Oxine (8-hydroxyquinoline, HQ) and its derivatives occupy a uniquely important place in analytical chemistry, perhaps second only to EDTA and its analogues. Indeed, few analytical reagents have merited multivolume monographs solely devoted to them (1) and new applications of oxine and its derivatives in modern analytical chemistry are continually being developed (2, 3). Of special interest to us is the intense fluorescence exhibited by many metal complexes of oxine and its derivatives which are themselves nonfluorescent except in concen-trated sulfuric and perchloric acids or anhydrous fluoroalcohols (4, 5). In a series of papers Rogers and co-workers (4, 6-8) and Stevens (9) have given an excellent account of the fluorescence or the lack thereof of oxine and its metal com-plexes and the effects of substituents and solvent media upon such fluorescence.