PEROXYOXALATE CHEMI-LUMINESCENCE IN MICROEMULSIONS
PEROXYOXALATE CHEMI-LUMINESCENCE IN MICROEMULSIONS
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DOI：
10.1021/la00079a018
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发表时间：
1988-01-01
期刊：
影响因子：
3.9
通讯作者：
MCBEE, SES
中科院分区：
文献类型：
--
作者：
THOMPSON, RB;MCBEE, SES
化学发光技术在临床化学、分析化学、照明和水生安全等领域发挥着越来越重要的作用。最有效的非酶催化的化学发光反应是过氧化氢与草酸衍生物的化学发光反应，称为过氧草酸化学发光。这个反应最早是由Chandross 1描述的，并由Rauhut、Mohan和他们的同事深入研究。2反应的轮廓如图1所示：草酸双酯1被过氧化氢氧化形成(推测)瞬时的二氧杂二酮中间体2®2，该中间体将其能量传递给荧光剂3，荧光剂3以光子的形式发射。尽管荧光剂的激发很可能是通过电子转移过程，但反应的细节仍未阐明。3反应的量子产率可达35%，选择合适的荧光剂可使发射波长变化较大。4.尽管过氧草酸盐化学发光效率高，用途广泛，但与鲁米诺衍生物相比，它在化学分析中的应用还很少。5这主要是由于草酸盐衍生物(和荧光剂)在水或质子型溶剂中的不溶性和不稳定性。Seitz和他的同事描述了他们在创建用于定量过氧化氢的过氧草酸盐化学发光流动注射分析系统时，在寻找兼容溶剂方面遇到的问题。5‘Rauhut、Mo-han和他们的合作者在水乳剂中的环己烷反应中几乎没有得到改善，但通过添加高于其临界胶束浓度的洗涤剂25或聚合物添加剂(B.H.Baretz，个人交流)，获得了更好的结果。美国的氰胺基团还合成了草酸盐衍生物和荧光剂，它们是有点水的。
Chemiluminescence technology is of growing importance in fields as diverse as clinical chemistry, analytical chem-istry, illumination, and aquatic safety. The most efficient chemiluminescent reaction not catalyzed by an enzyme is that of hydrogen peroxide with derivatives of oxalic acid, termed peroxyoxalate chemiluminescence. This reaction was first described by Chandross1 and studied in depth by Rauhut, Mohan, and their colleagues. 2 An outline of the reaction appears as Figure 1: the oxalate bis-ester 1 is oxidized by hydrogen peroxide to form the (putative) transient dioxetanedione intermediate2® 2, which then transfers its energy to a fluorescer, 3, which emits it as a photon. The details of the reaction remain unelucidated, although excitation of the fluorescer is probably via an electron-transfer process. 3 The quantum yield of the reaction ranges up to 35%, and the emission wavelength may be widely varied by choosing a suitable fluorescer. 4 Despite its efficiency and wide use for illumination, peroxyoxalate chemiluminescence has been little used for chemical analysis in comparison to luminol derivatives. 5 This is primarily due to the insolubility and lability of the oxalate derivatives (and fluorescers) in water or protic solvents. Seitz and his colleagues described their problems finding compatible solvents in creating a peroxyoxalate chemiluminescence flow injection analysis system for quantitating aqueous hydrogen peroxide. 5® Rauhut, Mo-han, and their collaborators obtained little improvement by performing the reaction in cyclohexane in water emulsions but obtained much betterresults by including a detergent above its critical micelle concentration25 or polymer additives (B. H. Baretz, personal communication). The American Cyanamide group has also synthesized ox-alate derivatives and fluorescers that are somewhat water