New Analytical Chemiluminescence System Using Energetic Species formed by the Decomposition of Peroxymonosulfate

过氧单硫酸盐KHSO_5催化分解生成活性化学物种(^1O_2、OH、SO_4^-、M^&lt；N+1&gt；等)。在存在某种过渡金属离子M^&lt；n+&gt；本研究的目的是从分析的角度探讨活性化学物种诱导的化学发光，并建立测定过渡金属离子和有机化合物的新的流动化学发光方法。所获得的结果如下所述。用21种过渡金属离子对HSO5+的发光分解进行了筛选实验，首次发现Co^&lt；2+&gt；-，Fe^&lt；2+&gt；-和VO^&lt；2+&gt；-催化分解伴随有发光。在测定发光强度的基础上，建立了在表面活性剂胶束介质中用增敏剂测定Co^&lt；2+-gt；，Fe^-lt；2+-gt；和VO^-lt；2+&gt；的灵敏和选择性的化学发光方法。该方法已成功应用于实际样品中。实验证实，单线态氧1O_2在上述化学发光反应中起重要作用。对活性化学物种与有机化合物的化学发光反应的研究表明，在无缓冲溶液中，Co~(2+)和Gt~(2+)的催化分解导致荧光有机物产生强烈的化学发光。这使得荧光有机化合物，如多芳化合物、染料和丹磺化氨基酸的流动化学发光检测可以在10^&lt；-6&gt；-8&gt；M水平上进行。发现活性化学物种对荧光化合物的化学发光保持了30min以上的活性。具有如此长寿命的化合物有望成为化学发光反应以外的分析试剂。

Peroxymonosulfate KHSO_5 catalytically decomposes to generate active chemical species(^1O_2, OH, SO_4^-, M^<N+1> etc.) in the presence of a certain transition metal ion M^<n+>. The objective of the present research is to explore the chemiluminescence(CL) induced by the active chemical species from the analytical point of view and to develop new flow CL methods for the determinations of the transition metal ions and organic compounds. The results obtained are described below.1. The screening test for the luminous decomposition of HSO_5^- with 21 transition metal ions was conducted and Co^<2+>-, Fe^<2+>-, and VO^<2+>- catalyzed decompositions were found for the first time to be accompanied by light emission. Based on the measurement of the intensity of the emitted CL, the sensitive and selective CL methods for the determinations of Co^<2+>, Fe^<2+> and VO^<2+> were established by use of a sensitizer in surfactant micellar medium. The method was successfully applied to real samples.2. It was confirmed experimentally that singlet oxygen ^1O_2 took an important role in the above CL reactions.3. The study on the CL reaction of the active chemical species with organic compounds revealed that the Co^<2+>-catalyzed decomposition in unbuffered solution gave rise to intense CL for fluorescent organic compounds. This permitted the flow CL detection of fluorescent organic compounds such as polyaromatic compounds, dyes and dansylated amino acids at 10^<-6> - 10^<-8> M levels.4. The active chemical species were found to remain active for the CL emission of the fluorescent compounds for more than 30 min. It is expected that they possessing such a long lifetime may be used as analytical reagents other than those for the CL reaction.