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Analysis of Electron Transfer Reactions in Solution with the Development of High-Sensitive Detection Method for Electrogenerated Chemiluminescence using Flow-Electrolysis.

利用流电解开发高灵敏度电化学发光检测方法来分析溶液中的电子转移反应。

基本信息

批准号：
07555567
负责人：
OYAMA Munetaka
金额：
$ 0.45万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
1995
资助国家：
日本
起止时间：
1995 至 1996
项目状态：
已结题

项目摘要

New method for the measurement of electrogenerated chemiluminescence (ECL) was developed by using a pulse-electrolysis stopped-flow method. While numerous studies have been devoted to the ECL caused in the reactions between cation and anion radicals of aromatic substances in aprotic solvents, the ECL reactions ever observed have been resticted to the systems having a smaller redox potential differences than those of a molecule concerned. These are so called "energy deficient" systems. By contrast, for example, the pure reaction between diphenylanthracene (DPA) cation radical and pyrene (PY) anion radical has been very difficult to be observed in the conventional methods because of the interference by the reduction of DPA which is concurrent with the reduction of PY.Although this sort of "energy sufficient" reaction has never been observed, its measurement will be effective to study the emission directly from the singlet state (S-route) and to obtain the information on the excited states explicity. In the present work, the ECL measurement on the energy sufficient systems composed of different kind of ion radicals has become possible by using a pulse-electrolysis stopped-flow apparatus having two electrolysis lines. In this apparatus, by generating cation radicals and anion radicals independently, the ECL is observed in an optical cell. Therefore, various reactions of the energy sufficient systems composed of different kind of ion radicals can be targeted including sort-lived species. In the reaction between thianthrene cation radical and PY anion radical, it was found that the emision spectra changed with the addition of the precursors reflecting the complex electron and energy transfers in solution. In addition, the emitting properties was clarified to depend on the sort of the molecules significantly through the measurements in which three Components were mixed.

采用脉冲电解停流法建立了一种新的电致化学发光（ECL）测定方法。尽管已经有许多研究致力于在非质子溶剂中芳香族物质的阳离子和阴离子自由基之间的反应中引起的ECL，但是所观察到的ECL反应一直局限于具有比所涉及的分子的氧化还原电位差小的氧化还原电位差的系统。这就是所谓的“能量不足”系统。相比之下，例如，由于与芘（PY）还原同时进行的二苯蒽（DPA）还原的干扰，在常规方法中很难观察到二苯蒽（DPA）阳离子自由基与芘（PY）阴离子自由基之间的纯反应。虽然从未观察到这种“能量充足”的反应，它的测量对于直接研究单重态（S-途径）的发射和明确获得激发态的信息是有效的。在本工作中，ECL测量的能量充足的系统组成的不同类型的离子自由基已成为可能，通过使用脉冲电解停流装置具有两个电解线。在该装置中，通过独立地产生阳离子自由基和阴离子自由基，在光学元件中观察ECL。因此，由不同种类的离子自由基组成的能量充足系统的各种反应可以作为目标，包括各种活性物种。在噻蒽阳离子自由基与PY阴离子自由基的反应中，发现随着前驱体的加入，反应产物的发射光谱发生了变化，反映了溶液中复杂的电子和能量转移。此外，通过对三种组分混合的测量，阐明了发射性质显著依赖于分子的种类。