Spectroscopic Detection and Reaction Analysis of Short-lived Species Generated in Solution Using an Electron-Transfer Stopped-Flow Method

使用电子转移停流方法对溶液中产生的短寿命物质进行光谱检测和反应分析

基本信息

批准号：
13640602
负责人：
OYAMA Munetaka
金额：
$ 2.56万
依托单位：
KYOTO UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (C)
财政年份：
2001
资助国家：
日本
起止时间：
2001 至 2003
项目状态：
已结题

项目摘要

Using an electron transfer stopped-flow method, spectroscopic detection and reaction analysis were carried out for various aromatic amine cation radicals. In the reaction of 4-bromo-N, N-dimethylaniline cation radical, the dimerization reaction mechanism accompanying the release of bromo-subsutituent was clarified. In the case of triphenylamine cation radical, a stabilized state was clarified to be formed with the presence of precursor molecules. In the reaction of N, N-dimethyl-toluidine cation radical, while the cation radicals was stable without the precursors, the cation radical decreased in the presence of precursors due to the acid-base reaction. The reaction of N, N-dimethyl-anisidine cation radical is the same, but the dimerization rate was ca. 1/100 due to the stabilization effect of methoxy group. The reactions of N-methylanisidine and anisidine cation radicals were also examined as well as the meta-and ortho-derivatives.Furthermore, the reactions of carbazole derivative cation radicals could be analyzed using the proposed method. Finally, the study moved toward the detection and analysis of monomer cation radicals to form the electro-conducting polymer materials. In particular, for the thiophene derivatives, it was found that terthiophene canon radical can be detected to follow the decrease. In the cases of ethylenedioxithiophene derivative cation radicals, the study is now in underway.

使用电子转移停止流量法，对各种芳香胺阳离子自由基进行了光谱检测和反应分析。在4-溴-N，n-二甲基苯胺阳离子自由基的反应中，阐明了伴随Bromo-Subsutitutent释放的二聚化反应机制。在三苯胺阳离子自由基的情况下，阐明了稳定的状态，以形成前体分子的存在。在n，n-二甲基二苯甲酸阳离子自由基的反应中，而阳离子自由基在没有前体的情况下是稳定的，在存在酸碱反应引起的前体的存在下，阳离子自由基降低。 N，N-二甲基 - 氨基烷阳离子自由基的反应是相同的，但二聚化速率为CA。 1/100由于甲氧基的稳定作用。还检查了N-甲基酶苷和苯胺阳离子自由基的反应以及元和正源性。Furthermore可以使用所提出的方法分析甲壳唑衍生物阳离子自由基的反应。最后，该研究转向对单体阳离子自由基的检测和分析，形成了电导的聚合物材料。特别是，对于噻吩衍生物，发现可以检测到terthiphene Canon自由基遵循减少。在乙二醇二苯乙烯衍生物自由基的情况下，该研究正在进行中。