权益分类	功能权益	普通用户	{{item.name}}会员
{{category.name}}	{{benefitItem.name}}

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.

用电子转移停流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反应中，阐明了伴随溴取代基释放的二聚反应机理。在三苯胺阳离子自由基的情况下，澄清了在前体分子的存在下形成的稳定状态。在N，N-二甲基甲苯胺阳离子自由基反应中，没有前体时，阳离子自由基是稳定的，而前体存在时，由于酸碱反应，阳离子自由基减少。N，N-二甲基-茴香胺阳离子自由基的反应也是一样，但二聚速率约为1000。1/100，这是由于甲氧基的稳定作用。研究了N-甲基茴香胺和茴香胺阳离子自由基以及间位和邻位衍生物的反应，并对咔唑衍生物阳离子自由基的反应进行了分析。最后，研究转向单体阳离子自由基的检测和分析，以形成导电聚合物材料。特别地，对于噻吩衍生物，发现可以检测到三噻吩正离子自由基跟随减少。对于乙撑二氧噻吩衍生物阳离子自由基的研究正在进行中。