Development of Highly Sensitive and Selective Fluorogenic Chemdosimeters

在该项目中，匹兹堡大学化学系的化学结构、动态和机理B计划和化学测量和成像计划将开发具有有用荧光特性的新型化学试剂。这项研究的目的是利用过氧化氢和汞的特性来开发荧光检测方法。该项目位于有机化学、分析化学、无机化学和生物化学的交界处，因此非常适合各级科学家的教育。这一群体也处于有利地位，可以为本科生和研究生以及博士后研究人员提供跨学科的教育和培训。包括一年级大学生在内的外展活动将是该项目的一部分。具体地说，将开发暴露在汞或过氧化氢中时会发出荧光的化学传感器。对于汞的检测，首席研究员建议利用汞催化的有机反应。催化系统将放大荧光信号，产生高度灵敏的分析方法。催化反应包括S型重排和环化反应，这两种反应都会使非荧光起始物质接触到汞物种而生成荧光产物。这些方法将应用于燃煤电厂废水的分析。汞将被量化到0.1 ppb以下。对于过氧化氢的检测和定量，将使用由过氧化氢介导的[2，3]-Sigmatrotic重排，该重排从非荧光前体产生绿色荧光染料。其目的是开发新的探针来检测和定量活的人类细胞中的过氧化氢。为了实现这一目标，将制造非荧光重排底物。当底物与过氧化氢反应并发生重排时，将生成绿色荧光荧光素衍生物。

In this project funded by the Chemical Structure, Dynamic & Mechanism B program and the Chemical Measurement & Imaging program of the Chemistry Division, Professor Kazunori Koide of the Department of Chemistry at the University of Pittsburgh will develop new classes of chemical reagents with useful fluorescence properties. The goal of this research is to exploit the characteristics of hydrogen peroxide and mercury for the development of fluorescence detection methods. The project lies at the interface of organic, analytical, inorganic, and biological chemistry, and is therefore well suited to the education of scientists at all levels. This group is also well-positioned to provide interdisciplinary education and training for undergraduate and graduate students and post-doctoral researchers. Outreach activities involving freshman college students will be part of the project. Specifically, chemosensors that fluoresce when exposed to mercury or hydrogen peroxide will be developed. For mercury detection, the principal investigator proposes to exploit organic reactions catalyzed by mercury. The catalytic systems will amplify fluorescence signals, yielding highly sensitive analytical methods. The catalytic reactions include a sigmatropic rearrangement and a cyclization reaction, both of which will produce a fluorescent product from a nonfluorescent starting material upon exposure to mercury species. These methods will be applied to the analyses of wastewater from coal-fired power plants. Mercury will be quantified below 0.1 ppb levels. For hydrogen peroxide detection and quantification, a [2,3]-sigmatropic rearrangement mediated by hydrogen peroxide, which creates a green fluorescent dye from a nonfluorescent precursor, will be used. The objective is to develop new probes for detecting and quantifying hydrogen peroxide in living human cells. Toward this objective, nonfluorescent rearrangement substrates will be made. When the substrates react with hydrogen peroxide and the rearrangement occurs, a green fluorescent fluorescein derivative will be produced.