Development of Highly Sensitive and Selective Fluorogenic Chemdosimeters

在这个由化学学部化学结构、动力学与机制B项目和化学测量与成像项目资助的项目中，匹兹堡大学化学系的小出和纪教授将开发具有有用荧光特性的新型化学试剂。本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、分析、无机和生物化学的界面，因此非常适合各级科学家的教育。该小组也有能力为本科生、研究生和博士后研究人员提供跨学科的教育和培训。涉及大学新生的外展活动将是该项目的一部分。具体来说，当暴露于汞或过氧化氢时会发出荧光的化学传感器将被开发出来。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，产生高灵敏度的分析方法。催化反应包括异位重排和环化反应，这两种反应都将在接触汞物种时从非荧光起始材料产生荧光产物。这些方法将应用于燃煤电厂废水的分析。汞将被量化为低于0.1 ppb的水平。对于过氧化氢的检测和定量，将使用过氧化氢介导的[2,3]-异位重排，该重排从非荧光前体产生绿色荧光染料。目的是开发新的探针检测和定量过氧化氢在活的人细胞。为了实现这一目标，将制作非荧光重排底物。当底物与过氧化氢反应并发生重排时，将产生绿色荧光素衍生物。

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.