Organic Free Radical Chemistry

有机自由基化学

• 批准号: 0235293
• 负责人: Martin Newcomb
• 金额: $ 43.5万
• 依托单位: University of Illinois at Chicago
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2003
• 资助国家: 美国
• 起止时间: 2003-02-01 至 2006-01-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0235293&HistoricalAwards=false
• 关键词: Organic; Free; Radical; Chemistry

The focus of this research is to develop a systematic study of radical heterolysis reactions. The research will include kinetic and mechanistic studies of radical cations, focusing on radical cations believed to be involved in the rearrangement of methylmalonyl/coenzyme-A to succinate in vivo. Strained 3-membered ring "reporter groups" will be synthesized and opened photolytically to measure the rate of radical formation by UV spectroscopy. This approach is well suited for the study of alpha- and beta-carboxylate functionalized radicals believed to be involved in the chemistry of B12 dependent enzymes. With this Renewal award, the Organic and Macromolecular Chemistry Program is supporting the research and educational efforts of Dr. Martin E. Newcomb of the Department of Chemistry at the University of Illinois, Chicago. Professor Newcomb will focus his research on the use of lasers to break critical bonds related to the function of vitamin B12 in the human body. This work will have impact on the design of new methods for catalysis in the pharmaceutical industry, as well as important impacts on the understanding of enzyme function. The educational activity of the award revolves around the training of graduate students in the study of short-lived chemical intermediates.

本研究的重点是对自由基异裂解反应进行系统的研究。 该研究将包括自由基阳离子的动力学和机理研究，重点是自由基阳离子被认为是参与甲基丙二酰/辅酶-A在体内的琥珀酸重排。 应变3元环“报告基团”将被合成和光解打开，以通过UV光谱测量自由基形成的速率。 这种方法非常适合于研究α-和β-羧酸官能化的自由基，据信这些自由基参与B12依赖性酶的化学反应。 有了这个更新奖，有机和高分子化学计划是支持博士的研究和教育工作。芝加哥伊利诺斯大学化学系的纽科姆说。 纽科姆教授将把研究重点放在利用激光打破与人体维生素B12功能相关的关键键上。 这项工作将对制药工业中催化新方法的设计产生影响，并对酶功能的理解产生重要影响。 该奖项的教育活动围绕研究生在短期化学中间体的研究培训。