Activation/Driving Force Relationships for the Unimolecular Rearrangement of Radical Ions

有了这个奖项，有机和高分子化学计划支持教授詹姆斯M。Tanko博士，弗吉尼亚理工学院和弗吉尼亚州布莱克斯堡州立大学化学系，负责一个涉及自由基离子单分子重排研究的研究项目。 特别是，该研究将研究含有应变环的自由基离子的开环速率和热力学驱动力之间的关系的性质。 重排的速率将使用电化学技术和激光闪光光解来测量。结合实验和理论，包括伏安法，分子轨道计算，解离电子转移理论将被应用于分析这些系统，并确定反应速率和反应自由能之间的关系。这些研究的结果将促进我们对有机反应机理的理解，因为它们适用于生物过程。这项研究是特别重要的，其预期的影响，在该地区的机制为基础的药物设计。该项目将通过培训本科生、研究生和博士后人员，促进科学教育和人力资源开发。 参与者将接受现代有机，生物有机和物理化学的理论和实践教育。他们将接受有机化合物的处理和合成、现代分析技术、激光闪光光解、电化学以及安全处理和处置化学废物的适当程序等方面的实际培训。

With this award, the Organic and Macromolecular Chemistry Program supports the work of Professor James M. Tanko, of the Chemistry Department at Virginia Polytechnic Institute and State University, Blacksburg, VA, for a research project involving investigations of the unimolecular rearrangements of radical ions. In particular, the research will examine the nature of the relationship between the rate and thermodynamic driving force for the ring opening of radical ions containing strained rings. The rates of the rearrangement will be measured using electrochemical techniques and laser flash photolysis. A combination of experiment and theory, including voltametry, molecular orbital calculations, and the theory of dissociative electron transfer will be applied to analyze these systems and to determine the relationship between reaction rate and free energy of reaction.The results of these studies will advance our understanding of organic reaction mechanisms as they apply to biological processes. The research is of particular importance for its expected impact in the area of mechanism-based drug design. The project will contribute to science education and human resource development by training individuals at the undergraduate, graduate and postdoctoral levels. Participants will be educated in the theory and practice of modern organic, bioorganic, and physical chemistry. They will receive practical training in the handling and synthesis of organic compounds, modern analytical techniques, laser flash photolysis, electrochemistry, and proper procedures for the safe handling and disposal of chemical waste.