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

通过这一奖项，有机化学和高分子化学计划支持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詹姆斯·M·坦科教授的工作，该研究项目涉及研究自由基离子的单分子重排。特别是，这项研究将考察含有应变环的自由基离子开环的速率和热力学驱动力之间的关系的本质。重排的速率将使用电化学技术和激光闪光光解来测量。实验和理论相结合，包括伏安法、分子轨道计算和解离电子转移理论，将被用来分析这些体系，确定反应速度和反应自由能之间的关系，这些研究结果将促进我们对应用于生物过程的有机反应机理的理解。这项研究对于其在基于机制的药物设计领域的预期影响具有特别重要的意义。该项目将通过培训本科生、研究生和博士后人员，为科学教育和人力资源开发做出贡献。学员将学习现代有机、生物有机和物理化学的理论和实践。他们将接受有关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的实用培训。

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.