Activation - Driving Force Relationships in Radical Ion Rearrangements

本研究的重点是阐明有机自由基化学 阴离子和阳离子，被认为是关键的中间体， 化学和生物化学转化的数量。 腐烂的速度 在这些短暂的中间体中，化学产生的， 电化学地或光化学地从选定的前体， 作为前体结构、溶剂极性和 反离子 相应的热力学数据，主要是自由的 与环状自由基负离子开环有关的能量变化 和阳离子，将通过适当的电化学测定 热化学循环 使用已经或将要使用的特定前体 在实验过程中合成，并将 获得相应自由基的动力学和热力学数据 阴离子或阳离子，这些短寿命 将开发中间体。 有了这个奖项，有机和高分子化学计划 支持James Tanko教授的研究和教育活动 弗吉尼亚理工大学化学系的教授 Tanko教授的研究将集中在阐明 结构-反应性关系定义了反应性的化学性质， 阳离子和阴离子自由基中间体。 虽然众所周知， 在许多有机转化的中间体，这些 高活性、寿命短的中间体现在被认为是 在许多药理学和酶的中间体 转变 Tanko教授的教育活动涉及 博士后、研究生、本科生教育培养 学生

This research focuses on elucidating the chemistry of organic radical anions and cations that are considered to be key intermediates in a number of chemical and biochemical transformations. The rates of decay of these transient intermediates, generated chemically, electrochemically, or photochemically from selected precursors, will be measured as functions of precursor structure, solvent polarity and counter ion. Corresponding thermodynamic data, principally the free energy change associated with the ring opening of cyclic radical anions and cations, will be determined electrochemically by means of appropriate thermochemical cycles. Using selected precursors that have been or will be synthesized during the course of the experiments, and correlating the kinetic and thermodynamic data obtained for the corresponding radical anion or cation, structure-reactivity relationships of these short-lived intermediates will be developed. With this Award, the Organic and Macromolecular Chemistry Program supports the research and educational activities of Professor James Tanko of the Chemistry Department at Virginia Polytechnic University. Professor Tanko's research will focus on elucidating the structure-reactivity relationships that define the chemistry of reactive cationic and anionic radical intermediates. Although well known as intermediates in a number of organic transformations, these highly-reactive, short-lived intermediates are now thought to be intermediates in a number of pharmacological and enzymatic transformations. Professor Tanko's educational activities involve the education and training of postdoctoral, graduate and undergraduate students.