Reactions Involving Main-Group Radicals in Solution

奥本大学化学系的大卫斯坦伯里博士得到化学系无机、生物无机和有机化学项目的支持，研究主基自由基的反应动力学和机理。将开展一系列四个研究项目。第一部分是关于碘化物与单电子外层过渡金属氧化剂在非水溶液中的反应。在这些反应中的兴趣来自于它们与光电化学电池的相关性，其中通过相关氧化剂在非水介质中氧化碘化物是它们设计的重要组成部分。第二个重点是硫醇半胱氨酸和谷胱甘肽在水介质中与经典的外层过渡金属氧化剂的反应。在这种情况下，动机是工作与生物化学的相关性，因为这两种硫醇是生物体中主要的氧化还原活性硫化合物。第三部分研究了水相中经典外层氧化剂对羟胺的氧化反应。这个反应提出了一个难题，因为简单的电子转移氧化被排除热化学的考虑;氢原子转移机制的建议，这是非常不寻常的主族物种在水溶液中的反应。第四部分研究了水溶液中一氧化氮的氧化反应。在这里，电子转移似乎是不太可能的，并提出了各种原子转移机制;以前没有研究过该反应，但它是至关重要的石油化工行业的烟气洗涤器的操作。如上所述，碘化物项目将有助于开发太阳能技术。硫醇项目将有助于理解一般硫代谢。羟胺项目将有助于了解生物硝化作用。一氧化氮/氯酸盐项目将协助开发减少一氧化氮污染的改进技术。这些项目将通过对本科生、研究生和博士后学生的高级培训和教育，加强社会的科学基础设施。

Dr. David Stanbury, Department of Chemistry, Auburn University, is supported by the Inorganic, Bioinorganic and Organometallic Chemistry Program of the Chemistry Division for research into kinetics and mechanisms of reactions of main group radicals. A series of four research projects will be undertaken. The first will be on the reactions of iodide with one-electron outer-sphere transition-metal oxidants in nonaqueous solutions. Interest in these reactions arises from their relevance to photoelectrochemical cells, where oxidation of iodide in nonaqueous media by related oxidants is an essential component of their design. The second focuses on reactions of the thiols cysteine and glutathione in aqueous media with classical outer-sphere transition-metal oxidants. In this case the motivation is the relevance of the work to biochemistry, since these two thiols are the primary redox-active sulfur compounds in living organisms. The third is an investigation of the oxidation of hydroxylamine by classic outer-sphere oxidants in aqueous media. This reaction poses a conundrum, because simple electron-transfer oxidation is ruled out by thermochemical considerations; a hydrogen-atom-transfer mechanism is suggested, which is quite unusual among reactions of main-group species in aqueous solution. The fourth is a study of the aqueous oxidation of nitric oxide with chlorite. Here, electron transfer seems to be quite unlikely, and a variety of atom-transfer mechanisms are suggested; the reaction has not been studied before, but it is crucial to the operation of flue gas scrubbers in the petrochemical industry.In this project new classes of reactivity will be uncovered. As mentioned above, the iodide project will contribute to developing solar energy technology. The thiol project will contribute to the understanding of general sulfur metabolism. The hydroxylamine project will contribute to an understanding of biological nitrification. The nitric oxide/chlorate project will aid in the development of improved technologies for abatement of pollution by nitrogen oxides. The projects will strengthen the scientific infrastructure of society through the advanced training and education of undergraduate, graduate, and postdoctoral students.