Mechanistic Singlet Oxygen Chemistry

这项有机和大分子化学基金为怀俄明大学爱德华·克莱南博士的研究提供了支持。本文主要研究单线态氧的反应。这种形式的氧是受激的或有能量的氧。许多与衰老有关的生物过程被认为涉及单线态氧，因此，对其反应化学的基本理解与重要的生物学问题密切相关。对单线态氧与富电子二烯和与硫化物的反应机理进行了研究。本文将进行用于探测单线态氧反应的电子转移和嵌合辅助效应的底物的合成。溶剂、温度和添加剂对这些底物与单线态氧反应形成的产物分布的影响将被考察。低温核磁共振将用于检测中间体，并在这些底物存在的情况下监测1200nm单线态氧的发射，以获得重要的动力学信息。单线态氧中间体的分子内捕获将用亚砜捕获基团进行。分子内俘获的优点是可以确定中间体上的对称信息。取代基对亚砜基团捕获能力的影响将被仔细研究。

This grant in Organic and Macromolecular Chemistry provides support for the research of Dr. Edward Clennan, University of Wyoming. The work focuses on reactions of singlet oxygen. This form of oxygen is an excited or energetic one. A number of biological processes related to aging are thought to involve singlet oxygen and a fundamental understanding of its reaction chemistry is, thus, closely linked to important biological problems. Mechanistic studies of the reactions of singlet oxygen with electron rich dienes and with sulfides will be studied. The synthesis of substrates to probe singlet oxygen reactions for electron transfer and anchimeric assistance effects will be undertaken. The effect of solvent, temperature, and additives on product distributions formed in the reactions of these substrates with singlet oxygen will be examined. Low temperature NMR will be utilized to detect intermediates and the emission of singlet oxygen at 1200nm will be monitored in the presence of these substrates in order to obtain important kinetic information. Intramolecular trapping of singlet oxygen intermediates will be pursued with sulfoxide trapping groups. Intramolecular trapping has the advantage that symmetry information on the intermediate can be ascertained. The effect of substitutents on the trapping ability of the sulfoxide groups will be carefully examined.