Mechanistic Singlet Oxygen Chemistry

这笔有机化学和高分子化学方面的拨款为怀俄明大学的爱德华·克伦南博士的研究提供了支持。这项工作的重点是单线态氧的反应。这种形式的氧是一种激发的或高能的氧。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了解与重要的生物学问题密切相关。我们将研究单线态氧与富电子双烯和硫化物的反应机理。将进行底物的合成，以探测电子转移和锚链辅助效应的单线态氧反应。我们将考察溶剂、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。低温核磁共振将被用来检测中间体，并将在这些底物存在的情况下监测1200 nm处的单线态氧发射，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通过亚砜捕获基团来进行。分子内捕获的优点是可以确定中间体上的对称信息。将仔细研究取代基对亚砜基团捕集能力的影响。

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.