Organic Radical Chemistry

有了这个更新奖，有机和高分子化学计划继续支持教授马丁E。芝加哥的伊利诺斯大学化学系的纽科姆说。 研究将集中在导致有机自由基反应的机械理解的实验。 有机自由基将通过具有特征紫外-可见发色团的设计前体的光解产生，这允许高精度的动力学测量和容易的产品识别。 将进行异裂解反应，得到具有高区域选择性的自由基阳离子，以产生烯烃自由基阳离子，研究由自由基阳离子和阴离子组成的离子对的动力学，并测量自由基阳离子的反应动力学。 进一步的研究将集中在自由基反应的刘易斯酸催化，DNA自由基阴离子的电子转移速率，在酶系统中观察到的自由基重排，以及硫酰基自由基与不饱和脂肪酸的反应。这些研究将提供有机自由基的重要动力学信息，所有的基本利益，一些在合成和其他将提供更好地理解相关的生物过程的潜在应用。该项目将培养学生在当代有机化学的许多方面，包括合成，GC-质谱，HPLC，NMR光谱和激光闪光光解动力学研究。 拟议的研究结果将有助于解决化学中的重要问题，以及化学和生物学的界面。

With this renewal award, the Organic and Macromolecular Chemistry Program continues its support of the work of Professor Martin E. Newcomb, of the Chemistry Department at University of Illinois at Chicago. The research will focus on experiments that lead to mechanistic understanding of organic radical reactions. Organic radicals will be produced by photolysis of designed precursors with characteristic UV-visible chromophores, which allow high precision kinetic measurements and facile product identifications. Heterolysis reactions that give radical cations with high regioselectivity will be carried out to generate alkene radical cations, to study the dynamics of ion pairs comprised of radical cations and anions, and to measure the kinetics of reactions of radical cations. Additional studies will focus on the Lewis acid catalysis of radical reactions, electron transfer rates of DNA radical anions, radical rearrangements observed in enzymatic systems, and the reaction of thiyl radicals with unsaturated fatty acids. These studies will provide important kinetic information on organic radicals, all of fundamental interest, some with potential applications in synthesis and others that will provide a better understanding of relevant biological processes.The project will train students in many aspects of contemporary organic chemistry including synthesis, GC-mass spectrometry, HPLC, NMR spectroscopy, and laser flash photolysis kinetic studies. The results of the proposed research will contribute to the solution of important problems in chemistry and at the interface of chemistry and biology.