Organic Radical Chemistry

有了这个新的奖项，有机和大分子化学项目继续支持芝加哥伊利诺伊大学化学系的Martin E. Newcomb教授的工作。这项研究将集中在导致有机自由基反应机理理解的实验上。有机自由基将由设计的具有特征紫外可见发色团的前驱体光解产生，这允许高精度的动力学测量和容易的产品识别。通过产生具有高区域选择性的自由基阳离子的异解反应生成烯烃自由基阳离子，研究由自由基阳离子和阴离子组成的离子对的动力学，测量自由基阳离子的反应动力学。进一步的研究将集中在Lewis酸催化自由基反应、DNA自由基阴离子的电子转移速率、酶系统中观察到的自由基重排以及巯基自由基与不饱和脂肪酸的反应上。这些研究将提供有关有机自由基的重要动力学信息，这些信息都是基本的兴趣，有些在合成方面有潜在的应用，有些将提供更好地理解相关的生物过程。该项目将培养学生在当代有机化学的许多方面，包括合成，气相色谱-质谱，高效液相色谱，核磁共振光谱和激光闪光光解动力学研究。所提出的研究结果将有助于解决化学中的重要问题，并在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.