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.
