Formation of compound I in P450: Photooxidation from compound II to compound I

ORGN 89

James A. Halgrimson, james.halgrimson@gmail.com1, Martin Newcomb, men@uic.edu2, Rui Zhang3, R. Esala P. Chandrasena, esala@yahoo.com1, John H. Horner, Horner@uic.edu2, Thomas M. Makris4, and Stephen G. Sligar, sligar@scs.uiuc.edu5. (1) Chemistry, University of Illinois at Chicago, 845 West Taylor St., Chicago, IL 60607, (2) Department of Chemistry, University of Illinois at Chicago, 845 W. Taylor St., Chicago, IL 60607, (3) Department of Chemistry, University of Illnios at Chicago, 845 W. Taylor St., Chicago, IL 60607, (4) Department of Biochemistry, University of Illinois, 405 North Mathews Ave., Urbana, IL 61801, (5) Departments of Biochemistry, Chemistry, and College of Medicine, University of Illinois, 505 S. Goodwin Ave., Urbana, IL 61801
Most recently, P450 research has focused on the isolation and characterization of intermediates directly responsible for hydrogen abstraction and hydroxylation of hydrocarbons. Compound I, the believed natural oxidant in P450, has previously never been observed. Using focused 355nm laser light, we have effectively initiated an oxidative environment about the porphyrin causing the ejection of a single electron allowing us to observe highly oxidized P450 enzyme iron-oxygen-porphyrin species. Compound I has been observed in this study using these methods by photooxidizing Compound II, the one electron reduced form of Compound I generated from the oxidation of Fe III by peroxynitrite under stopped flow mixing conditions. We have effectively generated Compound I in P450 119 and obtained the first real UV-visible spectrum of Compound I in a P450 enzyme.
 

Process R&D, Physical Organic Chemistry, Heterocycles, Aromatics, Metal-Mediated Reactions
8:00 PM-10:00 PM, Sunday, March 25, 2007 Hyatt Regency Chicago -- Riverside Center, Poster

Division of Organic Chemistry

The 233rd ACS National Meeting, Chicago, IL, March 25-29, 2007