Model systems for flavoenzyme activity: Synthetic flavoenzyme mimics via nanoparticle and polymeric scaffolds

ORGN 608

Brian J Jordan, bjjordan@chem.umass.edu1, Graeme Cooke, graemec@chem.gla.ac.uk2, James F Garety2, Michael A Pollier, mpollier@chem.umass.edu1, Nadiya Kryvokhyzha2, Ali Bayir, abayir@chemistry.umass.edu3, Gouher Rabani2, Ayush Verma3, and Vincent M. Rotello, rotello@chem.umass.edu1. (1) Department of Chemistry, University of Massachusetts, 710 North Pleasant Street, Amherst, MA 01003, (2) Department of Chemistry, University of Glasgow, Joseph Black Building, Glasgow, United Kingdom, (3) Department of Chemistry, University of Massachusetts Amherst, 701 Lederle Graduate Research Tower A, 710 North Pleasant Street, Amherst, MA 01003
Flavoenzymes catalyze a series of biological processes including electron transfer and signal transduction through redox modulation of a flavin cofactor (FMN or FAD). Non-covalent supramolecular interactions fine-tune the cofactor redox properties to generate specific enzymatic function and isolate the cofactor in a hydrophobic binding pocket. Previous synthetic models have provided a general understanding of the role of hydrogen bonding, pi-stacking, and donor atom pi interactions, but have failed to regenerate the specific microenvironment within the apoenzyme. We report two distinct approaches to mimic the biological environment of the flavin cofactor using either nanoparticle or polymeric scaffolds in aqueous media. First, we use cationic nanoparticles to electrostatically bind to FMN, resulting in high affinity and modulation of the FMN reduction potential. Second, we use a water soluble flavin polymer synthesized via ATRP that provides both a relative hydrophobic environment and redox modulation of the appended flavin unit typical of some flavoenzymes.
 

Molecular Recognition and Self-Assembly
1:00 PM-5:00 PM, Wednesday, March 28, 2007 McCormick Place Lakeside -- Room E352, Level 3, Oral

Division of Organic Chemistry

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