RUI: Mechanistic Studies of Encapsulated Metalloenzymes

Hamilton College, Clinton NY

Investigators

Abstract

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor Timothy Elgren at Hamilton College to use sol-gel encapsulation of enzymes as a method for isolating and characterizing intermediates in the enzyme catalytic cycle. Encapsulation of the enzymes 1) inhibits intermolecular disproportionation, 2) slows reaction kinetics, and 3) allows reactions to be run in aprotic solvents creating a water-limiting environment. The proposed studies take advantage of these aspects of the sol-gel materials and will provide mechanistic insight into: 1) Oxygen activation in copper-containing amine oxidase, 2) Halogenations catalyzed by peroxidases, 3) Oxidative dehalogenations catalyzed by peroxidases. Sol-gels can be routinely cast in a variety of sampling configurations which, when combined with the transparent nature of the sol-gel materials, allows for spectroscopic characterization, including UV-Vis absorption, resonance Raman, and EPR. This proposal outlines a unique approach to trapping and characterizing catalytic intermediates in the turnover cycles of enzymes. The work will be done entirely in collaboration with undergraduate students. Two Native American high school students participating in the Oneida Nation/Hamilton College Joint Summer Science Program will be invited each year to participate in the project during the two-week summer program. Students will be encouraged to present the work at the national meeting of the American Chemical Society.