CAS: Metallopeptide Artificial Enzymes

With the support of the Chemistry of Life Processes (CLP) Program in the Division of Chemistry, Professor Kara Bren of the University of Rochester will develop and study small biomolecule catalysts for reactions relevant to developing alternative energy resources and to removing toxic species from water. One of the targeted reactions is the production of the clean-burning fuel hydrogen from water.

The other reaction is the transformation of nitrite, a common groundwater pollutant, into ammonia and hydroxylamine, which are useful products. The planned studies will elucidate mechanistic details of these reactions. Furthermore, light-driven hydrogen production will be studied as a means for storing solar energy.

These studies will yield information broadly applicable to the development of alternative energy resources and environmental remediation. This project will also contribute to growing a diverse scientific workforce by enhancing the Rochester Early Connection Opportunity program for undergraduates by addition of an independent study and research component.

The research supported by this award will focus on the development and study of the mechanism of multi-electron, multi-proton reactions catalyzed by cobalt peptides from the amino terminal, copper- and nickel-binding family. Targeted reactions include proton reduction to dihydrogen and nitrite reduction to ammonia and hydroxylamine. Emphasis is on the understanding of the impact of diffusing proton shuttles and protonatable catalyst moieties on reaction activity, efficiency, and mechanism.

The role of proton-coupled electron transfer (PCET) in these reactions will also be investigated. The results of the electrochemical studies will be applied to the development of photochemical systems with enhanced hydrogen evolution activity. Success in this project is expected to yield improved catalysts for nitrogen oxyanion reduction and proton reduction and enhance the understanding of the role of PCET in the catalysis of proton-requiring reactions in water.

This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.