Grantee Research Project Results

Enzymes are nature’s catalysts for performing highly efficient and specific chemical transformations typically resulting in low levels of pollutive byproducts; they can be used for bioremediation, conversion of chemical energy, and production of medicinal agents in an environmentally-friendly manner. We propose to develop a mechanistic understanding of intermediates employed by biological systems that will serve as a basis for synthetic design or directed evolution to generate green synthetic processes and agents of bioremediation. The challenge of creating catalysts that match the efficiency of nature and are economically viable, while contributing a minimal amount of pollution to the environment requires insight into how these enzymes work. Three iron-containing enzyme systems, methane monooxygenase (MMO), benzoate 1,2-dihydrodiol oxygenase (BZDOS) and the halogenase SyrB2, catalyze environmentally- or commercially-important processes and the insight obtained of their reaction mechanisms will be used as templates for bioinspired design and directed evolution. We have initiated spectroscopic and computational studies on these species and related model complexes. The results from these show that the nuclear resonance vibrational scattering (NRVS) method (vide infra) is highly sensitive to the geometric structure of high-valent and hydroperoxo intermediates.