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The Enigmatic P450 Decarboxylase OleT Is Capable of, but Evolved To Frustrate, Oxygen Rebound Chemistry

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Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, United States
Department of Chemistry, Princeton University, Princeton, New Jersey 08544, United States
§ Department of Chemistry, Barnard College, Columbia University, New York, New York 10027, United States
*Department of Chemistry and Biochemistry, University of South Carolina, 631 Sumter St., Columbia, SC 29208. Telephone: 803-777-6626. Fax: 803-777-9521. E-mail: [email protected]
Cite this: Biochemistry 2017, 56, 26, 3347–3357
Publication Date (Web):June 12, 2017
https://doi.org/10.1021/acs.biochem.7b00338
Copyright © 2017 American Chemical Society

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    Abstract

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    OleT is a cytochrome P450 enzyme that catalyzes the removal of carbon dioxide from variable chain length fatty acids to form 1-alkenes. In this work, we examine the binding and metabolic profile of OleT with shorter chain length (n ≤ 12) fatty acids that can form liquid transportation fuels. Transient kinetics and product analyses confirm that OleT capably activates hydrogen peroxide with shorter substrates to form the high-valent intermediate Compound I and largely performs C–C bond scission. However, the enzyme also produces fatty alcohol side products using the high-valent iron oxo chemistry commonly associated with insertion of oxygen into hydrocarbons. When presented with a short chain fatty acid that can initiate the formation of Compound I, OleT oxidizes the diagnostic probe molecules norcarane and methylcyclopropane in a manner that is reminiscent of reactions of many CYP hydroxylases with radical clock substrates. These data are consistent with a decarboxylation mechanism in which Compound I abstracts a substrate hydrogen atom in the initial step. Positioning of the incipient substrate radical is a crucial element in controlling the efficiency of activated OH rebound.

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    • Additional results, including UV–vis binding titrations of C6, C8, C10, and C12 FAs (Figure S1), gas chromatogram of the reaction headspace from OleT:DA reactions (Figure S2), gas chromatograms of the products of OleT reactions of C8, C10, and C12 FAs (Figure S3), time course and fitting for Ole-I decay with DA-d19 (Figure S4), decoy CL screening using guaiacol oxidation as a probe (Figure S5), gas chromatograms and reaction products from MCP oxidations (Figure S6), and MS of ring-opened norcarane reaction products (Figure S7) (PDF)

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