Journal
BIOCHEMISTRY
Volume 48, Issue 27, Pages 6288-6290Publisher
AMER CHEMICAL SOC
DOI: 10.1021/bi9009049
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- Syracuse University
- University of Ottawa
- Canadian Foundation for Innovation
- National Institutes of Health [R01GM085128]
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Zearalenone, a fungal macrocyclic polyketide, is a member of the resorcylic acid lactone family. Herein, we characterize in vitro the thioesterase from PKS13 in zearalenone biosynthesis (Zea TE). The excised Zea TE catalyzes macrocyclization of a linear thioester-activated model of zearalenone. Zea TE also catalyzes the cross coupling of a benzoyl thioester with alcohols and amines. Kinetic characterization of the cross coupling is consistent with a ping-pong bi-bi mechanism, confirming an acyl-enzyme intermediate. Finally, the Substrate specificity of the Zea TE indicates the TE may help control iterative cycling on PKS13 by rapidly offloading the final resorcylate-containing product.
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