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A Customizable Approach for the Enzymatic Production and Purification of Diterpenoid Natural Products
Published on: October 4, 2019
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Substrate geometry controls the cyclization cascade in multiproduct terpene synthases from Zea mays.
Abith Vattekkatte1, Nathalie Gatto, Tobias G Köllner
1Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Hans-Knöll-Strasse 8, D-07745 Jena, Germany. boland@ice.mpg.de.
Organic & Biomolecular Chemistry
|May 6, 2015
Summary
Maize terpene synthases TPS4 and TPS5 show altered product formation and increased efficiency with specific substrate geometries. This suggests controlling substrate configuration can optimize the production of valuable cyclic terpenoids.
Area of Science:
- Biochemistry
- Plant Molecular Biology
- Enzymology
Background:
- Maize terpene synthases (TPS) are crucial enzymes in plant secondary metabolism.
- Multiproduct TPS enzymes produce complex mixtures of terpenoids from common precursors.
Purpose of the Study:
- To investigate the role of substrate geometry in the catalytic mechanism of maize TPS4 and TPS5.
- To explore the potential for optimizing terpenoid biosynthesis through substrate modification.
Main Methods:
- Synthesis of isotopically labeled geometric isomers of geranyl diphosphate (GDP) and farnesyl diphosphate (FDP).
- Enzymatic assays using maize TPS4 and TPS5 with natural (2E) and modified (2Z) substrates.
- Analysis of kinetic isotope effects and product distributions.
Main Results:
- Maize TPS4 and TPS5 exhibited lower kinetic isotope effects with (2Z) substrates compared to (2E) substrates.
- Deuterated (2Z)-precursors led to a preference for cyclic products and enhanced enzyme turnover.
- The (2E) → (2Z) isomerization step was identified as a potential rate-limiting factor.
Conclusions:
- Substrate geometry significantly influences the reaction cascade of multiproduct terpene synthases.
- Optimizing substrate configuration, specifically favoring the (2Z) form, can enhance the production of desired cyclic terpenoids.
- This provides a potential strategy for metabolic engineering of valuable terpenoid compounds.
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