Biosynthesis of barley wax β-diketones: a type-III polyketide synthase condensing two fatty acyl units

Yulin Sun, Alberto Ruiz Orduna, Zhonghang Zhang, Sarah J. Feakins and Reinhard Jetter ()
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Yulin Sun: University of British Columbia
Alberto Ruiz Orduna: University of British Columbia
Zhonghang Zhang: University of British Columbia
Sarah J. Feakins: University of Southern California
Reinhard Jetter: University of British Columbia

Nature Communications, 2023, vol. 14, issue 1, 1-16

Abstract: Abstract The surface coatings of cereal plants are dominated by waxy β-diketones crucial for drought resistance and, therefore, grain yield. Here, barley (Hordeum vulgare) wax analyses reveal β-diketone and associated 2-alkanol ester profiles suggesting a common C16 3-ketoacid precursor. Isotope analysis further shows that the major (C31) diketone is synthesized from two plastidial C16 acyl units. Previous studies identified a gene cluster encoding enzymes responsible for β-diketone formation in barley, but left their biochemical functions unknown. Various assays now characterize one of these enzymes as a thioesterase producing long-chain (mainly C16) 3-ketoacids, and another one as a polyketide synthase (PKS) condensing the 3-ketoacids with long-chain (mainly C16) acyl-CoAs into β-diketones. The two enzymes are localized to the plastids and Endoplasmic Reticulum (ER), respectively, implying substrate transfer between these two sub-cellular compartments. Overall, our findings define a two-step pathway involving an unprecedented PKS reaction leading directly to the β-diketone products.

Date: 2023
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DOI: 10.1038/s41467-023-42917-9

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