Δ4-dn-iso-OPDA, a bioactive plant hormone of Marchantia polymorpha

Summary Significant progress has been recently made in our understanding of the evolution of jasmonates biosynthesis and signaling. The bioactive jasmonate activating COI1-JAZ co-receptor differs in bryophytes and vascular plants. Dinor-iso-12-oxo-phytodienoic acid (dn-iso-OPDA) is the bioactive hormone in bryophytes and lycophytes. However, further studies showed that the full activation of hormone signaling in Marchantia polymorpha requires additional unidentified hormones. Δ4-dn-OPDAs were previously identified as novel bioactive jasmonates in M. polymorpha. In this paper, we describe the major bioactive isomer of Δ4-dn-OPDAs as Δ4-dn-iso-OPDA through chemical synthesis, receptor binding assay, and biological activity in M. polymorpha. In addition, we disclosed that Δ4-dn-cis-OPDA is a biosynthetic precursor of Δ4-dn-iso-OPDA. We demonstrated that in planta cis-to-iso conversion of Δ4-dn-cis-OPDA occurs in the biosynthesis of Δ4-dn-iso-OPDA, defining a key biosynthetic step in the chemical evolution of hormone structure. We predict that these findings will facilitate further understanding of the molecular evolution of plant hormone signaling.


Figure S2 .
Figure S2.Structure determination of Compound 3, related to Figure 2. (A) 1 HNMR and 13 C NMR Spectroscopic Data for Compound 3 in pyridine-d5 (δ in ppm and J in Hz).

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Figure S2 (continued).(B-E)Whole and expanded views of COSY of 3.

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Figure S2 (continued).(F-J)Whole and expanded views of HSQC of 3.

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Figure S2 (continued).(K-N)Whole and expanded views of HMBC of 3.

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Figure S5 Co-expression of GST-MpCOI1 and AtASK1 in Sf9 and expression of MBP-MpJAZ in E. coli, related to Figure 5.

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Figure S6 (continued).(D)The quantitative data of (A).(E)The quantitative data of (B).(F)The quantitative data of (C).

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Figure S7 The docking structure of the MpCOI1-MpJAZ with Δ 4 -dn-cis-OPDA, related to Figure 6.(A) Top view of the docking structure of the MpCOI1-MpJAZ (gray and red ribbons, respectively) and Δ 4dn-cis-OPDA in pink space-fill representation.(B) Side view of the docking structure.The sectional view is shown at the ligand binding site for visibility.