Journal
NEW PHYTOLOGIST
Volume 229, Issue 4, Pages 2288-2301Publisher
WILEY
DOI: 10.1111/nph.16975
Keywords
C‐ C oxidative cleavage; cytochrome P450; iridoid biosynthesis; Olea europaea; oleoside methyl ester; oleuropein; olive; phenolic secoiridoids
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Funding
- Alexander von Humboldt Foundation
- Max-Planck-Gesellschaft
- European Union's Horizon 2020 Research and Innovation Program Marie Sklodowska-Curie - Before Project [645595]
- Italian National Research Council
- Rural Development Program of Umbria Region [16.2.1]
- MIUR [856]
- Mint Consortium
- Riparto Fondo Ordinario Enti di Ricerca - Anno 2019 - Assegnazione CNR per Progettualita di carattere Straordinario - Progetto 'Economia Circolare' (Green & Circular Economy - GECE)
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The discovery of new bifunctional enzymes influencing olive oil quality sheds light on the biosynthetic pathway of olive oil. Experimental evidence revealed the key role of these enzymes in product specificity, uncovering a new mechanism for seco-iridoid production in plants. Furthermore, the study identified a genetic link between cultivated and wild olives.
Olive (Olea europaea) is an important crop in Europe, with high cultural, economic and nutritional significance. Olive oil flavor and quality depend on phenolic secoiridoids, but the biosynthetic pathway of these iridoids remains largely uncharacterized. We discovered two bifunctional cytochrome P450 enzymes, catalyzing the rare oxidative C-C bond cleavage of 7-epi-loganin to produce oleoside methyl ester (OeOMES) and secoxyloganin (OeSXS), both through a ketologanin intermediary. Although these enzymes are homologous to the previously reported Catharanthus roseus secologanin synthase (CrSLS), the substrate and product profiles differ. Biochemical assays provided mechanistic insights into the two-step OeOMES and CrSLS reactions. Model-guided mutations of OeOMES changed the product profile in a predictable manner, revealing insights into the molecular basis for this change in product specificity. Our results suggest that, in contrast to published hypotheses, in planta production of secoxy-iridoids is secologanin-independent. Notably, sequence data of cultivated and wild olives point to a relation between domestication and OeOMES expression. Thus, the discovery of this key biosynthetic gene suggests a link between domestication and secondary metabolism, and could potentially be used as a genetic marker to guide next-generation breeding programs.
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