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Two novel methylesterases from Olea europaea contribute to the catabolism of oleoside-type secoiridoid esters


Main conclusion

Two newly identified phytohormone cleaving esterases from Olea europaea are responsible for the glucosidase-initiated activation of the specialized metabolites ligstroside and oleuropein.


Biosynthetic routes leading to the formation of plant natural products are tightly orchestrated enzymatic sequences usually involving numerous specialized catalysts. After their accumulation in plant cells and tissues, otherwise non-reactive compounds can be enzymatically activated, e.g., in response to environmental threats, like pathogen attack. In olive (Olea europaea), secoiridoid-derived phenolics, such as oleuropein or ligstroside, can be converted by glucosidases and as yet unidentified esterases to oleoside aldehydes. These are not only involved in pathogen defense, but also bear considerable promise as pharmaceuticals or neutraceuticals. Making use of the available olive genomic data, we have identified four novel methylesterases that showed significant homology to the polyneuridine aldehyde esterase (PNAE) from Rauvolfia serpentina, an enzyme acting on a distantly related metabolite group (monoterpenoid indole alkaloids, MIAs) also featuring a secoiridoid structural component. The four olive enzymes belong to the α/ß-hydrolase fold family and showed variable in vitro activity against methyl esters of selected plant hormones, namely jasmonic acid (MeJA), indole acetic acid (MeIAA), as well as salicylic acid (MeSA). None of the identified catalysts were directly active against the olive metabolites oleuropein, ligstroside, or oleoside 11-methyl ester. When employed in a sequential reaction with an appropriate glucosidase, however, two were capable of hydrolyzing these specialized compounds yielding reactive dialdehydes. This suggests that the esterases play a pivotal role in the activation of the olive secoiridoid polyphenols. Finally, we show that several of the investigated methylesterases exhibit a concomitant in vitro transesterification capacity—a novel feature, yielding ethyl esters of jasmonic acid (JA) or indole-3-acetic acid (IAA).

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Data availability

The sequences reported herein are deposited with GenBank under accession numbers MK23485, MK160486, MK236351, and MK236352.

Change history

  • 01 November 2019

    Page 5, paragraph 3, line 14, GenBank Accession Number which should read MK234850 instead of MK23485.



Jasmonic acid


Methyl jasmonate


Methyl salicylate


Polyneuridine aldehyde esterase


Salicylic acid


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This work was funded through a collaborative research grant from BMBF (NeurOliv, Förderkennzeichen 031A590B). The contribution of reference substances by Christopher Fuchs and Renate Kirsch is greatly appreciated. The authors also acknowledge the support of the COST Action FA1006, PlantEngine). Further, our thanks are due to Agata Staniek, ProofEdScience, for language editing.

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Volk, J., Sarafeddinov, A., Unver, T. et al. Two novel methylesterases from Olea europaea contribute to the catabolism of oleoside-type secoiridoid esters. Planta 250, 2083–2097 (2019). https://doi.org/10.1007/s00425-019-03286-0

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  • Secoiridoid
  • α/β-Hydrolase
  • Methylesterase
  • Ligstroside aglycone
  • Oleuropein aglycone
  • Phytohormone