Lipoxygenase pathway in model bryophytes: 12-oxo-9(13),15-phytodienoic acid is a predominant oxylipin in Physcomitrella patens

Abstract

The model moss Physcomitrella patens and liverwort Marchantia polymorpha possess all enzymatic machinery responsible for the initial stages of jasmonate pathway, including the active 13(S)-lipoxygenase, allene oxide synthase (AOS) and allene oxide cyclase (AOC). At the same time, the jasmonic acid is missing from both P. patens and M. polymorpha. Our GC-MS profiling of oxylipins of P. patens gametophores and M. polymorpha tissues revealed some distinctive peculiarities. The 15(Z)-cis-12-oxo-10,15-phytodienoic acid (12-OPDA) was the major oxylipin in M. polymorpha. In contrast, the 12-OPDA was only a minor constituent in P. patens, while another cyclopentenone 1 was the predominant oxylipin. Product 1 was identified by its MS, ¹H-NMR, ¹H-¹H-COSY, HSQC and HMBC data as 15(Z)-12-oxo-9(13),15-phytodienoic acid, i.e., the iso-12-OPDA. The corresponding C₁₆ homologue, 2,3-dinor-iso-12-OPDA (2), have also been detected as a minor component in P. patens and a prominent product in M. polymorpha. Besides, the 2,3-dinor-cis-12-OPDA (3) was also present in M. polymorpha. Apparently, the malfunction of cyclopentenone reduction by the 12-OPDA reductase in P. patens and (to a lesser extent) in M. polymorpha leads to the isomerization of 12-OPDA and formation of specific cyclopentenones 1 and 2, which are uncommon in flowering plants.

Keywords: Allene oxide synthase; Cyclopentenones; Dinor-cis-12-oxo-phytodienoic acid; Dinor-iso-12-oxo-phytodienoic acid; Marchantia polymorpha (Marchantiaceae); Oxylipins; Physcomitrella patens (Funariaceae); cis-12-Oxo-phytodienoic acid; iso-12-Oxo-phytodienoic acid.