title: Synthesis, metabolism and systemic transport of a fluorinated mimic of the endogenous jasmonate precursor OPC-8:0.
abstract: Jasmonates (JAs) are fatty acid derivatives that mediate many developmental processes and stress responses in plants. Synthetic jasmonate derivatives (commonly isotopically labeled), which mimic the action of the endogenous compounds are often employed as internal standards or probes to study metabolic processes. However, stable-isotope labeling of jasmonates does not allow the study of spatial and temporal distribution of these compounds in real time by positron emission tomography (PET). In this study, we explore whether a fluorinated jasmonate could mimic the action of the endogenous compound and therefore, be later employed as a tracer to study metabolic processes by PET. We describe the synthesis and the metabolism of (Z)-7-fluoro-8-(3-oxo-2-(pent-2-en-1-yl)cyclopentyl)octanoic acid (7F-OPC-8:0), a fluorinated analog of the JA precursor OPC-8:0. Like endogenous jasmonates, 7F-OPC-8:0 induces the transcription of marker jasmonate responsive genes (JRG) and the accumulation of jasmonates after its application to Arabidopsis thaliana plants. By using UHPLC-MS/MS, we could show that 7F-OPC-8:0 is metabolized in vivo similarly to the endogenous OPC-8:0. Furthermore, the fluorinated analog was successfully employed as a probe to show its translocation to undamaged systemic leaves when it was applied to wounded leaves. This result suggests that OPC-8:0 - and maybe other oxylipins - may contribute to the mobile signal which triggers systemic defense responses in plants. We highlight the potential of fluorinated oxylipins to study the mode of action of lipid-derived molecules in planta, either by conventional analytical methods or fluorine-based detection techniques.
authors.affiliation: Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Hans-Knöll-Straße 8, 07745 Jena, Germany.
authors.forename: Guillermo H
authors.initials: GH
authors.lastname: Jimenez-Aleman
authors.affiliation: Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Hans-Knöll-Straße 8, 07745 Jena, Germany.
authors.forename: Sandra S
authors.initials: SS
authors.lastname: Scholz
authors.affiliation: Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Hans-Knöll-Straße 8, 07745 Jena, Germany.
authors.forename: Monika
authors.initials: M
authors.lastname: Heyer
authors.affiliation: Department of Biochemistry, Max Planck Institute for Chemical Ecology, Hans-Knöll-Straße 8, 07745 Jena, Germany.
authors.forename: Michael
authors.initials: M
authors.lastname: Reichelt
authors.affiliation: Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Hans-Knöll-Straße 8, 07745 Jena, Germany.
authors.forename: Axel
authors.initials: A
authors.lastname: Mithöfer
authors.affiliation: Department of Bioorganic Chemistry, Max Planck Institute for Chemical Ecology, Hans-Knöll-Straße 8, 07745 Jena, Germany. Electronic address: boland@ice.mpg.de.
authors.forename: Wilhelm
authors.initials: W
authors.lastname: Boland
mesh_terms: D017360:Arabidopsis / Q000378:metabolism*; D040761:Biomimetic Materials / Q000378:metabolism / Q000494:pharmacology*; D002210:Caprylates / Q000378:metabolism*; D003517:Cyclopentanes / Q000378:metabolism*; D006845:Hydrocarbons, Fluorinated / Q000378:metabolism / Q000494:pharmacology*; D054883:Oxylipins / Q000378:metabolism*; D018515:Plant Leaves / Q000378:metabolism*
chemical_list: C483358:8-(3-oxo-2-cis-((Z)-2-pentenyl)cyclopentyl)octanoic acid; D002210:Caprylates; D003517:Cyclopentanes; D006845:Hydrocarbons, Fluorinated; D054883:Oxylipins; C011006:jasmonic acid
keywords: Arabidopsis thaliana; Fatty acid metabolism; JA-biosynthesis; Jasmonate; Signal translocation; Systemic response; UHPLC–MS