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Molecules 2018, 23(11), 2734; https://doi.org/10.3390/molecules23112734

A Metabolomic and HPLC-MS/MS Analysis of the Foliar Phenolics, Flavonoids and Coumarins of the Fraxinus Species Resistant and Susceptible to Emerald Ash Borer

1
Natural Resources Canada, Canadian Forest Service, Great Lake Forestry Centre, Sault Ste. Marie, ON P6A 2E5, Canada
2
Department of Chemical and Biochemical Engineering, University of Western Ontario, London, ON N6A 5B9, Canada
*
Author to whom correspondence should be addressed.
Received: 4 October 2018 / Revised: 15 October 2018 / Accepted: 20 October 2018 / Published: 23 October 2018
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Abstract

The Emerald Ash Borer (EAB), Agrilus planipennis, Fairmaire, an Asian invasive alien buprestid has devastated tens of millions of ash trees (Fraxinus spp.) in North America. Foliar phytochemicals of the genus Fraxinus (Oleaceae): Fraxinus pennsylvanica (Green ash), F. americana (White ash), F. profunda (Bush) Bush. (Pumpkin ash), F. quadrangulata Michx. (Blue ash), F. nigra Marsh. (Black ash) and F. mandshurica (Manchurian ash) were investigated using HPLC-MS/MS and untargeted metabolomics. HPLC-MS/MS help identified 26 compounds, including phenolics, flavonoids and coumarins in varying amounts. Hydroxycoumarins, esculetin, esculin, fraxetin, fraxin, fraxidin and scopoletin were isolated from blue, black and Manchurian ashes. High-throughput metabolomics revealed 35 metabolites, including terpenes, secoiridoids and lignans. Metabolomic profiling indicated several upregulated putative compounds from Manchurian ash, especially fraxinol, ligstroside, oleuropin, matairesinol, pinoresinol glucoside, 8-hydroxypinoresinol-4-glucoside, verbenalin, hydroxytyrosol-1-O-glucoside, totarol and ar-artemisene. Further, dicyclomine, aphidicolin, parthenolide, famciclovir, ar-turmerone and myriocin were identified upregulated in blue ash. Principal component analysis demonstrated a clear separation between Manchurian and blue ashes from black, green, white and pumpkin ashes. The presence of defensive compounds upregulated in Manchurian ash, suggests their potential role in providing constitutive resistance to EAB, and reflects its co-evolutionary history with A. planipennis, where they appear to coexist in their native habitats. View Full-Text
Keywords: Emerald Ash Borer (Agrilus planipennis); HPLC-MS/MS; metabolomics; Fraxinus spp. phenolics; flavonoids; coumarins; lignans; secoiridoids; invasive species Emerald Ash Borer (Agrilus planipennis); HPLC-MS/MS; metabolomics; Fraxinus spp. phenolics; flavonoids; coumarins; lignans; secoiridoids; invasive species
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited (CC BY 4.0).
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Qazi, S.S.; Lombardo, D.A.; Abou-Zaid, M.M. A Metabolomic and HPLC-MS/MS Analysis of the Foliar Phenolics, Flavonoids and Coumarins of the Fraxinus Species Resistant and Susceptible to Emerald Ash Borer. Molecules 2018, 23, 2734.

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