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Spatial mapping of lichen specialized metabolites using LDI-MSI: chemical ecology issues for Ophioparma ventosa

View Article: PubMed Central - PubMed

ABSTRACT

Imaging mass spectrometry techniques have become a powerful strategy to assess the spatial distribution of metabolites in biological systems. Based on auto-ionisability of lichen metabolites using LDI-MS, we herein image the distribution of major secondary metabolites (specialized metabolites) from the lichen Ophioparma ventosa by LDI-MSI (Mass Spectrometry Imaging). Such technologies offer tremendous opportunities to discuss the role of natural products through spatial mapping, their distribution patterns being consistent with previous chemical ecology reports. A special attention was dedicated to miriquidic acid, an unexpected molecule we first reported in Ophioparma ventosa. The analytical strategy presented herein offers new perspectives to access the sharp distribution of lichen metabolites from regular razor blade-sectioned slices.

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Molecular images of naphthazarine pigments in the Tyrol sample of Ophioparma ventosa (A): haemoventosin m/z 304 and (B): 4-hydroxyhaemoventosin m/z 320). Intensities of ions in the imaged spots are color coded using a heat map with relative intensities given as indicated on the color scale bars.
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f6: Molecular images of naphthazarine pigments in the Tyrol sample of Ophioparma ventosa (A): haemoventosin m/z 304 and (B): 4-hydroxyhaemoventosin m/z 320). Intensities of ions in the imaged spots are color coded using a heat map with relative intensities given as indicated on the color scale bars.

Mentions: Haemoventosin was localized in the red epihymenial layer. While this molecule remains the major pigment of the fruiting bodies, we recently isolated a variety of minor pyranonaphthoquinones from the apothecia of O. ventosa10. Their trace amounts limited their imaging but 4-hydroxyhaemoventosin could be ascribed to the red epihymenial layer, thus being co-localized with haemoventosin (Fig. 6). Usnic acid is densely distributed above the Trebouxia photobiont layer and along internal furrows. Thamnolic acid is confined to the hypothecium and upper medulla parts of the lichen, associated with faint pink-colored patches. At last, divaricatic and miriquidic acids are allocated to the lower medulla of the lichen extending downwards to the lichen/rock interface. Molecular images acquired from samples not displaying miriquidic acid in both Tyrol and Styria lichens are presented in Figures S4 and S5.


Spatial mapping of lichen specialized metabolites using LDI-MSI: chemical ecology issues for Ophioparma ventosa
Molecular images of naphthazarine pigments in the Tyrol sample of Ophioparma ventosa (A): haemoventosin m/z 304 and (B): 4-hydroxyhaemoventosin m/z 320). Intensities of ions in the imaged spots are color coded using a heat map with relative intensities given as indicated on the color scale bars.
© Copyright Policy - open-access
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC5121634&req=5

f6: Molecular images of naphthazarine pigments in the Tyrol sample of Ophioparma ventosa (A): haemoventosin m/z 304 and (B): 4-hydroxyhaemoventosin m/z 320). Intensities of ions in the imaged spots are color coded using a heat map with relative intensities given as indicated on the color scale bars.
Mentions: Haemoventosin was localized in the red epihymenial layer. While this molecule remains the major pigment of the fruiting bodies, we recently isolated a variety of minor pyranonaphthoquinones from the apothecia of O. ventosa10. Their trace amounts limited their imaging but 4-hydroxyhaemoventosin could be ascribed to the red epihymenial layer, thus being co-localized with haemoventosin (Fig. 6). Usnic acid is densely distributed above the Trebouxia photobiont layer and along internal furrows. Thamnolic acid is confined to the hypothecium and upper medulla parts of the lichen, associated with faint pink-colored patches. At last, divaricatic and miriquidic acids are allocated to the lower medulla of the lichen extending downwards to the lichen/rock interface. Molecular images acquired from samples not displaying miriquidic acid in both Tyrol and Styria lichens are presented in Figures S4 and S5.

View Article: PubMed Central - PubMed

ABSTRACT

Imaging mass spectrometry techniques have become a powerful strategy to assess the spatial distribution of metabolites in biological systems. Based on auto-ionisability of lichen metabolites using LDI-MS, we herein image the distribution of major secondary metabolites (specialized metabolites) from the lichen Ophioparma ventosa by LDI-MSI (Mass Spectrometry Imaging). Such technologies offer tremendous opportunities to discuss the role of natural products through spatial mapping, their distribution patterns being consistent with previous chemical ecology reports. A special attention was dedicated to miriquidic acid, an unexpected molecule we first reported in Ophioparma ventosa. The analytical strategy presented herein offers new perspectives to access the sharp distribution of lichen metabolites from regular razor blade-sectioned slices.

No MeSH data available.


Related in: MedlinePlus