Five French ferns belonging to different families were investigated for volatile organic compounds (VOC) by GC-MS using organic solvent extraction. Fifty-five VOC biosynthesized from the shikimic, lipidic and terpenic pathways including monoterpenes, sesquiterpenes and carotenoid-type compounds were identified. The main volatile compound of Adiantum capillus-veneris L. (Pteridaceae) was (E)-2-decenal with a plastic or "stink bug" odor. The volatile profiles of Athyrium filixfemina (L.) Roth (Woodsiaceae) and Blechnum spicant (L.) Roth (Blechnaceae) showed similarities, with small amounts of isoprenoids and the same main volatile compounds, i.e., 2-phenylethanal (odor of lilac and hyacinth) and 1-octen-3-ol (mushroom-like odor). The main volatile compound of Dryopteris filix-mas (L.) Schott (Dryopteridaceae) was (E)-nerolidol with a woody or fresh bark note. Polyketides, as acylfilicinic acids, were mainly identified in this fern. Oreopteris limbosperma (Bellardi ex. All.) J. Holub (Thelypteridaceae), well-known for its lemon smell, contained the highest biodiversity of VOC. Eighty percent of the volatiles was issued from the terpenic pathway. The main volatiles were (E)-nerolidol, α-terpineol, β-caryophyllene and other minor monoterpenes (for example, linalool, pinenes, limonene, and γ-terpinen-7-al). It was also the fern with the highest number of carotenoid-type derivatives, which were identified in large amounts. Our results were of great interest underlying new industrial valorisation for ferns based on their broad spectrum of volatiles.
Twelve French Asplenioideae ferns (genera Asplenium and subgenera Ceterach and Phyllitis) were investigated for the first time for volatile organic compounds (VOC) using GC-MS. Sixty-two VOC biosynthesized from the lipidic, shikimic, terpenic and carotenoid pathways were identified. Several VOC profiles can be highlighted from Asplenium jahandiezii and A. ×alternifolium with exclusively lipidic derivatives to A. onopteris with an equal ratio of lipidic/shikimic compounds. Very few terpenes as caryophyllene derivatives were identified, but only in A. obovatum subsp. bilotii. The main odorous lipidic derivatives were (E)-2-decenal (waxy and fatty odor), nonanal (aldehydic and waxy odor with a fresh green nuance), (E)-2-heptenal (green odor with a fatty note) and 1-octen-3-ol (mushroom-like odor), reported for all species. A few VOC are present in several species in high content, i.e., 9-oxononanoic acid used as a precursor for biopolymers (19% in A. jahandiezii), 4-hydroxyacetophenone with a sweet and heavy floral odor (17.1% in A. onopteris), and 4-hydroxybenzoic acid used as a precursor in the synthesis of parabens (11.3% in A. foreziense). Most of the identified compounds have pharmacological activities, i.e., octanoic acid as antimicrobial, in particular against Salmonellas, with fatty and waxy odor (41.1% in A. petrarchae), tetradecanoic acid with trypanocidal activity (13.3% in A. obovatum subsp. bilotii), 4-hydroxybenzoic acid (8.7% in A. onopteris) with antimicrobial and anti-aging effects, 3,4-dihydroxybenzaldehyde as an inhibitor of growth of human cancer cells (6.7% in Ceterach officinarum), and phenylacetic acid with antifungal and antibacterial activities (5.8% in A. onopteris). Propionylfilicinic acid was identified in the twelve species. The broad spectrum of odorous and bioactive VOC identified from the Asplenium, Ceterach and Phyllitis species are indeed of great interest to the cosmetic and food industries.
Six horsetails were investigated for volatile organic compounds (VOC) by GC-MS using organic solvent extraction. Seventy-five VOC biosynthesized from the shikimic, lipidic and terpenic pathways including isoprenoid derivatives were detected from these putative natural resources. E. palustre var. americana contained mainly lipidic derivatives, i.e., 1-octen-3-ol (mushroom-like odor), (E)-2-hexenoic acid (fruity odor) and (E)-2-hexenal (green odor). Many isoprenoid flavour precursors, i.e., 3-oxo--ionol (spicy odor) and (E,E)-pseudoionone (balsamic odor), as well as odorous benzenic derivatives, i.e, phenylethanal (hyacinth, lilac note) and 2-phenylethanol (rose odor) contributed to the odor of E. arvense. The volatile pattern of E. telmateia is dominated by high amounts of isoprenoids and benzenic derivatives. The complex volatile profiles of E. hyemale and E. ramosissimum are based on ferulic acid isomers, along with either (E)-2-heptenal (green vegetable-like odor) or 4-vinylguaiacol (spicy clove smoky odor) for E. hyemale and E. ramosissimum, respectively. The broad spectrum of E. scirpioides shows the lowest VOC content with high amount of isoprenoids (46.9%), mainly ionone derivatives. Equisetum resources are of great interest as bioactive litter and new potential functional feed ingredients.
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