Lignin phenols derivatives in lichens

Abstract

Lignin monophenols have been measured in the cupric oxide oxidation products from lichens of different systematic groups. It is shown for the first time that syringyl structures in most lichens strongly dominate over vanillyl and p-hydroxyl ones (S/V 7-583, S/P 3-30). This distinguishes lichens from algae and mosses (p-hydroxyl phenols are dominant) and from higher plants (S/V ratios are from 0 in gymnosperms to 1.1-5.2 in angiosperms). Molecular ratios of phenols as well as the ratios of acids to aldehydes in lichens were different from lignin of higher plants, suggesting contribution of non-lignin phenols in CuO oxidation products. The contents of syringyl and vanillyl phenols in some lichen species were comparable to non-woody tissues of higher plants. Results of the study suggest that lichens can be important source of aromatic structures in soils and hydrosphere, particularly in the regions were lichens are abundant.

Water‐soluble phenolic metabolites in lichens and their potential role in soil organic matter formation at the pre‐vascular stage

“…Soluble syringyl structures (acids, aldehydes and ketones) in lichens generally dominate over vanillyl and even over p ‐hydroxyl types (Table ). This confirms the trends reported earlier by Zavarzina et al () and distinguishes lichens from other primary producers that colonize soil. The p ‐hydroxybenzoic structures predominate in algae and mosses, whereas vanillyl and hydroxycinnamyl structures are abundant in vascular plants (Hedges & Mann, ).…”

“…The p-hydroxybenzoic structures predominate in algae and mosses, whereas vanillyl and hydroxycinnamyl structures are abundant in vascular plants (Hedges & Mann, 1979). The contents of watersoluble S-and V-type monophenols in lichens (this study) were three to four orders of magnitude less than their total amount in lichen tissues (Zavarzina et al, 2015), suggesting that the majority of these compounds in lichens occurs in a water-insoluble form. Among soluble PCs identified in lichens, syringic, vanillic, protocatechuic and caffeic acids, as well as S-and V-type aldehydes and ketones, are readily oxidized by phenoloxidases and undergo oligomerization and polymerization (Canas & Camarero, 2010;Canfora et al, 2008).…”

“…With thin layer chromatography, we found that lichens contain water‐soluble phenolic metabolites, including conjugates of p ‐hydroxybenzoic, vanillic and protocatechuic acids, which can be leached out by water from intact lichen thalli (Zagoskina, Nikolaeva, Lapshin, Zavarzin, & Zavarzina, ). More recently, a group of phenolic acids, aldehydes and ketones of p‐ hydroxyl, vanillyl and syringyl type (so‐called lignin monophenols) were detected in lichens after oxidation of their tissue with CuO (Zavarzina et al, ). Compounds with methoxy‐groups and o ‐diphenols, detected in lichens, are known for their strong reactivities in adsorption reactions (Zavarzina et al, ) and oxidative coupling in the presence of both biotic (Canfora, Iamarino, Rao, & Gianfreda, ; Zavarzina, ) and abiotic catalysts (Huang & Hardie, ).…”

Symbiotic Interplay of Fungi, Algae, and Bacteria within the Lung Lichen Lobaria pulmonaria L. Hoffm. as Assessed by State-of-the-Art Metaproteomics

“…We suggest that methanol or other C1-compounds might result from the metabolism/catabolism of secondary phenolic products that are synthesized by the mycobiont. Lichens and seeds often produce secondary phenolic compounds with antioxidative properties, including lignin phenol derivatives with antioxidant activities . It was shown recently that methyl- or methanotrophic bacteria are associated with plants because of their emission of methanol or methane .…”

“…Lichens and seeds often produce secondary phenolic compounds with antioxidative properties, 57 including lignin phenol derivatives with antioxidant activities. 58 It was shown recently that methyl-or methanotrophic bacteria are associated with plants because of their emission of methanol or methane. 59 Furthermore, in the case of the Darß sample, wet moors, which surround the sampling site and emit methanol/ methane, might explain the presence of such methyl-/ methanotrophic bacteria.…”