Structural Investigation of Lignins in Three Different Ferns (Pteridopbytes)

This paper examines the structural characteristics of fern lignins (deer fern (Blechnum spicant), sword fern (Polystichum munitum) and maidenhair fern (Adiantum pedatum)) by chemical degradation methods of thioacidolysis and nitrobenzene oxidation as well as 13C NMR. Phloroglucinol-HCI staining indicates that the lignins are specifically accumulated at the sclerenchyma cells beneath the epidermis and vascular bundles. The fern lignins consist of only guaiacyl units. Remarkably, the frequency of the -O-4 linkages is extremely low in fern lignins (only 9 to 11 %). Furthermore, the presence of lignin is ambiguous in maidenhair fern, due to very rare amount of -O-4 linkage. Biphenyl (5-5) and 1,2 bis arylpropane (-1) are main condensed dimeric substructures in fern lignins over 70%. In addition, 13C NMR analysis strongly evidenced the integration of phenolics or their derivatives into the fern lignins.