Analysis of lignin-carbohydrate and lignin-lignin linkages after hydrolase treatment of xylan-lignin, glucomannan-lignin and glucan-lignin complexes from spruce wood

KTH, Träkemi och massateknologi 2014

Du, Xueyu
Perez-Boada, Marta
Fernandez, Carmen
Rencoret, Jorge
del Rio, Jose C.
Jimenez-Barbero, Jesus
Li, Jiebing
Gutierrez, Ana
Martinez, Angel T.

Xylan-lignin (XL), glucomannan-lignin (GML) and glucan-lignin (GL) complexes were isolated from spruce wood, hydrolyzed with xylanase or endoglucanase/beta-glucosidase, and analyzed by analytical pyrolysis and 2D-NMR. The enzymatic hydrolysis removed most of the polysaccharide moieties in the complexes, and the lignin content and relative abundance of lignin-carbohydrate linkages increased. Analytical pyrolysis confirmed the action of the enzymatic hydrolysis, with strong decreases of levoglucosane and other carbohydrate-derived products. Unexpectedly it also revealed that the hydrolase treatment alters the pattern of lignin breakdown products, resulting in higher amounts of coniferyl alcohol. From the anomeric carbohydrate signals in the 2D-NMR spectra, phenyl glycoside linkages (undetectable in the original complexes) could be identified in the hydrolyzed GML complex. Lower amounts of glucuronosyl and benzyl ether linkages were also observed after the hydrolysis. From the 2D-NMR spectra of the hydrolyzed complexes, it was concluded that the lignin in GML is less condensed than in XL due to its higher content in beta-O-4' ether substructures (62 % of side chains in GML vs 53 % in XL) accompanied by more coniferyl alcohol end units (16 vs 13 %). In contrast, the XL lignin has more pinoresinols (11 vs 6 %) and dibenzodioxocins (9 vs 2 %) than the GML (and both have similar to 13 % phenylcoumarans and 1 % spirodienones). Direct 2D-NMR analysis of the hydrolyzed GL complex was not possible due to its low solubility. However, after sample acetylation, an even less condensed lignin than in the GML complex was found (with up to 72 % beta-O-4' substructures and only 1 % pinoresinols). The study provides evidence for the existence of structurally different lignins associated to hemicelluloses (xylan and glucomannan) and cellulose in spruce wood and, at the same time, offers information on some of the chemical linkages between the above polymers.
QC 20140604

Spruce wood; Picea abies; Lignin-carbohydrate complexes (LCCs); Enzymatic hydrolysis; Analytical pyrolysis; 2D-NMR; Lignin structure; Paper, Pulp and Fiber Technology; Pappers-, massa- och fiberteknik; Article in journal; info:eu-repo/semantics/article; text

10.1007.s00425-014-2037-y

English

UPE oai:DiVA.org:kth-145819
0000-0002-4521-1122
doi:10.1007/s00425-014-2037-y
PMID 24531838
ISI:000335158700012
Scopus 2-s2.0-84921437885
1234999348

UPPSALA UNIV LIBR
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