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Spruce milled wood lignin: Linear, branched or cross-linked?
Aalto University, Finland.
RISE Research Institutes of Sweden, Bioeconomy and Health, Biorefinery and Energy.ORCID iD: 0000-0001-6495-0492
Aalto University, Finland; Chinese Academy of Sciences, China.
BOKU University of Natural Resources and Life Sciences, Austria.
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2020 (English)In: Green Chemistry, ISSN 1463-9262, E-ISSN 1463-9270, Vol. 22, no 13, p. 3985-4001Article in journal (Refereed) Published
Abstract [en]

The subject of lignin structure, critical for fundamental and practical reasons, is addressed in this study that includes a review of the methods applied to elucidate macromolecular branching. The recently available approaches for determination of the absolute molecular mass of spruce milled wood lignin (MWL) along with the quantification of terminal groups clearly indicate that MWL is significantly branched and cross-linked (with ∼36% lignin units partaking in these linkages). Results from independent methods imply that about half of the branching and crosslinking linkages involve aromatic rings, predominantly 5-5′ etherified units; meanwhile, a significant number of linkages are located in the side chains. Quantitative 13C NMR analyses suggest that the branches involve different aliphatic ether (alkyl-O-alkyl) types at the α- and γ-positions of the side chain, with intact β-O-4 linkages. While the exact structures of these moieties require further investigation, our results point to the fact that conventional lignification theory disagrees with the presence of such key moieties in softwood MWL and the observed high degree of branching/crosslinking. Potential reasons for the noted discrepancies are discussed.

Place, publisher, year, edition, pages
Royal Society of Chemistry , 2020. Vol. 22, no 13, p. 3985-4001
Keywords [en]
Lignin, Aliphatic ethers, Aromatic rings, Degree of branching, Lignin structure, Lignin units, Milled wood lignin, Side-chains, Terminal groups, Wood, Chains, Joints, Lignins, Methods, Rings, Sides, Structures
National Category
Natural Sciences
Identifiers
URN: urn:nbn:se:ri:diva-45615DOI: 10.1039/d0gc00926aScopus ID: 2-s2.0-85087700987OAI: oai:DiVA.org:ri-45615DiVA, id: diva2:1458069
Note

Funding details: Academy of Finland, 318891, 318890; Funding text 1: This is supported by detailed analysis of 2D NMR spectra of spruce MWL. There are some signals which surprisingly have not been considered until now in spite of the extensive work on the characterization of native lignins. We assign these signals based on the data available in the literature33–40 and ChemDraw modeling of some hypothetical moieties when the literature data are lacking. This analysis indicates that significant signal overlap is plausible even in the 2D spectrum (Fig. 8). γ-Methylene (CH2) signals of potential γ-ether moieties; Funding text 2: The authors are grateful to Dr J. Ralph for valuable discussion. We are also grateful for support by the Academy of Finland’s Flagship Programme under Projects No. 318890 and 318891 (Competence Center for Materials Bioeconomy, FinnCERES) and the Austrian Biorefinery Center Tulln (ABCT).

Available from: 2020-08-13 Created: 2020-08-13 Last updated: 2021-11-25Bibliographically approved

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Capanema, Ewellyn

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