Carbohydrate-aromatic interface and molecular architecture of lignocellulose

Kirui, Alex; Zhao, Wancheng; Deligey, Fabien; Yang, Hui; Kang, Xue; Mentink-Vigier, Frederic; Wang, Tuo

doi:10.1038/s41467-022-28165-3

Title: Carbohydrate-aromatic interface and molecular architecture of lignocellulose

Journal Article · 26 January 2022 · Nature Communications

DOI: https://doi.org/10.1038/s41467-022-28165-3 · OSTI ID:1842379

; Zhao, Wancheng; Deligey, Fabien;

; Kang, Xue;

;

Abstract Plant cell walls constitute the majority of lignocellulosic biomass and serve as a renewable resource of biomaterials and biofuel. Extensive interactions between polysaccharides and the aromatic polymer lignin make lignocellulose recalcitrant to enzymatic hydrolysis, but this polymer network remains poorly understood. Here we interrogate the nanoscale assembly of lignocellulosic components in plant stems using solid-state nuclear magnetic resonance and dynamic nuclear polarization approaches. We show that the extent of glycan-aromatic association increases sequentially across grasses, hardwoods, and softwoods. Lignin principally packs with the xylan in a non-flat conformation via non-covalent interactions and partially binds the junction of flat-ribbon xylan and cellulose surface as a secondary site. All molecules are homogeneously mixed in softwoods; this unique feature enables water retention even around the hydrophobic aromatics. These findings unveil the principles of polymer interactions underlying the heterogeneous architecture of lignocellulose, which may guide the rational design of more digestible plants and more efficient biomass-conversion pathways.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Lignocellulose Structure and Formation; Louisiana State Univ., Baton Rouge, LA (United States); Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Science Foundation (NSF); State of Florida; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001090; SC0021210; SC0021314

OSTI ID:: 1842379

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 13; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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