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J Phys Chem Lett. 2015 Jan 2;6(1):206-11. doi: 10.1021/jz502298q. Epub 2014 Dec 24.

Supramolecular Interactions in Secondary Plant Cell Walls: Effect of Lignin Chemical Composition Revealed with the Molecular Theory of Solvation.

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†National Institute for Nanotechnology, 11421 Saskatchewan Drive NW, Edmonton, Alberta T6G 2M9, Canada.
‡Institute of Chemistry, University of Campinas, Caixa Postal 6154, Campinas CEP 13083-970, São Paulo, Brazil.
§Department of Mechanical Engineering, University of Alberta, 4-9 Mechanical Engineering Building, Edmonton T6G 2G8, Alberta, Canada.
∥Department of Chemical and Materials Engineering, University of Alberta, 9107 - 116 Street, Edmonton T6G 2V4, Alberta, Canada.


Plant biomass recalcitrance, a major obstacle to achieving sustainable production of second generation biofuels, arises mainly from the amorphous cell-wall matrix containing lignin and hemicellulose assembled into a complex supramolecular network that coats the cellulose fibrils. We employed the statistical-mechanical, 3D reference interaction site model with the Kovalenko-Hirata closure approximation (or 3D-RISM-KH molecular theory of solvation) to reveal the supramolecular interactions in this network and provide molecular-level insight into the effective lignin-lignin and lignin-hemicellulose thermodynamic interactions. We found that such interactions are hydrophobic and entropy-driven, and arise from the expelling of water from the mutual interaction surfaces. The molecular origin of these interactions is carbohydrate-π and π-π stacking forces, whose strengths are dependent on the lignin chemical composition. Methoxy substituents in the phenyl groups of lignin promote substantial entropic stabilization of the ligno-hemicellulosic matrix. Our results provide a detailed molecular view of the fundamental interactions within the secondary plant cell walls that lead to recalcitrance.


3D-RISM-KH molecular theory of solvation; biofuel; hemicellulose; hydrophobic interactions; plant biomass recalcitrance; solvation free energy

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