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

Autor(es)

Silveira, Rodrigo L. ^{[1, 2]} ; Stoyanov, Stanislav R. ^{[2, 3, 4]} ; Gusarov, Sergey ^[2] ; Skaf, Munir S. ^[1] ; Kovalenko, Andriy ^{[2, 3]}

Afiliação do(s) autor(es)

^[1] Univ Estadual Campinas, Inst Chem, BR-13083970 Sao Paulo - Brazil

^[2] Natl Inst Nanotechnol, Edmonton, AB T6G 2M9 - Canada

^[3] Univ Alberta, Dept Chem & Mat Engn, Edmonton, AB T6G 2V4 - Canada

^[4] Univ Alberta, Dept Mech Engn, Edmonton, AB T6G 2G8 - Canada

• Tipo de documento: Artigo Científico
• Fonte: Journal of Physical Chemistry Letters; v. 6, n. 1, p. 206-211, JAN 1 2015.
• Citações Web of Science: 28

Resumo

Plant biomass recalcitrance, a major obstacle to achieving sustainable production of second generation biofiiels, 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-pi and pi-pi 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. (AU)

• Processo FAPESP: 13/08293-7 - CECC - Centro de Engenharia e Ciências Computacionais
• Beneficiário: Munir Salomao Skaf
• Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
• Processo FAPESP: 14/10448-1 - Aspectos moleculares da arquitetura de paredes celulares de plantas
• Beneficiário: Rodrigo Leandro Silveira
• Modalidade de apoio: Bolsas no Brasil - Pós-Doutorado