Supramolecular Interactions in Secondary Plant Cell Walls: Effect of Lignin Chemical Composition Revealed with the Molecular Theory of Solvation
Full text
| |
| Author(s): |
Silveira, Rodrigo L.
[1, 2]
;
Stoyanov, Stanislav R.
[2, 3, 4]
;
Gusarov, Sergey
[2]
;
Skaf, Munir S.
[1]
;
Kovalenko, Andriy
[2, 3]
Total Authors: 5
|
| Affiliation: | [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
Total Affiliations: 4
|
| Document type: | Journal article |
| Source: | Journal of Physical Chemistry Letters; v. 6, n. 1, p. 206-211, JAN 1 2015. |
| Web of Science Citations: | 29 |
| Abstract | |
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) | |
| FAPESP's process: | 14/10448-1 - Molecular aspects of plant cell wall architecture |
| Grantee: | Rodrigo Leandro Silveira |
| Support type: | Scholarships in Brazil - Post-Doctorate |
| FAPESP's process: | 13/08293-7 - CCES - Center for Computational Engineering and Sciences |
| Grantee: | Munir Salomao Skaf |
| Support type: | Research Grants - Research, Innovation and Dissemination Centers - RIDC |