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Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels
Joint BioEnergy Institute (JBEI), Emeryville, CA 94550, USA
Sandia National Laboratories, Albuquerque, NM 87185, USA
Biology Department, Northern New Mexico College, Espanola, NM 87532, USA
Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
Sandia National Laboratories, Livermore, CA 94550, USA
* Author to whom correspondence should be addressed.
Received: 15 October 2010; in revised form: 22 November 2010 / Accepted: 25 November 2010 / Published: 29 November 2010
Abstract: Phenylpropanoid metabolism yields a mixture of monolignols that undergo chaotic, non-enzymatic reactions such as free radical polymerization and spontaneous self-assembly in order to form the polyphenolic lignin which is a barrier to cost-effective lignocellulosic biofuels. Post-synthesis lignin integration into the plant cell wall is unclear, including how the hydrophobic lignin incorporates into the wall in an initially hydrophilic milieu. Self-assembly, self-organization and aggregation give rise to a complex, 3D network of lignin that displays randomly branched topology and fractal properties. Attempts at isolating lignin, analogous to archaeology, are instantly destructive and non-representative of in planta. Lack of plant ligninases or enzymes that hydrolyze specific bonds in lignin-carbohydrate complexes (LCCs) also frustrate a better grasp of lignin. Supramolecular self-assembly, nano-mechanical properties of lignin-lignin, lignin-polysaccharide interactions and association-dissociation kinetics affect biomass deconstruction and thereby cost-effective biofuels production.
Keywords: lignin; supramolecular self-assembly; cell wall; deconstruction; enzymes; LCC; fractal; lignocellulosic biofuels
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Cite This Article
MDPI and ACS Style
Achyuthan, K.E.; Achyuthan, A.M.; Adams, P.D.; Dirk, S.M.; Harper, J.C.; Simmons, B.A.; Singh, A.K. Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels. Molecules 2010, 15, 8641-8688.
Achyuthan KE, Achyuthan AM, Adams PD, Dirk SM, Harper JC, Simmons BA, Singh AK. Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels. Molecules. 2010; 15(12):8641-8688.
Achyuthan, Komandoor Elayavalli; Achyuthan, Ann Mary; Adams, Paul David; Dirk, Shawn Matthew; Harper, Jason Carl; Simmons, Blake Alexander; Singh, Anup Kumar. 2010. "Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels." Molecules 15, no. 12: 8641-8688.