Molecules 2010, 15(12), 8641-8688; doi:10.3390/molecules15118641
Review

Supramolecular Self-Assembled Chaos: Polyphenolic Lignin’s Barrier to Cost-Effective Lignocellulosic Biofuels

1 Joint BioEnergy Institute (JBEI), Emeryville, CA 94550, USA 2 Sandia National Laboratories, Albuquerque, NM 87185, USA 3 Biology Department, Northern New Mexico College, Espanola, NM 87532, USA 4 Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA 5 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
(This article belongs to the Special Issue Phenolics and Polyphenolics)
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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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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.

AMA Style

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.

Chicago/Turabian Style

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.

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