Supramolecular self-assembled chaos: polyphenolic lignin's barrier to cost-effective lignocellulosic biofuels.
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.
Joint BioEnergy Institute, Emeryville, CA 94550, USA. kachyut@sandia.gov
Komandoor Elayavalli
KE
Achyuthan
Ann Mary
AM
Achyuthan
Paul David
PD
Adams
Shawn Matthew
SM
Dirk
Jason Carl
JC
Harper
Blake Alexander
BA
Simmons
Anup Kumar
AK
Singh
D056804:Biofuels / Q000191:economics*; D018533:Biomass; D002473:Cell Wall / Q000737:chemistry / Q000378:metabolism; D005419:Flavonoids / Q000737:chemistry* / Q000378:metabolism; D008031:Lignin / Q000737:chemistry* / Q000378:metabolism; D010636:Phenols / Q000737:chemistry* / Q000378:metabolism; D010944:Plants / Q000737:chemistry* / Q000378:metabolism; D059808:Polyphenols; D020005:Propanols / Q000737:chemistry* / Q000378:metabolism
D056804:Biofuels; D005419:Flavonoids; D010636:Phenols; D059808:Polyphenols; D020005:Propanols; C439395:1-phenylpropanol; D008031:Lignin