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Title: The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers

Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H) and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10 and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid state NMR spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions formore » the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.« less
Authors:
 [1] ;  [1] ;  [2] ;  [1]
  1. National Renewable Energy Lab. (NREL), Golden, CO (United States). Biosciences Center and Bioenergy Science Center
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)
Publication Date:
Report Number(s):
NREL/JA-5100-68785
Journal ID: ISSN 1754-6834
Grant/Contract Number:
AC36-08GO28308; AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Biotechnology for Biofuels
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 1754-6834
Publisher:
BioMed Central
Research Org:
National Renewable Energy Lab. (NREL), Golden, CO (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC), Office of Biological and Environmental Research; USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; lignin; dehydrogenation polymer; coumaryl alcohol; biomass recalcitrance
OSTI Identifier:
1413907
Alternate Identifier(s):
OSTI ID: 1460174

Harman-Ware, Anne E., Happs, Renee M., Davison, Brian H., and Davis, Mark F.. The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers. United States: N. p., Web. doi:10.1186/s13068-017-0962-2.
Harman-Ware, Anne E., Happs, Renee M., Davison, Brian H., & Davis, Mark F.. The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers. United States. doi:10.1186/s13068-017-0962-2.
Harman-Ware, Anne E., Happs, Renee M., Davison, Brian H., and Davis, Mark F.. 2017. "The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers". United States. doi:10.1186/s13068-017-0962-2. https://www.osti.gov/servlets/purl/1413907.
@article{osti_1413907,
title = {The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers},
author = {Harman-Ware, Anne E. and Happs, Renee M. and Davison, Brian H. and Davis, Mark F.},
abstractNote = {Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processes. Here, DHPs were synthesized using a Zutropfverfahren method with horseradish peroxidase and three lignin monomers, sinapyl (S), coumaryl (H) and coniferyl (G) alcohols, in the presence of hydrogen peroxide. The H monomer was reacted with G and a 1:1 molar mixture of S:G monomers at H molar compositions of 0, 5, 10 and 20 mol% to study how the presence of the H monomer affected the structure and composition of the recovered polymers. At low H concentrations, solid state NMR spectra suggest that the H and G monomers interact to form G:H polymers that have a lower average molecular weight than the solely G-based polymer or the G:H polymer produced at higher H concentrations. Solid-state NMR and pyrolysis-MBMS analyses suggest that at higher H concentrations, the H monomer primarily self-polymerizes to produce clusters of H-based polymer that are segregated from clusters of G- or S:G-based polymers. Thioacidolysis generally showed higher recoveries of thioethylated products from S:G or S:G:H polymers made with higher H content, indicating an increase in the linear ether linkages. Overall, the experimental results support theoretical predictions for the reactivity and structural influences of the H monomer on the formation of lignin-like polymers.},
doi = {10.1186/s13068-017-0962-2},
journal = {Biotechnology for Biofuels},
number = 1,
volume = 10,
place = {United States},
year = {2017},
month = {11}
}

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