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

Abstract

Background: Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processesMethods: 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.Results: 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.Conclusions: 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:
; ; ;
Publication Date:
Research Org.:
National Renewable Energy Laboratory (NREL), Golden, CO (United States); Oak Ridge National Laboratory (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)
OSTI Identifier:
1618707
Alternate Identifier(s):
OSTI ID: 1413907; OSTI ID: 1460174
Report Number(s):
NREL/JA-5100-68785
Journal ID: ISSN 1754-6834; 281; PII: 962
Grant/Contract Number:  
AC36-08-GO28308; AC05-00OR22725; AC36-08GO28308
Resource Type:
Published Article
Journal Name:
Biotechnology for Biofuels
Additional Journal Information:
Journal Name: Biotechnology for Biofuels Journal Volume: 10 Journal Issue: 1; Journal ID: ISSN 1754-6834
Publisher:
Springer Science + Business Media
Country of Publication:
Netherlands
Language:
English
Subject:
09 BIOMASS FUELS; lignin; dehydrogenation polymer; coumaryl alcohol; biomass recalcitrance

Citation Formats

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. Netherlands: N. p., 2017. Web. doi:10.1186/s13068-017-0962-2.
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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. Netherlands. https://doi.org/10.1186/s13068-017-0962-2
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Harman-Ware, Anne E., Happs, Renee M., Davison, Brian H., and Davis, Mark F. Thu . "The effect of coumaryl alcohol incorporation on the structure and composition of lignin dehydrogenation polymers". Netherlands. https://doi.org/10.1186/s13068-017-0962-2.
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@article{osti_1618707,
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 = {Background: Lignin dehydrogenation polymers (DHPs) are polymers generated from phenolic precursors for the purpose of studying lignin structure and polymerization processesMethods: 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.Results: 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.Conclusions: 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 = {Netherlands},
year = {Thu Nov 30 00:00:00 EST 2017},
month = {Thu Nov 30 00:00:00 EST 2017}
}
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Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1186/s13068-017-0962-2
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Cited by: 19 works
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Figures / Tables:

Fig. 1 Fig. 1: Zutropfverfahren synthesis of lignin dehydrogenation polymers
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Works referenced in this record:

Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014

  • Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
  • Science, Vol. 344, Issue 6185, p. 1246843-1246843
  • DOI: 10.1126/science.1246843

A potential role for sinapyl p-coumarate as a radical transfer mechanism in grass lignin formation
journal, July 2008

Radical Coupling Reactions in Lignin Synthesis: A Density Functional Theory Study
journal, April 2012

  • Sangha, Amandeep K.; Parks, Jerry M.; Standaert, Robert F.
  • The Journal of Physical Chemistry B, Vol. 116, Issue 16
  • DOI: 10.1021/jp2122449

Quantitative Analysis of Detailed Lignin Monomer Composition by Pyrolysis-Gas Chromatography Combined with Preliminary Acetylation of the Samples
journal, November 2001

  • Sonoda, Tetsuya; Ona, Toshihiro; Yokoi, Hiroaki
  • Analytical Chemistry, Vol. 73, Issue 22
  • DOI: 10.1021/ac010557c

Impact of the Brown-Midrib bm 5 Mutation on Maize Lignins
journal, May 2014

  • Méchin, Valérie; Laluc, Aurélia; Legée, Frédéric
  • Journal of Agricultural and Food Chemistry, Vol. 62, Issue 22
  • DOI: 10.1021/jf5019998

Oxidative cross coupling of p-hydroxycinnamic alcohols with dimeric arylglycerol β-aryl ether lignin model compounds. The effect of oxidation potentials
journal, January 1998

  • Syrjänen, Kaisa; Brunow, Gösta
  • Journal of the Chemical Society, Perkin Transactions 1, Issue 20
  • DOI: 10.1039/a805349i

Polymerization of Monolignols by Redox Shuttle–Mediated Enzymatic Oxidation: A New Model in Lignin Biosynthesis I
journal, August 2002

  • Önnerud, Hans; Zhang, Liming; Gellerstedt, Göran
  • The Plant Cell, Vol. 14, Issue 8
  • DOI: 10.1105/tpc.001487

Parameters affecting in vitro monolignol couplings during dehydrogenative polymerization in the presence of peroxidase and H2O2
journal, June 2015

  • Hwang, Hyewon; Moon, Sun-Joo; Won, Keehoon
  • Journal of Industrial and Engineering Chemistry, Vol. 26
  • DOI: 10.1016/j.jiec.2014.12.014

A thioacidolysis method tailored for higher-throughput quantitative analysis of lignin monomers
journal, September 2016

  • Harman-Ware, Anne E.; Foster, Cliff; Happs, Renee M.
  • Biotechnology Journal, Vol. 11, Issue 10
  • DOI: 10.1002/biot.201600266

Influence of Syringyl to Guaiacyl Ratio on the Structure of Natural and Synthetic Lignins
journal, January 2010

  • Kishimoto, Takao; Chiba, Wakako; Saito, Kaori
  • Journal of Agricultural and Food Chemistry, Vol. 58, Issue 2
  • DOI: 10.1021/jf9035172

Identifying the Characteristic Secondary Ions of Lignin Polymer Using ToF−SIMS
journal, March 2005

  • Saito, Kaori; Kato, Toshiyuki; Tsuji, Yukiko
  • Biomacromolecules, Vol. 6, Issue 2
  • DOI: 10.1021/bm049521v

Impact of Lignin Structure and Cell Wall Reticulation on Maize Cell Wall Degradability
journal, September 2011

  • Zhang, Yu; Culhaoglu, Tanya; Pollet, Brigitte
  • Journal of Agricultural and Food Chemistry, Vol. 59, Issue 18
  • DOI: 10.1021/jf2028279

Chemical Factors that Control Lignin Polymerization
journal, December 2013

  • Sangha, Amandeep K.; Davison, Brian H.; Standaert, Robert F.
  • The Journal of Physical Chemistry B, Vol. 118, Issue 1
  • DOI: 10.1021/jp411998t

Molecular-Level Consequences of Biomass Pretreatment by Dilute Sulfuric Acid at Various Temperatures
journal, April 2011

  • Kobayashi, Takeshi; Kohn, Benjamin; Holmes, Lesley
  • Energy & Fuels, Vol. 25, Issue 4
  • DOI: 10.1021/ef1017219

Plant Biomass Characterization: Application of Solution- and Solid-State NMR Spectroscopy
book, April 2013

  • Pu, Yunqiao; Hallac, Bassem; Ragauskas, Arthur J.
  • Aqueous Pretreatment of Plant Biomass for Biological and Chemical Conversion to Fuels and Chemicals
  • DOI: 10.1002/9780470975831.ch18

The Effects on Lignin Structure of Overexpression of Ferulate 5-Hydroxylase in Hybrid Poplar 1
journal, April 2009

  • Stewart, Jaclyn J.; Akiyama, Takuya; Chapple, Clint
  • Plant Physiology, Vol. 150, Issue 2
  • DOI: 10.1104/pp.109.137059

Increase in 4-Coumaryl Alcohol Units during Lignification in Alfalfa ( Medicago sativa ) Alters the Extractability and Molecular Weight of Lignin
journal, October 2010

  • Ziebell, Angela; Gracom, Kristen; Katahira, Rui
  • Journal of Biological Chemistry, Vol. 285, Issue 50
  • DOI: 10.1074/jbc.M110.137315

Arabidopsis peroxidase-catalyzed copolymerization of coniferyl and sinapyl alcohols: Kinetics of an endwise process
journal, October 2010

EPR Investigation into the Effects of Substrate Structure on Peroxidase-Catalyzed Phenylpropanoid Oxidation
journal, January 2006

  • Russell, Wendy R.; Burkitt, Mark J.; Scobbie, Lorraine
  • Biomacromolecules, Vol. 7, Issue 1
  • DOI: 10.1021/bm050636o

Lignin valorization through integrated biological funneling and chemical catalysis
journal, August 2014

  • Linger, J. G.; Vardon, D. R.; Guarnieri, M. T.
  • Proceedings of the National Academy of Sciences, Vol. 111, Issue 33, p. 12013-12018
  • DOI: 10.1073/pnas.1410657111

Mass Spectrometry-Based Sequencing of Lignin Oligomers
journal, June 2010

Enhancing alfalfa conversion efficiencies for sugar recovery and ethanol production by altering lignin composition
journal, June 2011

Lignins: Natural polymers from oxidative coupling of 4-hydroxyphenyl- propanoids
journal, January 2004

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