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Title: An “ideal lignin” facilitates full biomass utilization

Abstract

Lignin, a major component of lignocellulosic biomass, is crucial to plant growth and development but is a major impediment to efficient biomass utilization in various processes. Valorizing lignin is increasingly realized as being essential. However, rapid condensation of lignin during acidic extraction leads to the formation of recalcitrant condensed units that, along with similar units and structural heterogeneity in native lignin, drastically limits product yield and selectivity. Catechyl lignin (C-lignin), which is essentially a benzodioxane homopolymer without condensed units, might represent an ideal lignin for valorization, as it circumvents these issues. We discovered that C-lignin is highly acid-resistant. Hydrogenolysis of C-lignin resulted in the cleavage of all benzodioxane structures to produce catechyl-type monomers in near-quantitative yield with a selectivity of 90% to a single monomer.

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5];  [5]; ORCiD logo [6]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Wisconsin, Madison, WI (United States)
  2. Univ. of Wisconsin, Madison, WI (United States); Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  3. Univ. of Wisconsin, Madison, WI (United States); Kyoto Univ. (Japan)
  4. State Univ. of New Jersey, New Brunswick, NJ (United States); Bakto Flavors LLC, North Brunswick, NJ (United States)
  5. Univ. of North Texas, Denton, TX (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  6. École Polytechnique Fédérale de Lausanne (Switzerland)
Publication Date:
Research Org.:
Great Lakes Bioenergy Research Center (GLBRC), Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER)
OSTI Identifier:
1543278
Grant/Contract Number:  
SC0018409; FC02-07ER64494; AC05-000R22725
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Science Advances
Additional Journal Information:
Journal Volume: 4; Journal Issue: 9; Journal ID: ISSN 2375-2548
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Li, Yanding, Shuai, Li, Kim, Hoon, Motagamwala, Ali Hussain, Mobley, Justin K., Yue, Fengxia, Tobimatsu, Yuki, Havkin-Frenkel, Daphna, Chen, Fang, Dixon, Richard A., Luterbacher, Jeremy S., Dumesic, James A., and Ralph, John. An “ideal lignin” facilitates full biomass utilization. United States: N. p., 2018. Web. doi:10.1126/sciadv.aau2968.
Li, Yanding, Shuai, Li, Kim, Hoon, Motagamwala, Ali Hussain, Mobley, Justin K., Yue, Fengxia, Tobimatsu, Yuki, Havkin-Frenkel, Daphna, Chen, Fang, Dixon, Richard A., Luterbacher, Jeremy S., Dumesic, James A., & Ralph, John. An “ideal lignin” facilitates full biomass utilization. United States. https://doi.org/10.1126/sciadv.aau2968
Li, Yanding, Shuai, Li, Kim, Hoon, Motagamwala, Ali Hussain, Mobley, Justin K., Yue, Fengxia, Tobimatsu, Yuki, Havkin-Frenkel, Daphna, Chen, Fang, Dixon, Richard A., Luterbacher, Jeremy S., Dumesic, James A., and Ralph, John. 2018. "An “ideal lignin” facilitates full biomass utilization". United States. https://doi.org/10.1126/sciadv.aau2968. https://www.osti.gov/servlets/purl/1543278.
@article{osti_1543278,
title = {An “ideal lignin” facilitates full biomass utilization},
author = {Li, Yanding and Shuai, Li and Kim, Hoon and Motagamwala, Ali Hussain and Mobley, Justin K. and Yue, Fengxia and Tobimatsu, Yuki and Havkin-Frenkel, Daphna and Chen, Fang and Dixon, Richard A. and Luterbacher, Jeremy S. and Dumesic, James A. and Ralph, John},
abstractNote = {Lignin, a major component of lignocellulosic biomass, is crucial to plant growth and development but is a major impediment to efficient biomass utilization in various processes. Valorizing lignin is increasingly realized as being essential. However, rapid condensation of lignin during acidic extraction leads to the formation of recalcitrant condensed units that, along with similar units and structural heterogeneity in native lignin, drastically limits product yield and selectivity. Catechyl lignin (C-lignin), which is essentially a benzodioxane homopolymer without condensed units, might represent an ideal lignin for valorization, as it circumvents these issues. We discovered that C-lignin is highly acid-resistant. Hydrogenolysis of C-lignin resulted in the cleavage of all benzodioxane structures to produce catechyl-type monomers in near-quantitative yield with a selectivity of 90% to a single monomer.},
doi = {10.1126/sciadv.aau2968},
url = {https://www.osti.gov/biblio/1543278}, journal = {Science Advances},
issn = {2375-2548},
number = 9,
volume = 4,
place = {United States},
year = {Fri Sep 28 00:00:00 EDT 2018},
month = {Fri Sep 28 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
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Citation Metrics:
Cited by: 138 works
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Figures / Tables:

Table 1 Table 1: Mass balance and total organic carbon (TOC) on hydrogenolysis of C-LBL and its resulting product oil.

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Works referenced in this record:

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Catechol-Based Biomimetic Functional Materials
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Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β-O-4 Linkages in Lignin
journal, November 2014


Paving the Way for Lignin Valorisation: Recent Advances in Bioengineering, Biorefining and Catalysis
journal, June 2016


Towards Quantitative Catalytic Lignin Depolymerization
journal, April 2011


Designer lignins: harnessing the plasticity of lignification
journal, February 2016


NMR Assignment for Diaryl Ether Structures (4–O–5 Structures) in Pine Wood Lignin
journal, April 2016


Bright Side of Lignin Depolymerization: Toward New Platform Chemicals
journal, January 2018


Life Cycle Assessment of Catechols from Lignin Depolymerization
journal, December 2015


Aromatic Monomers by in Situ Conversion of Reactive Intermediates in the Acid-Catalyzed Depolymerization of Lignin
journal, June 2015


Quantitative 13 C NMR Analysis of Lignins with Internal Standards
journal, August 2001


Selective production of arenes via direct lignin upgrading over a niobium-based catalyst
journal, July 2017


A polymer of caffeyl alcohol in plant seeds
journal, January 2012


Toward engineering E. coli with an autoregulatory system for lignin valorization
journal, March 2018


Coexistence but Independent Biosynthesis of Catechyl and Guaiacyl/Syringyl Lignin Polymers in Seed Coats
journal, July 2013


Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization
journal, October 2016


Preparative Thioacidolysis of Spruce Lignin: Isolation and Identification of Main Monomeric Products
journal, January 1986


Works referencing / citing this record:

Self-supported hydrogenolysis of aromatic ethers to arenes
journal, November 2019


Chemodivergent hydrogenolysis of eucalyptus lignin with Ni@ZIF-8 catalyst
journal, January 2019


Convergent production of 2,5-furandicarboxylic acid from biomass and CO 2
journal, January 2019


Selective utilization of methoxy groups in lignin for N -methylation reaction of anilines
journal, January 2019


Kinetic and mechanistic insights into hydrogenolysis of lignin to monomers in a continuous flow reactor
journal, January 2019


Enzymatic basis for C‐lignin monomer biosynthesis in the seed coat of Cleome hassleriana
journal, May 2019


Lignin biosynthesis: old roads revisited and new roads explored
journal, December 2019


Lignin biosynthesis: old roads revisited and new roads explored
journal, December 2019


Self-supported hydrogenolysis of aromatic ethers to arenes
journal, November 2019


Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.