Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin
Abstract
Lignin may serve as a renewable feedstock for the production of chemicals and fuels if mild, scalable processes for its depolymerization can be devised. The use of small organic thiols represents a bioinspired strategy to cleave the β–O–4 bond, the most common linkage in lignin. In the present study, synthetic β–O–4 linked polymers were treated with organic thiols, yielding up to 90 % cleaved monomer products. Lignin extracted from poplar was also treated with organic thiols resulting in molecular weight reductions as high as 65 % (Mn) in oxidized lignin. Thiol–based cleavage of other lignin linkages was also explored in small–molecule model systems to uncover additional potential pathways by which thiols might depolymerize lignin. The success of thiol–mediated cleavage on model dimers, polymers, and biomass–derived lignin illustrates the potential utility of small redox–active molecules to penetrate complex polymer matrices for depolymerization and subsequent valorization of lignin into fuels and chemicals.
- Authors:
-
[1];
[1];
[2];
[2];
[2];
[1];
[1]
- Michigan State University, East Lansing, MI (United States)
- University of Wisconsin, Madison, WI (United States)
- Publication Date:
- Research Org.:
- Great Lakes Bioenergy Research Center, East Lansing, MI (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1680057
- Grant/Contract Number:
- SC0018409; FC02-07ER64494
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ChemSusChem
- Additional Journal Information:
- Journal Volume: 13; Journal Issue: 17; Journal ID: ISSN 1864-5631
- Publisher:
- ChemPubSoc Europe
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Ether; homogeneous catalysis; lignin; polymers; sulfur
Citation Formats
Klinger, Grace E., Zhou, Yuting, Foote, Juliet A., Wester, Abby M., Cui, Yanbin, Alherech, Manar, Stahl, Shannon S., Jackson, James E., and Hegg, Eric L. Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin. United States: N. p., 2020.
Web. doi:10.1002/cssc.202001238.
Klinger, Grace E., Zhou, Yuting, Foote, Juliet A., Wester, Abby M., Cui, Yanbin, Alherech, Manar, Stahl, Shannon S., Jackson, James E., & Hegg, Eric L. Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin. United States. https://doi.org/10.1002/cssc.202001238
Klinger, Grace E., Zhou, Yuting, Foote, Juliet A., Wester, Abby M., Cui, Yanbin, Alherech, Manar, Stahl, Shannon S., Jackson, James E., and Hegg, Eric L. Wed .
"Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin". United States. https://doi.org/10.1002/cssc.202001238. https://www.osti.gov/servlets/purl/1680057.
@article{osti_1680057,
title = {Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin},
author = {Klinger, Grace E. and Zhou, Yuting and Foote, Juliet A. and Wester, Abby M. and Cui, Yanbin and Alherech, Manar and Stahl, Shannon S. and Jackson, James E. and Hegg, Eric L.},
abstractNote = {Lignin may serve as a renewable feedstock for the production of chemicals and fuels if mild, scalable processes for its depolymerization can be devised. The use of small organic thiols represents a bioinspired strategy to cleave the β–O–4 bond, the most common linkage in lignin. In the present study, synthetic β–O–4 linked polymers were treated with organic thiols, yielding up to 90 % cleaved monomer products. Lignin extracted from poplar was also treated with organic thiols resulting in molecular weight reductions as high as 65 % (Mn) in oxidized lignin. Thiol–based cleavage of other lignin linkages was also explored in small–molecule model systems to uncover additional potential pathways by which thiols might depolymerize lignin. The success of thiol–mediated cleavage on model dimers, polymers, and biomass–derived lignin illustrates the potential utility of small redox–active molecules to penetrate complex polymer matrices for depolymerization and subsequent valorization of lignin into fuels and chemicals.},
doi = {10.1002/cssc.202001238},
journal = {ChemSusChem},
number = 17,
volume = 13,
place = {United States},
year = {Wed Jul 15 00:00:00 EDT 2020},
month = {Wed Jul 15 00:00:00 EDT 2020}
}
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Figure 1: $β$-aryl ether cleavage via thiol nucleophilic attack. A) Enzymatic $β$-aryl ether cleavage of C$α$-oxidized lignin dimers with glutathione (GSH). B) Our previous work, focusing on $β$-O-4 model dimers cleavage with organic thiols (RSH). C) This work, focusing on lignin and lignin-like polymer cleavage using organic thiols to formmore »
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Works referenced in this record:
Structural and Biochemical Characterization of the Early and Late Enzymes in the Lignin β-Aryl Ether Cleavage Pathway from Sphingobium sp. SYK-6
journal, March 2016
- Pereira, Jose Henrique; Heins, Richard A.; Gall, Daniel L.
- Journal of Biological Chemistry, Vol. 291, Issue 19
Synthesis of β-O-4-type artificial lignin polymers and their analysis by NMR spectroscopy
journal, January 2008
- Kishimoto, Takao; Uraki, Yasumitsu; Ubukata, Makoto
- Organic & Biomolecular Chemistry, Vol. 6, Issue 16
Fractionation of lignocellulosic biomass to produce uncondensed aldehyde-stabilized lignin
journal, February 2019
- Talebi Amiri, Masoud; Dick, Graham R.; Questell-Santiago, Ydna M.
- Nature Protocols, Vol. 14, Issue 3
Effective alkaline metal-catalyzed oxidative delignification of hybrid poplar
journal, February 2016
- Bhalla, Aditya; Bansal, Namita; Stoklosa, Ryan J.
- Biotechnology for Biofuels, Vol. 9, Issue 1
Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis
journal, January 2010
- Hoyle, Charles E.; Lowe, Andrew B.; Bowman, Christopher N.
- Chemical Society Reviews, Vol. 39, Issue 4
A heterodimeric glutathione S -transferase that stereospecifically breaks lignin's β( R )-aryl ether bond reveals the diversity of bacterial β-etherases
journal, December 2018
- Kontur, Wayne S.; Olmsted, Charles N.; Yusko, Larissa M.
- Journal of Biological Chemistry, Vol. 294, Issue 6
Formic-acid-induced depolymerization of oxidized lignin to aromatics
journal, November 2014
- Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J.
- Nature, Vol. 515, Issue 7526, p. 249-252
A Group of Sequence-Related Sphingomonad Enzymes Catalyzes Cleavage of β-Aryl Ether Linkages in Lignin β-Guaiacyl and β-Syringyl Ether Dimers
journal, October 2014
- Gall, Daniel L.; Ralph, John; Donohue, Timothy J.
- Environmental Science & Technology, Vol. 48, Issue 20
Bright Side of Lignin Depolymerization: Toward New Platform Chemicals
journal, January 2018
- Sun, Zhuohua; Fridrich, Bálint; de Santi, Alessandra
- Chemical Reviews, Vol. 118, Issue 2
Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β-O-4 Linkages in Lignin
journal, November 2014
- Lancefield, Christopher S.; Ojo, O. Stephen; Tran, Fanny
- Angewandte Chemie International Edition, Vol. 54, Issue 1
Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β-O-4 Linkages in Lignin
journal, November 2014
- Lancefield, Christopher S.; Ojo, O. Stephen; Tran, Fanny
- Angewandte Chemie, Vol. 127, Issue 1
Electrocatalytic upgrading of model lignin monomers with earth abundant metal electrodes
journal, January 2015
- Lam, Chun Ho; Lowe, Christy B.; Li, Zhenglong
- Green Chemistry, Vol. 17, Issue 1
Highly Selective Oxidation and Depolymerization of α,γ‐Diol‐Protected Lignin
journal, February 2019
- Lan, Wu; de Bueren, Jean Behaghel; Luterbacher, Jeremy S.
- Angewandte Chemie International Edition, Vol. 58, Issue 9
DFRC Method for Lignin Analysis. 1. New Method for β-Aryl Ether Cleavage: Lignin Model Studies
journal, December 1997
- Lu, Fachuang; Ralph, John
- Journal of Agricultural and Food Chemistry, Vol. 45, Issue 12
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals
journal, June 2010
- Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L.
- Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599
Dithiothreitol, a New Protective Reagent for SH Groups *
journal, April 1964
- Cleland, W. W.
- Biochemistry, Vol. 3, Issue 4
Acid Degradation of Lignin. IV. Analysis of Lignin Acidolysis Products by Gas Chromatography, Using Trimethylsilyl Derivatives.
journal, January 1971
- Lundquist, Knut; Kirk, T. Kent; Fredlund, Folke
- Acta Chemica Scandinavica, Vol. 25
Structural Basis of Stereospecificity in the Bacterial Enzymatic Cleavage of β-Aryl Ether Bonds in Lignin
journal, December 2015
- Helmich, Kate E.; Pereira, Jose Henrique; Gall, Daniel L.
- Journal of Biological Chemistry, Vol. 291, Issue 10
Catalytic Transformation of Lignin for the Production of Chemicals and Fuels
journal, October 2015
- Li, Changzhi; Zhao, Xiaochen; Wang, Aiqin
- Chemical Reviews, Vol. 115, Issue 21, p. 11559-11624
Protection Group Effects During α,γ-Diol Lignin Stabilization Promote High-Selectivity Monomer Production
journal, January 2018
- Lan, Wu; Amiri, Masoud Talebi; Hunston, Christopher M.
- Angewandte Chemie, Vol. 130, Issue 5
Electrocatalytic Upgrading of Phenolic Compounds Observed after Lignin Pyrolysis
journal, March 2019
- Garedew, Mahlet; Young-Farhat, Daniel; Jackson, James E.
- ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 9
A Photochemical Strategy for Lignin Degradation at Room Temperature
journal, January 2014
- Nguyen, John D.; Matsuura, Bryan S.; Stephenson, Corey R. J.
- Journal of the American Chemical Society, Vol. 136, Issue 4
Electrocatalytic hydrogenation of lignin models at Raney nickel and palladium-based electrodes
journal, March 2000
- Cyr, André; Chiltz, Florence; Jeanson, Paul
- Canadian Journal of Chemistry, Vol. 78, Issue 3, p. 307-315
Electrocatalytic cleavage of lignin model dimers using ruthenium supported on activated carbon cloth
journal, January 2020
- Garedew, Mahlet; Young-Farhat, Daniel; Bhatia, Souful
- Sustainable Energy & Fuels, Vol. 4, Issue 3
Novosphingobium aromaticivorans uses a Nu-class glutathione S -transferase as a glutathione lyase in breaking the β-aryl ether bond of lignin
journal, February 2018
- Kontur, Wayne S.; Bingman, Craig A.; Olmsted, Charles N.
- Journal of Biological Chemistry, Vol. 293, Issue 14
Noble-metal catalyzed hydrodeoxygenation of biomass-derived lignin to aromatic hydrocarbons
journal, January 2014
- Laskar, Dhrubojyoti D.; Tucker, Melvin P.; Chen, Xiaowen
- Green Chemistry, Vol. 16, Issue 2
Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin
journal, April 2012
- Wang, Xingyu; Rinaldi, Roberto
- ChemSusChem, Vol. 5, Issue 8, p. 1455-1466
Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization
journal, September 2019
- Rafiee, Mohammad; Alherech, Manar; Karlen, Steven D.
- Journal of the American Chemical Society, Vol. 141, Issue 38
Thioacidolysis of Lignin: Comparison with Acidolysis
journal, January 1985
- Lapierre, Catherine; Monties, Bernard; Rolando, Christian
- Journal of Wood Chemistry and Technology, Vol. 5, Issue 2
Bacterial catabolism of lignin-derived aromatics: New findings in a recent decade: Update on bacterial lignin catabolism: Bacterial catabolism of lignin-derived aromatics
journal, November 2017
- Kamimura, Naofumi; Takahashi, Kenji; Mori, Kosuke
- Environmental Microbiology Reports, Vol. 9, Issue 6
Multiple Mechanisms Mapped in Aryl Alkyl Ether Cleavage via Aqueous Electrocatalytic Hydrogenation over Skeletal Nickel
journal, February 2020
- Zhou, Yuting; Klinger, Grace E.; Hegg, Eric L.
- Journal of the American Chemical Society, Vol. 142, Issue 8
Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin
journal, April 2013
- Rahimi, Alireza; Azarpira, Ali; Kim, Hoon
- Journal of the American Chemical Society, Vol. 135, Issue 17, p. 6415-6418
Thioacidolysis
book, January 1992
- Rolando, C.; Monties, B.; Lapierre, C.
- Methods in Lignin Chemistry
Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators
journal, June 2016
- Badalyan, Artavazd; Stahl, Shannon S.
- Nature, Vol. 535, Issue 7612
Highly Selective Oxidation and Depolymerization of α,γ‐Diol‐Protected Lignin
journal, January 2019
- Lan, Wu; de Bueren, Jean Behaghel; Luterbacher, Jeremy S.
- Angewandte Chemie, Vol. 131, Issue 9
Efficient valorization of biomass to biofuels with bifunctional solid catalytic materials
journal, July 2016
- Li, Hu; Fang, Zhen; Smith, Richard L.
- Progress in Energy and Combustion Science, Vol. 55
Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization
journal, October 2016
- Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M.
- Science, Vol. 354, Issue 6310
Study of liquid-phase molecular packing interactions and morphology of fatty acid methyl esters (biodiesel)
journal, January 2015
- Berman, Paula; Meiri, Nitzan; Colnago, Luiz
- Biotechnology for Biofuels, Vol. 8, Issue 1
Low-temperature Cleavage of Ethers
journal, July 1965
- Long, L. H.; Freeguard, G. F.
- Nature, Vol. 207, Issue 4995
Towards sustainable hydrocarbon fuels with biomass fast pyrolysis oil and electrocatalytic upgrading
journal, January 2017
- Lam, Chun Ho; Das, Sabyasachi; Erickson, Nichole C.
- Sustainable Energy & Fuels, Vol. 1, Issue 2
Biomimetic Reductive Cleavage of Keto Aryl Ether Bonds by Small‐Molecule Thiols
journal, September 2019
- Klinger, Grace E.; Zhou, Yuting; Hao, Pengchao
- ChemSusChem, Vol. 12, Issue 21
Stereochemical Features of Glutathione-dependent Enzymes in the Sphingobium sp. Strain SYK-6 β-Aryl Etherase Pathway
journal, February 2014
- Gall, Daniel L.; Kim, Hoon; Lu, Fachuang
- Journal of Biological Chemistry, Vol. 289, Issue 12
Protection Group Effects During α,γ-Diol Lignin Stabilization Promote High-Selectivity Monomer Production
journal, January 2018
- Lan, Wu; Amiri, Masoud Talebi; Hunston, Christopher M.
- Angewandte Chemie International Edition, Vol. 57, Issue 5
Easy synthesis of β-O-4 type lignin related polymers
journal, January 2005
- Kishimoto, Takao; Uraki, Yasumitsu; Ubukata, Makoto
- Org. Biomol. Chem., Vol. 3, Issue 6
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