Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin

Klinger, Grace E.; Zhou, Yuting; Foote, Juliet A.; Wester, Abby M.; Cui, Yanbin; Alherech, Manar; Stahl, Shannon S.; Jackson, James E.; Hegg, Eric L.

doi:10.1002/cssc.202001238

Nucleophilic Thiols Reductively Cleave Ether Linkages in Lignin Model Polymers and Lignin

Journal Article · Wed Jul 15 00:00:00 EDT 2020 · ChemSusChem

DOI:https://doi.org/10.1002/cssc.202001238· OSTI ID:1680057

^[1]; ^[2]; Foote, Juliet A. ^[2]; Wester, Abby M. ^[2]; ^[3]; ^[3]; ^[3]; ^[2]; ^[2]

Michigan State University, East Lansing, MI (United States); Michigan State University Department of Biochemistry and Molecular Biology
Michigan State University, East Lansing, MI (United States)
University of Wisconsin, Madison, WI (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Great Lakes Bioenergy Research Center, East Lansing, MI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: FC02-07ER64494; SC0018409

OSTI ID:: 1680057

Journal Information:: ChemSusChem, Journal Name: ChemSusChem Journal Issue: 17 Vol. 13; ISSN 1864-5631

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (44)

Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β-O-4 Linkages in Lignin Lancefield, Christopher S.; Ojo, O. Stephen; Tran, Fanny Angewandte Chemie, Vol. 127, Issue 1 https://doi.org/10.1002/ange.201409408	journal	November 2014
Protection Group Effects During α,γ-Diol Lignin Stabilization Promote High-Selectivity Monomer Production Lan, Wu; Amiri, Masoud Talebi; Hunston, Christopher M. Angewandte Chemie, Vol. 130, Issue 5 https://doi.org/10.1002/ange.201710838	journal	January 2018
Highly Selective Oxidation and Depolymerization of α,γ‐Diol‐Protected Lignin Lan, Wu; de Bueren, Jean Behaghel; Luterbacher, Jeremy S. Angewandte Chemie, Vol. 131, Issue 9 https://doi.org/10.1002/ange.201811630	journal	January 2019
Isolation of Functionalized Phenolic Monomers through Selective Oxidation and CO Bond Cleavage of the β-O-4 Linkages in Lignin Lancefield, Christopher S.; Ojo, O. Stephen; Tran, Fanny Angewandte Chemie International Edition, Vol. 54, Issue 1 https://doi.org/10.1002/anie.201409408	journal	November 2014
Protection Group Effects During α,γ-Diol Lignin Stabilization Promote High-Selectivity Monomer Production Lan, Wu; Amiri, Masoud Talebi; Hunston, Christopher M. Angewandte Chemie International Edition, Vol. 57, Issue 5 https://doi.org/10.1002/anie.201710838	journal	January 2018
Highly Selective Oxidation and Depolymerization of α,γ‐Diol‐Protected Lignin Lan, Wu; de Bueren, Jean Behaghel; Luterbacher, Jeremy S. Angewandte Chemie International Edition, Vol. 58, Issue 9 https://doi.org/10.1002/anie.201811630	journal	February 2019
Solvent Effects on the Hydrogenolysis of Diphenyl Ether with Raney Nickel and their Implications for the Conversion of Lignin Wang, Xingyu; Rinaldi, Roberto ChemSusChem, Vol. 5, Issue 8, p. 1455-1466 https://doi.org/10.1002/cssc.201200040	journal	April 2012
Biomimetic Reductive Cleavage of Keto Aryl Ether Bonds by Small‐Molecule Thiols Klinger, Grace E.; Zhou, Yuting; Hao, Pengchao ChemSusChem, Vol. 12, Issue 21 https://doi.org/10.1002/cssc.201901742	journal	September 2019
Thioacidolysis Rolando, C.; Monties, B.; Lapierre, C. Methods in Lignin Chemistry https://doi.org/10.1007/978-3-642-74065-7_23	book	January 1992
Efficient valorization of biomass to biofuels with bifunctional solid catalytic materials Li, Hu; Fang, Zhen; Smith, Richard L. Progress in Energy and Combustion Science, Vol. 55 https://doi.org/10.1016/j.pecs.2016.04.004	journal	July 2016
Catalytic Transformation of Lignin for the Production of Chemicals and Fuels Li, Changzhi; Zhao, Xiaochen; Wang, Aiqin Chemical Reviews, Vol. 115, Issue 21, p. 11559-11624 https://doi.org/10.1021/acs.chemrev.5b00155	journal	October 2015
Bright Side of Lignin Depolymerization: Toward New Platform Chemicals Sun, Zhuohua; Fridrich, Bálint; de Santi, Alessandra Chemical Reviews, Vol. 118, Issue 2 https://doi.org/10.1021/acs.chemrev.7b00588	journal	January 2018
Electrocatalytic Upgrading of Phenolic Compounds Observed after Lignin Pyrolysis Garedew, Mahlet; Young-Farhat, Daniel; Jackson, James E. ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 9 https://doi.org/10.1021/acssuschemeng.9b00019	journal	March 2019
Dithiothreitol, a New Protective Reagent for SH Groups ^* Cleland, W. W. Biochemistry, Vol. 3, Issue 4 https://doi.org/10.1021/bi00892a002	journal	April 1964
The Catalytic Valorization of Lignin for the Production of Renewable Chemicals Zakzeski, Joseph; Bruijnincx, Pieter C. A.; Jongerius, Anna L. Chemical Reviews, Vol. 110, Issue 6, p. 3552-3599 https://doi.org/10.1021/cr900354u	journal	June 2010
A Group of Sequence-Related Sphingomonad Enzymes Catalyzes Cleavage of β-Aryl Ether Linkages in Lignin β-Guaiacyl and β-Syringyl Ether Dimers Gall, Daniel L.; Ralph, John; Donohue, Timothy J. Environmental Science & Technology, Vol. 48, Issue 20 https://doi.org/10.1021/es503886d	journal	October 2014
Chemoselective Metal-Free Aerobic Alcohol Oxidation in Lignin Rahimi, Alireza; Azarpira, Ali; Kim, Hoon Journal of the American Chemical Society, Vol. 135, Issue 17, p. 6415-6418 https://doi.org/10.1021/ja401793n	journal	April 2013
A Photochemical Strategy for Lignin Degradation at Room Temperature Nguyen, John D.; Matsuura, Bryan S.; Stephenson, Corey R. J. Journal of the American Chemical Society, Vol. 136, Issue 4 https://doi.org/10.1021/ja4113462	journal	January 2014
Multiple Mechanisms Mapped in Aryl Alkyl Ether Cleavage via Aqueous Electrocatalytic Hydrogenation over Skeletal Nickel Zhou, Yuting; Klinger, Grace E.; Hegg, Eric L. Journal of the American Chemical Society, Vol. 142, Issue 8 https://doi.org/10.1021/jacs.0c00199	journal	February 2020
Electrochemical Aminoxyl-Mediated Oxidation of Primary Alcohols in Lignin to Carboxylic Acids: Polymer Modification and Depolymerization Rafiee, Mohammad; Alherech, Manar; Karlen, Steven D. Journal of the American Chemical Society, Vol. 141, Issue 38 https://doi.org/10.1021/jacs.9b07243	journal	September 2019
DFRC Method for Lignin Analysis. 1. New Method for β-Aryl Ether Cleavage: Lignin Model Studies Lu, Fachuang; Ralph, John Journal of Agricultural and Food Chemistry, Vol. 45, Issue 12 https://doi.org/10.1021/jf970539p	journal	December 1997
Low-temperature Cleavage of Ethers Long, L. H.; Freeguard, G. F. Nature, Vol. 207, Issue 4995 https://doi.org/10.1038/207403a0	journal	July 1965
Formic-acid-induced depolymerization of oxidized lignin to aromatics Rahimi, Alireza; Ulbrich, Arne; Coon, Joshua J. Nature, Vol. 515, Issue 7526, p. 249-252 https://doi.org/10.1038/nature13867	journal	November 2014
Cooperative electrocatalytic alcohol oxidation with electron-proton-transfer mediators Badalyan, Artavazd; Stahl, Shannon S. Nature, Vol. 535, Issue 7612 https://doi.org/10.1038/nature18008	journal	June 2016
Fractionation of lignocellulosic biomass to produce uncondensed aldehyde-stabilized lignin Talebi Amiri, Masoud; Dick, Graham R.; Questell-Santiago, Ydna M. Nature Protocols, Vol. 14, Issue 3 https://doi.org/10.1038/s41596-018-0121-7	journal	February 2019
Easy synthesis of β-O-4 type lignin related polymers Kishimoto, Takao; Uraki, Yasumitsu; Ubukata, Makoto Org. Biomol. Chem., Vol. 3, Issue 6 https://doi.org/10.1039/B416699J	journal	January 2005
Electrocatalytic upgrading of model lignin monomers with earth abundant metal electrodes Lam, Chun Ho; Lowe, Christy B.; Li, Zhenglong Green Chemistry, Vol. 17, Issue 1 https://doi.org/10.1039/C4GC01632G	journal	January 2015
Towards sustainable hydrocarbon fuels with biomass fast pyrolysis oil and electrocatalytic upgrading Lam, Chun Ho; Das, Sabyasachi; Erickson, Nichole C. Sustainable Energy & Fuels, Vol. 1, Issue 2 https://doi.org/10.1039/C6SE00080K	journal	January 2017
Electrocatalytic cleavage of lignin model dimers using ruthenium supported on activated carbon cloth Garedew, Mahlet; Young-Farhat, Daniel; Bhatia, Souful Sustainable Energy & Fuels, Vol. 4, Issue 3 https://doi.org/10.1039/C9SE00912D	journal	January 2020
Synthesis of β-O-4-type artificial lignin polymers and their analysis by NMR spectroscopy Kishimoto, Takao; Uraki, Yasumitsu; Ubukata, Makoto Organic & Biomolecular Chemistry, Vol. 6, Issue 16 https://doi.org/10.1039/b805460f	journal	January 2008
Thiol-click chemistry: a multifaceted toolbox for small molecule and polymer synthesis Hoyle, Charles E.; Lowe, Andrew B.; Bowman, Christopher N. Chemical Society Reviews, Vol. 39, Issue 4 https://doi.org/10.1039/b901979k	journal	January 2010
Noble-metal catalyzed hydrodeoxygenation of biomass-derived lignin to aromatic hydrocarbons Laskar, Dhrubojyoti D.; Tucker, Melvin P.; Chen, Xiaowen Green Chemistry, Vol. 16, Issue 2 https://doi.org/10.1039/c3gc42041h	journal	January 2014
Stereochemical Features of Glutathione-dependent Enzymes in the Sphingobium sp. Strain SYK-6 β-Aryl Etherase Pathway Gall, Daniel L.; Kim, Hoon; Lu, Fachuang Journal of Biological Chemistry, Vol. 289, Issue 12 https://doi.org/10.1074/jbc.M113.536250	journal	February 2014
Structural Basis of Stereospecificity in the Bacterial Enzymatic Cleavage of β-Aryl Ether Bonds in Lignin Helmich, Kate E.; Pereira, Jose Henrique; Gall, Daniel L. Journal of Biological Chemistry, Vol. 291, Issue 10 https://doi.org/10.1074/jbc.M115.694307	journal	December 2015
Structural and Biochemical Characterization of the Early and Late Enzymes in the Lignin β-Aryl Ether Cleavage Pathway from Sphingobium sp. SYK-6 Pereira, Jose Henrique; Heins, Richard A.; Gall, Daniel L. Journal of Biological Chemistry, Vol. 291, Issue 19 https://doi.org/10.1074/jbc.M115.700427	journal	March 2016
Novosphingobium aromaticivorans uses a Nu-class glutathione S -transferase as a glutathione lyase in breaking the β-aryl ether bond of lignin Kontur, Wayne S.; Bingman, Craig A.; Olmsted, Charles N. Journal of Biological Chemistry, Vol. 293, Issue 14 https://doi.org/10.1074/jbc.RA117.001268	journal	February 2018
A heterodimeric glutathione S -transferase that stereospecifically breaks lignin's β( R )-aryl ether bond reveals the diversity of bacterial β-etherases Kontur, Wayne S.; Olmsted, Charles N.; Yusko, Larissa M. Journal of Biological Chemistry, Vol. 294, Issue 6 https://doi.org/10.1074/jbc.RA118.006548	journal	December 2018
Thioacidolysis of Lignin: Comparison with Acidolysis Lapierre, Catherine; Monties, Bernard; Rolando, Christian Journal of Wood Chemistry and Technology, Vol. 5, Issue 2 https://doi.org/10.1080/02773818508085193	journal	January 1985
Bacterial catabolism of lignin-derived aromatics: New findings in a recent decade: Update on bacterial lignin catabolism: Bacterial catabolism of lignin-derived aromatics Kamimura, Naofumi; Takahashi, Kenji; Mori, Kosuke Environmental Microbiology Reports, Vol. 9, Issue 6 https://doi.org/10.1111/1758-2229.12597	journal	November 2017
Formaldehyde stabilization facilitates lignin monomer production during biomass depolymerization Shuai, Li; Amiri, Masoud Talebi; Questell-Santiago, Ydna M. Science, Vol. 354, Issue 6310 https://doi.org/10.1126/science.aaf7810	journal	October 2016
Electrocatalytic hydrogenation of lignin models at Raney nickel and palladium-based electrodes Cyr, André; Chiltz, Florence; Jeanson, Paul Canadian Journal of Chemistry, Vol. 78, Issue 3, p. 307-315 https://doi.org/10.1139/v00-009	journal	March 2000
Study of liquid-phase molecular packing interactions and morphology of fatty acid methyl esters (biodiesel) Berman, Paula; Meiri, Nitzan; Colnago, Luiz Biotechnology for Biofuels, Vol. 8, Issue 1 https://doi.org/10.1186/s13068-014-0194-7	journal	January 2015
Effective alkaline metal-catalyzed oxidative delignification of hybrid poplar Bhalla, Aditya; Bansal, Namita; Stoklosa, Ryan J. Biotechnology for Biofuels, Vol. 9, Issue 1 https://doi.org/10.1186/s13068-016-0442-0	journal	February 2016
Acid Degradation of Lignin. IV. Analysis of Lignin Acidolysis Products by Gas Chromatography, Using Trimethylsilyl Derivatives. Lundquist, Knut; Kirk, T. Kent; Fredlund, Folke Acta Chemica Scandinavica, Vol. 25 https://doi.org/10.3891/acta.chem.scand.25-0889	journal	January 1971