A Multifunctional Cosolvent Pair Reveals Molecular Principles of Biomass Deconstruction

Patri, Abhishek S.; Mostofian, Barmak; Pu, Yunqiao; Ciaffone, Nicholas; Soliman, Mikhael; Smith, Micholas Dean; Kumar, Rajeev; Cheng, Xiaolin; Wyman, Charles E.; Tetard, Laurene; Ragauskas, Arthur J.; Smith, Jeremy C.; Petridis, Loukas; Cai, Charles M.

doi:10.1021/jacs.8b10242

Title: A Multifunctional Cosolvent Pair Reveals Molecular Principles of Biomass Deconstruction

Journal Article · Mon Jul 15 00:00:00 EDT 2019 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.8b10242· OSTI ID:1558519

Patri, Abhishek S. ^[1];

^[2];

^[3]; Ciaffone, Nicholas ^[4]; Soliman, Mikhael ^[4];

^[5]; Kumar, Rajeev ^[6];

^[7]; Wyman, Charles E. ^[6]; Tetard, Laurene ^[4];

^[8];

^[5];

^[6]

Univ. of California, Riverside, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). UT/ORNL Center for Molecular Biophysics; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. for Biological Sciences
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. for Biological Sciences
Univ. of Central Florida, Orlando, FL (United States). NanoScience Technology Center
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). UT/ORNL Center for Molecular Biophysics; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Biochemistry
Univ. of California, Riverside, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Bioenergy Innovation (CBI)
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). UT/ORNL Center for Molecular Biophysics; The Ohio State Univ., Columbus, OH (United States). College of Pharmacy
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Joint Inst. for Biological Sciences; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Chemical and Biomolecular Engineering; Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Bioenergy Innovation (CBI)

The complex structure of plant cell walls resists chemical or biological degradation, challenging the breakdown of lignocellulosic biomass into renewable chemical precursors that could form the basis of future production of green chemicals and transportation fuels. In this report, experimental and computational results reveal that the effect of the tetrahydrofuran (THF)–water cosolvents on the structure of lignin and on its interactions with cellulose in the cell wall drives multiple synergistic mechanisms leading to the efficient breakdown and fractionation of biomass into valuable chemical precursors. Molecular simulations reflect that THF–water is an excellent “theta” solvent, such that lignin dissociates from itself and from cellulose and expands to form a random coil. The expansion of the lignin molecules exposes interunit linkages, rendering them more susceptible to depolymerization by acid-catalyzed cleavage of aryl-ether bonds. Nanoscale infrared sensors confirm cosolvent-mediated molecular rearrangement of lignin in the cell wall of micrometer-thick hardwood slices and track the disappearance of lignin. At bulk scale, adding dilute acid to the cosolvent mixture liberates the majority of the hemicellulose and lignin from biomass, allowing unfettered access of cellulolytic enzymes to the remaining cellulose-rich material, allowing them to sustain high rates of hydrolysis to glucose without enzyme deactivation. Through this multiscale analysis, synergistic mechanisms for biomass deconstruction are confirmed, portending a paradigm shift toward first-principles design and evaluation of other cosolvent methods to realize low cost fuels and bioproducts.

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Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

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

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1558519

Journal Information:: Journal of the American Chemical Society, Vol. 141, Issue 32; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 47 works

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A Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization in Acidic Environments Sturgeon, Matthew R.; Kim, Seonah; Lawrence, Kelsey ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 3, p. 472-485 https://doi.org/10.1021/sc400384w	journal	November 2013
Molecular-Level Consequences of Biomass Pretreatment by Dilute Sulfuric Acid at Various Temperatures Kobayashi, Takeshi; Kohn, Benjamin; Holmes, Lesley Energy & Fuels, Vol. 25, Issue 4 https://doi.org/10.1021/ef1017219	journal	April 2011
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

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Performance of three delignifying pretreatments on hardwoods: hydrolysis yields, comprehensive mass balances, and lignin properties Bhalla, Aditya; Cai, Charles M.; Xu, Feng Biotechnology for Biofuels, Vol. 12, Issue 1 https://doi.org/10.1186/s13068-019-1546-0	journal	September 2019
Pretreatment for biorefineries: a review of common methods for efficient utilisation of lignocellulosic materials Galbe, Mats; Wallberg, Ola Biotechnology for Biofuels, Vol. 12, Issue 1 https://doi.org/10.1186/s13068-019-1634-1	journal	December 2019