DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Atomic-level structure characterization of biomass pre- and post-lignin treatment by dynamic nuclear polarization-enhanced solid-state NMR

Abstract

Here, lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear 13C–13C correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic-level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determine structure–function relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.

Authors:
 [1];  [2];  [3];  [3]; ORCiD logo [4];  [2]
  1. Ames Lab., Ames, IA (United States)
  2. Purdue Univ., West Lafayette, IN (United States); Univ. of California, Santa Barbara, CA (United States)
  3. Purdue Univ., West Lafayette, IN (United States)
  4. Ames Lab. and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1347417
Report Number(s):
IS-J-9223
Journal ID: ISSN 1089-5639
Grant/Contract Number:  
SC000097; EEC- 0813570; AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 121; Journal Issue: 3; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Perras, Frederic A., Luo, Hao, Zhang, Ximing, Mosier, Nathan S., Pruski, Marek, and Abu-Omar, Mahdi M. Atomic-level structure characterization of biomass pre- and post-lignin treatment by dynamic nuclear polarization-enhanced solid-state NMR. United States: N. p., 2016. Web. doi:10.1021/acs.jpca.6b11121.
Perras, Frederic A., Luo, Hao, Zhang, Ximing, Mosier, Nathan S., Pruski, Marek, & Abu-Omar, Mahdi M. Atomic-level structure characterization of biomass pre- and post-lignin treatment by dynamic nuclear polarization-enhanced solid-state NMR. United States. https://doi.org/10.1021/acs.jpca.6b11121
Perras, Frederic A., Luo, Hao, Zhang, Ximing, Mosier, Nathan S., Pruski, Marek, and Abu-Omar, Mahdi M. Tue . "Atomic-level structure characterization of biomass pre- and post-lignin treatment by dynamic nuclear polarization-enhanced solid-state NMR". United States. https://doi.org/10.1021/acs.jpca.6b11121. https://www.osti.gov/servlets/purl/1347417.
@article{osti_1347417,
title = {Atomic-level structure characterization of biomass pre- and post-lignin treatment by dynamic nuclear polarization-enhanced solid-state NMR},
author = {Perras, Frederic A. and Luo, Hao and Zhang, Ximing and Mosier, Nathan S. and Pruski, Marek and Abu-Omar, Mahdi M.},
abstractNote = {Here, lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear 13C–13C correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic-level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determine structure–function relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.},
doi = {10.1021/acs.jpca.6b11121},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 3,
volume = 121,
place = {United States},
year = {Tue Dec 27 00:00:00 EST 2016},
month = {Tue Dec 27 00:00:00 EST 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 49 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Transformations of biomass-derived platform molecules: from high added-value chemicals to fuels via aqueous-phase processing
journal, January 2011

  • Serrano-Ruiz, Juan Carlos; Luque, Rafael; Sepúlveda-Escribano, Antonio
  • Chemical Society Reviews, Vol. 40, Issue 11, p. 5266-5281
  • DOI: 10.1039/c1cs15131b

Lignin depolymerisation strategies: towards valuable chemicals and fuels
journal, January 2014

  • Xu, Chunping; Arancon, Rick Arneil D.; Labidi, Jalel
  • Chemical Society Reviews, Vol. 43, Issue 22, p. 7485-7500
  • DOI: 10.1039/C4CS00235K

Lignocellulose conversion: an introduction to chemistry, process and economics
journal, January 2007

  • Lange, Jean-Paul
  • Biofuels, Bioproducts and Biorefining, Vol. 1, Issue 1, p. 39-48
  • DOI: 10.1002/bbb.7

The Path Forward for Biofuels and Biomaterials
journal, January 2006

  • Ragauskas, Arthur J.; Williams, Charlotte K.; Davison, Brian H.
  • Science, Vol. 311, Issue 5760, p. 484-489
  • DOI: 10.1126/science.1114736

From fossil to green
journal, January 1999

  • Okkerse, C.; van Bekkum, H.
  • Green Chemistry, Vol. 1, Issue 2
  • DOI: 10.1039/a809539f

The Study of Cellulose Structure and Depolymerization Through Single-Molecule Methods
journal, February 2015

  • Rose, Markus; Babi, Mouhanad; Moran-Mirabal, Jose
  • Industrial Biotechnology, Vol. 11, Issue 1
  • DOI: 10.1089/ind.2014.0019

Biomass recalcitrance. Part I: the chemical compositions and physical structures affecting the enzymatic hydrolysis of lignocellulose
journal, March 2012

  • Zhao, Xuebing; Zhang, Lihua; Liu, Dehua
  • Biofuels, Bioproducts and Biorefining, Vol. 6, Issue 4
  • DOI: 10.1002/bbb.1331

Ionic liquid-mediated selective extraction of lignin from wood leading to enhanced enzymatic cellulose hydrolysis
journal, April 2009

  • Lee, Sang Hyun; Doherty, Thomas V.; Linhardt, Robert J.
  • Biotechnology and Bioengineering, Vol. 102, Issue 5, p. 1368-1376
  • DOI: 10.1002/bit.22179

Cellulose crystallinity - a key predictor of the enzymatic hydrolysis rate: Cellulose crystallinity
journal, February 2010


Variations in Cellulosic Ultrastructure of Poplar
journal, October 2009


Novel enzymes for the degradation of cellulose
journal, January 2012

  • Horn, Svein; Vaaje-Kolstad, Gustav; Westereng, Bjørge
  • Biotechnology for Biofuels, Vol. 5, Issue 1, Article No. 45
  • DOI: 10.1186/1754-6834-5-45

Methods for Pretreatment of Lignocellulosic Biomass for Efficient Hydrolysis and Biofuel Production
journal, April 2009

  • Kumar, Parveen; Barrett, Diane M.; Delwiche, Michael J.
  • Industrial & Engineering Chemistry Research, Vol. 48, Issue 8, p. 3713-3729
  • DOI: 10.1021/ie801542g

Saccharification of recalcitrant biomass and integration options for lignocellulosic sugars from Catchlight Energy’s sugar process (CLE Sugar)
journal, January 2013

  • Gao, Johnway; Anderson, Dwight; Levie, Benjamin
  • Biotechnology for Biofuels, Vol. 6, Issue 1
  • DOI: 10.1186/1754-6834-6-10

Features of promising technologies for pretreatment of lignocellulosic biomass
journal, April 2005


Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment
journal, January 2011

  • Chundawat, Shishir P. S.; Donohoe, Bryon S.; da Costa Sousa, Leonardo
  • Energy & Environmental Science, Vol. 4, Issue 3, 973
  • DOI: 10.1039/c0ee00574f

CP/MAS 13C NMR analysis of cellulase treated bleached softwood kraft pulp
journal, April 2006


One step catalytic conversion of cellulose to sustainable chemicals utilizing cooperative ionic liquid pairs
journal, January 2011

  • Long, Jinxing; Guo, Bin; Li, Xuehui
  • Green Chemistry, Vol. 13, Issue 9
  • DOI: 10.1039/c1gc15597k

Catalytic Conversion of Cellulose into Sugar Alcohols
journal, August 2006


Catalytic Conversion of Carbohydrates into 5-Hydroxymethylfurfural by Germanium(IV) Chloride in Ionic Liquids
journal, December 2010


Catalytic conversion of biomass-derived carbohydrates into fuels and chemicals via furanic aldehydes
journal, January 2012


Kinetics of Maleic Acid and Aluminum Chloride Catalyzed Dehydration and Degradation of Glucose
journal, March 2015

  • Zhang, Ximing; Hewetson, Barron B.; Mosier, Nathan S.
  • Energy & Fuels, Vol. 29, Issue 4
  • DOI: 10.1021/ef502461s

Maleic acid and aluminum chloride catalyzed conversion of glucose to 5-(hydroxymethyl) furfural and levulinic acid in aqueous media
journal, January 2016

  • Zhang, Ximing; Murria, Priya; Jiang, Yuan
  • Green Chemistry, Vol. 18, Issue 19
  • DOI: 10.1039/C6GC01395C

Speciation and kinetic study of iron promoted sugar conversion to 5-hydroxymethylfurfural (HMF) and levulinic acid (LA)
journal, January 2015

  • Jiang, Yuan; Yang, Linan; Bohn, Christine M.
  • Organic Chemistry Frontiers, Vol. 2, Issue 10
  • DOI: 10.1039/C5QO00194C

Conversion of Hemicellulose to Furfural and Levulinic Acid using Biphasic Reactors with Alkylphenol Solvents
journal, January 2012

  • Gürbüz, Elif I.; Wettstein, Stephanie G.; Dumesic, James A.
  • ChemSusChem, Vol. 5, Issue 2, p. 383-387
  • DOI: 10.1002/cssc.201100608

Recent Development in Chemical Depolymerization of Lignin: A Review
journal, January 2013

  • Wang, Hai; Tucker, Melvin; Ji, Yun
  • Journal of Applied Chemistry, Vol. 2013, p. 1-9
  • DOI: 10.1155/2013/838645

Studies on the Vanadium-Catalyzed Nonoxidative Depolymerization of Miscanthus giganteus-Derived Lignin
journal, April 2013

  • Chan, Julian M. W.; Bauer, Stefan; Sorek, Hagit
  • ACS Catalysis, Vol. 3, Issue 6
  • DOI: 10.1021/cs400333q

Catalytic Lignin Valorization Process for the Production of Aromatic Chemicals and Hydrogen
journal, June 2012

  • Zakzeski, Joseph; Jongerius, Anna L.; Bruijnincx, Pieter C. A.
  • ChemSusChem, Vol. 5, Issue 8
  • DOI: 10.1002/cssc.201100699

Lignin depolymerization (LDP) in alcohol over nickel-based catalysts via a fragmentation–hydrogenolysis process
journal, January 2013

  • Song, Qi; Wang, Feng; Cai, Jiaying
  • Energy & Environmental Science, Vol. 6, Issue 3, p. 994-1007
  • DOI: 10.1039/c2ee23741e

A synergistic biorefinery based on catalytic conversion of lignin prior to cellulose starting from lignocellulosic biomass
journal, January 2015

  • Parsell, Trenton; Yohe, Sara; Degenstein, John
  • Green Chemistry, Vol. 17, Issue 3
  • DOI: 10.1039/C4GC01911C

Total Utilization of Miscanthus Biomass, Lignin and Carbohydrates, Using Earth Abundant Nickel Catalyst
journal, February 2016


Lignin depolymerization over Ni/C catalyst in methanol, a continuation: effect of substrate and catalyst loading
journal, January 2015

  • Klein, Ian; Saha, Basudeb; Abu-Omar, Mahdi M.
  • Catalysis Science & Technology, Vol. 5, Issue 6
  • DOI: 10.1039/C5CY00490J

Advances in solid-state NMR of cellulose
journal, June 2014


Biomass Characterization of Buddleja davidii: A Potential Feedstock for Biofuel Production
journal, February 2009

  • Hallac, Bassem B.; Sannigrahi, Poulomi; Pu, Yunqiao
  • Journal of Agricultural and Food Chemistry, Vol. 57, Issue 4
  • DOI: 10.1021/jf8030277

Multidimensional solid-state NMR spectroscopy of plant cell walls
journal, September 2016


Dynamic nuclear polarization at high magnetic fields
journal, February 2008

  • Maly, Thorsten; Debelouchina, Galia T.; Bajaj, Vikram S.
  • The Journal of Chemical Physics, Vol. 128, Issue 5
  • DOI: 10.1063/1.2833582

Topical Developments in High-Field Dynamic Nuclear Polarization
journal, February 2014

  • Michaelis, Vladimir K.; Ong, Ta-Chung; Kiesewetter, Matthew K.
  • Israel Journal of Chemistry, Vol. 54, Issue 1-2
  • DOI: 10.1002/ijch.201300126

Is solid-state NMR enhanced by dynamic nuclear polarization?
journal, April 2015


Rapid Natural-Abundance 2D 13 C- 13 C Correlation Spectroscopy Using Dynamic Nuclear Polarization Enhanced Solid-State NMR and Matrix-Free Sample Preparation
journal, October 2012

  • Takahashi, Hiroki; Lee, Daniel; Dubois, Lionel
  • Angewandte Chemie International Edition, Vol. 51, Issue 47
  • DOI: 10.1002/anie.201206102

Dynamic Nuclear Polarization NMR Spectroscopy of Microcrystalline Solids
journal, September 2012

  • Rossini, Aaron J.; Zagdoun, Alexandre; Hegner, Franziska
  • Journal of the American Chemical Society, Vol. 134, Issue 40
  • DOI: 10.1021/ja308135r

Matrix-free dynamic nuclear polarization enables solid-state NMR 13C–13C correlation spectroscopy of proteins at natural isotopic abundance
journal, January 2013

  • Takahashi, Hiroki; Hediger, Sabine; De Paëpe, Gaël
  • Chemical Communications, Vol. 49, Issue 82
  • DOI: 10.1039/c3cc45195j

Quantitative Structural Constraints for Organic Powders at Natural Isotopic Abundance Using Dynamic Nuclear Polarization Solid-State NMR Spectroscopy
journal, March 2015

  • Mollica, Giulia; Dekhil, Myriam; Ziarelli, Fabio
  • Angewandte Chemie International Edition, Vol. 54, Issue 20
  • DOI: 10.1002/anie.201501172

Unique aspects of the grass cell wall
journal, June 2008


π-Complexes of Lignols with Manganese(I) and Ruthenium(II)
journal, June 2009

  • Morvan, Didier; Rauchfuss, Thomas B.; Wilson, Scott R.
  • Organometallics, Vol. 28, Issue 11
  • DOI: 10.1021/om9001445

Cell wall cross-linking by ferulates and diferulates in grasses
journal, March 1999


A dehydrotrimer of ferulic acid from maize bran
journal, August 2003


Comparative sugar recovery and fermentation data following pretreatment of poplar wood by leading technologies
journal, March 2009

  • Wyman, Charles E.; Dale, Bruce E.; Elander, Richard T.
  • Biotechnology Progress, Vol. 25, Issue 2
  • DOI: 10.1002/btpr.142

Engineering plant cell walls: tuning lignin monomer composition for deconstructable biofuel feedstocks or resilient biomaterials
journal, January 2014

  • Ciesielski, Peter N.; Resch, Michael G.; Hewetson, Barron
  • Green Chemistry, Vol. 16, Issue 5, p. 2627-2635
  • DOI: 10.1039/c3gc42422g

Physical and chemical characterizations of corn stover and poplar solids resulting from leading pretreatment technologies
journal, September 2009


Adsorption of enzyme onto lignins of liquid hot water pretreated hardwoods: Enzyme Adsorption by Lignin in Hardwood
journal, September 2014

  • Ko, Ja Kyong; Ximenes, Eduardo; Kim, Youngmi
  • Biotechnology and Bioengineering, Vol. 112, Issue 3
  • DOI: 10.1002/bit.25359

An NMR technique for tracing out the carbon skeleton of an organic molecule
journal, April 1981

  • Bax, Ad; Freeman, Ray; Frenkiel, Thomas A.
  • Journal of the American Chemical Society, Vol. 103, Issue 8
  • DOI: 10.1021/ja00398a044

Through-Bond Carbon−Carbon Connectivities in Disordered Solids by NMR
journal, December 1999

  • Lesage, Anne; Bardet, Michel; Emsley, Lyndon
  • Journal of the American Chemical Society, Vol. 121, Issue 47
  • DOI: 10.1021/ja992272b

Mesoporous Silica Nanoparticles Loaded with Surfactant: Low Temperature Magic Angle Spinning 13 C and 29 Si NMR Enhanced by Dynamic Nuclear Polarization
journal, January 2013

  • Lafon, Olivier; Thankamony, Aany S. Lilly; Kobayashi, Takeshi
  • The Journal of Physical Chemistry C, Vol. 117, Issue 3
  • DOI: 10.1021/jp310109s

Sensitivity-enhanced solid-state NMR detection of expansin's target in plant cell walls
journal, September 2013

  • Wang, T.; Park, Y. B.; Caporini, M. A.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 41
  • DOI: 10.1073/pnas.1316290110

Highly Efficient, Water-Soluble Polarizing Agents for Dynamic Nuclear Polarization at High Frequency
journal, August 2013

  • Sauvée, Claire; Rosay, Melanie; Casano, Gilles
  • Angewandte Chemie International Edition, Vol. 52, Issue 41
  • DOI: 10.1002/anie.201304657

CP/MAS 13 C NMR Study of Cellulose and Cellulose Derivatives. 1. Complete Assignment of the CP/MAS 13 C NMR Spectrum of the Native Cellulose
journal, June 2002

  • Kono, Hiroyuki; Yunoki, Shunji; Shikano, Tamio
  • Journal of the American Chemical Society, Vol. 124, Issue 25
  • DOI: 10.1021/ja010704o

Exploring the conformational space of amorphous cellulose using NMR chemical shifts
journal, October 2012


Broadband dipolar recoupling in the nuclear magnetic resonance of rotating solids: A compensated C7 pulse sequence
journal, February 1998

  • Hohwy, M.; Jakobsen, H. J.; Edén, M.
  • The Journal of Chemical Physics, Vol. 108, Issue 7
  • DOI: 10.1063/1.475661

Binding-site analysis of the ether linkages between lignin and hemicelluloses in lignin-carbohydrate complexes by DDQ-oxidation.
journal, January 1989

  • Watanabe, Takashi; Ohnishi, Jiro; Yamasaki, Yuko
  • Agricultural and Biological Chemistry, Vol. 53, Issue 8
  • DOI: 10.1271/bbb1961.53.2233

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

Using Neural Networks for 13C NMR Chemical Shift Prediction–Comparison with Traditional Methods
journal, August 2002

  • Meiler, Jens; Maier, Walter; Will, Martin
  • Journal of Magnetic Resonance, Vol. 157, Issue 2
  • DOI: 10.1006/jmre.2002.2599

Works referencing / citing this record:

Lignin extraction and catalytic upgrading from genetically modified poplar
journal, January 2018


Structure, chemistry and physicochemistry of lignin for material functionalization
journal, August 2019

  • Erfani Jazi, Mehdi; Narayanan, Ganesh; Aghabozorgi, Fatemeh
  • SN Applied Sciences, Vol. 1, Issue 9
  • DOI: 10.1007/s42452-019-1126-8

Molecular-level driving forces in lignocellulosic biomass deconstruction for bioenergy
journal, October 2018


Structural Characterization of Lignin and Its Degradation Products with Spectroscopic Methods
journal, January 2017


A two-stage pretreatment using acidic dioxane followed by dilute hydrochloric acid on sugar production from corn stover
journal, January 2017

  • An, Shengxin; Li, Wenzhi; Liu, Qiyu
  • RSC Advances, Vol. 7, Issue 52
  • DOI: 10.1039/c7ra05280d

Selective Cleavage of C−O Bonds in Lignin Catalyzed by Rhenium(VII) Oxide (Re 2 O 7 )
journal, May 2018


Large-scale ab initio simulations of MAS DNP enhancements using a Monte Carlo optimization strategy
journal, October 2018

  • Perras, Frédéric A.; Pruski, Marek
  • The Journal of Chemical Physics, Vol. 149, Issue 15
  • DOI: 10.1063/1.5042651

Atomic resolution of cotton cellulose structure enabled by dynamic nuclear polarization solid-state NMR
journal, November 2018


Lignin-polysaccharide interactions in plant secondary cell walls revealed by solid-state NMR
journal, January 2019


Selective Cleavage of C−O Bonds in Lignin Catalyzed by Rhenium(VII) Oxide (Re 2 O 7 )
journal, March 2018


Lignin-polysaccharide interactions in plant secondary cell walls revealed by solid-state NMR
journal, January 2019