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Title: A review of whole cell wall NMR by the direct-dissolution of biomass

Abstract

To fully realize the potential of lignocellulosic biomass as a renewable resource for the production of fuels, chemicals, and materials, an improved understanding of the chemical and molecular structures within biomass and how those structures are formed during biosynthesis and transformed during (thermochemical and biological) conversion must be developed. This effort will require analytical techniques which are not only in-depth, rapid, and cost-effective, but also leave native cell wall features intact. Whole plant cell wall nuclear magnetic resonance (NMR) analysis facilitates unparalleled structural characterization of lignocellulosic biomass without causing (or with minimal) structural modification. The objective of this review is to summarize research pertaining to solution- or gel-state whole plant cell wall NMR analysis of biomass, demonstrating the capability of NMR to delineate the structural features and transformations of biomass. In particular, this review will focus on the application of a two-dimensional solution-state NMR technique and perdeuterated ionic liquid based organic electrolyte solvents for the direct dissolution and analysis of biomass. Furthermore, we believe this type of analysis will be critical to advancing biofuel research, improving bioprocessing methodology, and enhancing plant bioengineering efforts.

Authors:
 [1];  [2];  [3];  [4]
  1. Dept. of Energy (DOE) Bioenergy Science Center (BESC) (United States); Washington Univ., St. Louis, MO (United States)
  2. Georgia Inst. of Technology, Atlanta, GA (United States)
  3. Washington Univ., St. Louis, MO (United States)
  4. Dept. of Energy (DOE) Bioenergy Science Center (BESC) (United States); Georgia Inst. of Technology, Atlanta, GA (United States); Univ. of Tennessee, Knoxville, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1266000
Alternate Identifier(s):
OSTI ID: 1327727
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 18; Journal Issue: 3; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
09 BIOMASS FUELS

Citation Formats

Foston, Marcus B., Samuel, Reichel, He, Jian, and Ragauskas, Arthur J. A review of whole cell wall NMR by the direct-dissolution of biomass. United States: N. p., 2016. Web. doi:10.1039/C5GC02828K.
Foston, Marcus B., Samuel, Reichel, He, Jian, & Ragauskas, Arthur J. A review of whole cell wall NMR by the direct-dissolution of biomass. United States. https://doi.org/10.1039/C5GC02828K
Foston, Marcus B., Samuel, Reichel, He, Jian, and Ragauskas, Arthur J. Tue . "A review of whole cell wall NMR by the direct-dissolution of biomass". United States. https://doi.org/10.1039/C5GC02828K. https://www.osti.gov/servlets/purl/1266000.
@article{osti_1266000,
title = {A review of whole cell wall NMR by the direct-dissolution of biomass},
author = {Foston, Marcus B. and Samuel, Reichel and He, Jian and Ragauskas, Arthur J.},
abstractNote = {To fully realize the potential of lignocellulosic biomass as a renewable resource for the production of fuels, chemicals, and materials, an improved understanding of the chemical and molecular structures within biomass and how those structures are formed during biosynthesis and transformed during (thermochemical and biological) conversion must be developed. This effort will require analytical techniques which are not only in-depth, rapid, and cost-effective, but also leave native cell wall features intact. Whole plant cell wall nuclear magnetic resonance (NMR) analysis facilitates unparalleled structural characterization of lignocellulosic biomass without causing (or with minimal) structural modification. The objective of this review is to summarize research pertaining to solution- or gel-state whole plant cell wall NMR analysis of biomass, demonstrating the capability of NMR to delineate the structural features and transformations of biomass. In particular, this review will focus on the application of a two-dimensional solution-state NMR technique and perdeuterated ionic liquid based organic electrolyte solvents for the direct dissolution and analysis of biomass. Furthermore, we believe this type of analysis will be critical to advancing biofuel research, improving bioprocessing methodology, and enhancing plant bioengineering efforts.},
doi = {10.1039/C5GC02828K},
journal = {Green Chemistry},
number = 3,
volume = 18,
place = {United States},
year = {Tue Jan 19 00:00:00 EST 2016},
month = {Tue Jan 19 00:00:00 EST 2016}
}

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Cited by: 42 works
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Works referenced in this record:

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

Ester linkages between lignin and glucuronoxylan in a lignin-carbohydrate complex from beech (Fagus crenata) wood
journal, January 1988

  • Takahashi, N.; Koshijima, T.
  • Wood Science and Technology, Vol. 22, Issue 3
  • DOI: 10.1007/BF00386018

Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production
journal, February 2007

  • Himmel, M. E.; Ding, S.-Y.; Johnson, D. K.
  • Science, Vol. 315, Issue 5813, p. 804-807
  • DOI: 10.1126/science.1137016

Selective, Nickel-Catalyzed Hydrogenolysis of Aryl Ethers
journal, April 2011


Lignin-based carbon fibers for composite fiber applications
journal, January 2002


Bio-fuels from thermochemical conversion of renewable resources: A review
journal, February 2008

  • Goyal, H. B.; Seal, Diptendu; Saxena, R. C.
  • Renewable and Sustainable Energy Reviews, Vol. 12, Issue 2
  • DOI: 10.1016/j.rser.2006.07.014

Biomass Characterization: Recent Progress in Understanding Biomass Recalcitrance
journal, August 2012

  • Foston, Marcus; Ragauskas, Arthur J.
  • Industrial Biotechnology, Vol. 8, Issue 4
  • DOI: 10.1089/ind.2012.0015

Methods in Lignin Chemistry
book, January 1992


Elucidation of Lignin Structure through Degradative Methods:  Comparison of Modified DFRC and Thioacidolysis
journal, June 2003

  • Holtman, Kevin M.; Chang, Hou-Min; Jameel, Hasan
  • Journal of Agricultural and Food Chemistry, Vol. 51, Issue 12
  • DOI: 10.1021/jf0340411

Recent Advances in Characterization of Lignin Polymer by Solution-State Nuclear Magnetic Resonance (NMR) Methodology
journal, January 2013

  • Wen, Jia-Long; Sun, Shao-Long; Xue, Bai-Liang
  • Materials, Vol. 6, Issue 1
  • DOI: 10.3390/ma6010359

Hydrothermal Carbon from Biomass: Structural Differences between Hydrothermal and Pyrolyzed Carbons via 13 C Solid State NMR
journal, December 2011

  • Falco, Camillo; Perez Caballero, Fernando; Babonneau, Florence
  • Langmuir, Vol. 27, Issue 23
  • DOI: 10.1021/la202361p

Solution-State NMR of Lignocellulosic Biomass
journal, June 2011

  • Lu, Fachuang; Ralph, John
  • Journal of Biobased Materials and Bioenergy, Vol. 5, Issue 2
  • DOI: 10.1166/jbmb.2011.1131

Solvents applied in the field of cellulose chemistry: a mini review
journal, June 2005


Dissolution of Cellose with Ionic Liquids
journal, May 2002

  • Swatloski, Richard P.; Spear, Scott K.; Holbrey, John D.
  • Journal of the American Chemical Society, Vol. 124, Issue 18, p. 4974-4975
  • DOI: 10.1021/ja025790m

Ionic Liquids and Their Interaction with Cellulose
journal, December 2009

  • Pinkert, André; Marsh, Kenneth N.; Pang, Shusheng
  • Chemical Reviews, Vol. 109, Issue 12
  • DOI: 10.1021/cr9001947

Synthesis of Transportation Fuels from Biomass: Chemistry, Catalysts, and Engineering
journal, September 2006

  • Huber, George W.; Iborra, Sara; Corma, Avelino
  • Chemical Reviews, Vol. 106, Issue 9, p. 4044-4098
  • DOI: 10.1021/cr068360d

Can ionic liquids dissolve wood? Processing and analysis of lignocellulosic materials with 1-n-butyl-3-methylimidazolium chloride
journal, January 2007

  • Fort, Diego A.; Remsing, Richard C.; Swatloski, Richard P.
  • Green Chemistry, Vol. 9, Issue 1, p. 63-69
  • DOI: 10.1039/B607614A

Ionic Liquid as a Green Solvent for Lignin
journal, April 2007

  • Pu, Yunqiao; Jiang, Nan; Ragauskas, Arthur J.
  • Journal of Wood Chemistry and Technology, Vol. 27, Issue 1
  • DOI: 10.1080/02773810701282330

Dissolution of Wood in Ionic Liquids
journal, October 2007

  • Kilpeläinen, Ilkka; Xie, Haibo; King, Alistair
  • Journal of Agricultural and Food Chemistry, Vol. 55, Issue 22
  • DOI: 10.1021/jf071692e

Lignin solubility in non-imidazolium ionic liquids: Lignin solubility in non-imidazolium ILs
journal, August 2014

  • Glas, Daan; Van Doorslaer, Charlie; Depuydt, Daphne
  • Journal of Chemical Technology & Biotechnology, Vol. 90, Issue 10
  • DOI: 10.1002/jctb.4492

On the solubility of wood in non-derivatising ionic liquids
journal, January 2013

  • Kyllönen, Lasse; Parviainen, Arno; Deb, Somdatta
  • Green Chemistry, Vol. 15, Issue 9
  • DOI: 10.1039/c3gc41273c

Perdeuterated pyridinium molten salt (ionic liquid) for direct dissolution and NMR analysis of plant cell walls
journal, January 2009

  • Jiang, Nan; Pu, Yunqiao; Samuel, Reichel
  • Green Chemistry, Vol. 11, Issue 11
  • DOI: 10.1039/b913609f

Rapid Determination of Lignin Content via Direct Dissolution and 1H NMR Analysis of Plant Cell Walls
journal, September 2010


Comparing the Recalcitrance of Eucalyptus, Pine, and Switchgrass Using Ionic Liquid and Dilute Acid Pretreatments
journal, May 2012


Solution-State 2D NMR Spectroscopy of Plant Cell Walls Enabled by a Dimethylsulfoxide- d 6 /1-Ethyl-3-methylimidazolium Acetate Solvent
journal, March 2013

  • Cheng, Kun; Sorek, Hagit; Zimmermann, Herbert
  • Analytical Chemistry, Vol. 85, Issue 6
  • DOI: 10.1021/ac303529v

Dissolution and Gelation of Cellulose in TBAF/DMSO Solutions: The Roles of Fluoride Ions and Water
journal, September 2009

  • Östlund, Åsa; Lundberg, Dan; Nordstierna, Lars
  • Biomacromolecules, Vol. 10, Issue 9
  • DOI: 10.1021/bm900667q

Short Note: Rapid NMR Method for Determination of Threo: Erythro Ratios in Lignin Model Compounds
journal, January 1985


Evidence for Increased Steric Compression in Anti Compared to Syn Lignin Model Quinone Methides
journal, March 1990

  • Ede, Richard M.; Main, Lyndsay; Ralph, John
  • Journal of Wood Chemistry and Technology, Vol. 10, Issue 1
  • DOI: 10.1080/02773819008050229

Lignin–feruloyl ester cross-links in grasses. Part 2. Model compound syntheses
journal, January 1992

  • Ralph, John; Helm, Richard F.; Quideau, Stéphane
  • J. Chem. Soc., Perkin Trans. 1, Issue 21
  • DOI: 10.1039/P19920002971

1H NMR of acetylated β-ether/β-ether lignin model trimers
journal, April 1993


Preparation of synthetic lignins with superior NMR characteristics via isotopically labeled monolignols
journal, January 1998

  • Ralph, John; Zhang, Yingsheng; M. Ede, Richard
  • Journal of the Chemical Society, Perkin Transactions 1, Issue 16
  • DOI: 10.1039/a803281e

Assignment of 2D TOCSY Spectra of Lignins: the Role of Lignin Model Compounds
journal, April 1996


NMR Studies on the Occurrence of Spirodienone Structures in Lignins
journal, April 2006

  • Zhang, Liming; Gellerstedt, Göran; Ralph, John
  • Journal of Wood Chemistry and Technology, Vol. 26, Issue 1
  • DOI: 10.1080/02773810600580271

Lignin-hydroxycinnamyl model compounds related to forage cell wall structure. 1. Ether-linked structures
journal, November 1992

  • Helm, Richard F.; Ralph, John.
  • Journal of Agricultural and Food Chemistry, Vol. 40, Issue 11
  • DOI: 10.1021/jf00023a025

Lignin-hydroxycinnamoyl model compounds related to forage cell wall structure. 2. Ester-linked structures
journal, April 1993

  • Helm, Richard F.; Ralph, John.
  • Journal of Agricultural and Food Chemistry, Vol. 41, Issue 4
  • DOI: 10.1021/jf00028a013

NMR Studies of Lignins. 1. Signals Due to Protons in Formyl Groups.
journal, January 1977


NMR Studies of Lignins. 3. 1H NMR Spectroscopic Data for Lignin Model Compounds.
journal, January 1979


NMR Studies of Lignins. 5. Investigation of Non-derivatized Spruce and Birch Lignin by 1H NMR Spectroscopy.
journal, January 1981


On the Occurrence of β-1 Structures in Lignins
journal, January 1987


Quantitative 13C NMR Analysis of Kraft Lignins.
journal, January 1987


Identification of Lignin and Polysaccharide Modifications in Populus Wood by Chemometric Analysis of 2D NMR Spectra from Dissolved Cell Walls
journal, September 2009

  • Hedenström, Mattias; Wiklund-Lindström, Susanne; Öman, Tommy
  • Molecular Plant, Vol. 2, Issue 5
  • DOI: 10.1093/mp/ssp047

Solution-state 2D NMR of Ball-milled Plant Cell Wall Gels in DMSO-d 6
journal, March 2008


Unveiling the Structural Heterogeneity of Bamboo Lignin by In Situ HSQC NMR Technique
journal, June 2012


Heteronuclear Single-Quantum Coherence Nuclear Magnetic Resonance (HSQC NMR) Characterization of Acetylated Fir (Abies sachallnensis MAST) Wood Regenerated from Ionic Liquid
journal, May 2011

  • Qu, Chen; Kishimoto, Takao; Kishino, Masanori
  • Journal of Agricultural and Food Chemistry, Vol. 59, Issue 10
  • DOI: 10.1021/jf200498n

Characterization of nonderivatized plant cell walls using high-resolution solution-state NMR spectroscopy
journal, June 2008

  • Yelle, Daniel J.; Ralph, John; Frihart, Charles R.
  • Magnetic Resonance in Chemistry, Vol. 46, Issue 6
  • DOI: 10.1002/mrc.2201

Whole plant cell wall characterization using solution-state 2D NMR
journal, August 2012


Solution-state 2D NMR of ball-milled plant cell wall gels in DMSO-d6/pyridine-d5
journal, January 2010

  • Kim, Hoon; Ralph, John
  • Org. Biomol. Chem., Vol. 8, Issue 3
  • DOI: 10.1039/B916070A

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

  • Chen, F.; Tobimatsu, Y.; Havkin-Frenkel, D.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 5
  • DOI: 10.1073/pnas.1120992109

Changes in the Structure of the Cellulose Fiber Wall during Dilute Acid Pretreatment in Populus Studied by 1 H and 2 H NMR
journal, October 2010

  • Foston, Marcus; Ragauskas, Arthur J.
  • Energy & Fuels, Vol. 24, Issue 10
  • DOI: 10.1021/ef100882t

NMR Spectroscopy: Data Acquisition
book, September 2001


A comprehensive discussion of HSQC and HMQC pulse sequences
journal, January 2004

  • Mandal, Pravat K.; Majumdar, Ananya
  • Concepts in Magnetic Resonance, Vol. 20A, Issue 1
  • DOI: 10.1002/cmr.a.10095

Quantitative 2D HSQC NMR determination of polymer structures by selecting suitable internal standard references
journal, January 2007

  • Zhang, Liming; Gellerstedt, Göran
  • Magnetic Resonance in Chemistry, Vol. 45, Issue 1
  • DOI: 10.1002/mrc.1914

Quantitative 2D HSQC (Q-HSQC) via Suppression of J -Dependence of Polarization Transfer in NMR Spectroscopy:  Application to Wood Lignin
journal, April 2003

  • Heikkinen, Sami; Toikka, Merja M.; Karhunen, Pirkko T.
  • Journal of the American Chemical Society, Vol. 125, Issue 14
  • DOI: 10.1021/ja029035k

Elucidation of Lignin Structure by Quantitative 2D NMR
journal, June 2011

  • Sette, Marco; Wechselberger, Rainer; Crestini, Claudia
  • Chemistry - A European Journal, Vol. 17, Issue 34
  • DOI: 10.1002/chem.201003045

Structural changes in switchgrass lignin and hemicelluloses during pretreatments by NMR analysis
journal, November 2011


High-resolution 13C NMR studies of cellulose and cellulose oligomers in ionic liquid solutions
journal, January 2005

  • Moulthrop, Jason S.; Swatloski, Richard P.; Moyna, Guillermo
  • Chemical Communications, Issue 12
  • DOI: 10.1039/b417745b

1H NMR analysis of cellulose dissolved in non-deuterated ionic liquids
journal, May 2014


1 H NMR Evaluation of Polar and Nondeuterated Ionic Liquids for Selective Extraction of Cellulose and Xylan from Wheat Bran
journal, July 2014

  • Kuroda, Kosuke; Kunimura, Haruhito; Fukaya, Yukinobu
  • ACS Sustainable Chemistry & Engineering, Vol. 2, Issue 9
  • DOI: 10.1021/sc500407a

Chemical, ultrastructural and supramolecular analysis of tension wood in Populus tremula x alba as a model substrate for reduced recalcitrance
journal, January 2011

  • Foston, Marcus; Hubbell, Christopher A.; Samuel, Reichel
  • Energy & Environmental Science, Vol. 4, Issue 12
  • DOI: 10.1039/c1ee02073k

Structural characterization of alkaline hydrogen peroxide pretreated grasses exhibiting diverse lignin phenotypes
journal, January 2012

  • Li, Muyang; Foster, Cliff; Kelkar, Shantanu
  • Biotechnology for Biofuels, Vol. 5, Issue 1
  • DOI: 10.1186/1754-6834-5-38

Deuterium incorporation in biomass cell wall components by NMR analysis
journal, January 2012

  • Foston, Marcus B.; McGaughey, Joseph; O'Neill, Hugh
  • The Analyst, Vol. 137, Issue 5
  • DOI: 10.1039/c2an16025k

The effect of deuteration on the structure of bacterial cellulose
journal, June 2013


13C cell wall enrichment and ionic liquid NMR analysis: progress towards a high-throughput detailed chemical analysis of the whole plant cell wall
journal, January 2012

  • Foston, Marcus; Samuel, Reichel; Ragauskas, Arthur J.
  • The Analyst, Vol. 137, Issue 17
  • DOI: 10.1039/c2an35344j

Hydrophobic Interactions Determining Functionalized Lignocellulose Solubility in Dialkylimidazolium Chlorides, as Probed by 31 P NMR
journal, February 2009

  • King, Alistair W. T.; Kilpeläinen, Ilkka; Heikkinen, Sami
  • Biomacromolecules, Vol. 10, Issue 2
  • DOI: 10.1021/bm8010159

In Situ Determination of Lignin Phenolics and Wood Solubility in Imidazolium Chlorides Using 31 P NMR
journal, September 2009

  • King, Alistair W. T.; Zoia, Luca; Filpponen, Ilari
  • Journal of Agricultural and Food Chemistry, Vol. 57, Issue 18
  • DOI: 10.1021/jf901095w

Quantitative 31P NMR analysis of solid wood offers an insight into the acetylation of its components
journal, November 2014


Heterobimetallic complexes CpNiCo(CO)2(PPh3)(PhC2C6H4-R -p): their synthesis, electrochemistry and ESR
journal, November 1991

  • Sun, Shou-Heng; Meng, Qing-Jin; Zhu, Hui-Zhen
  • Chinese Journal of Chemistry, Vol. 9, Issue 6
  • DOI: 10.1002/cjoc.19910090602

Plant cell wall profiling by fast maximum likelihood reconstruction (FMLR) and region-of-interest (ROI) segmentation of solution-state 2D 1H–13C NMR spectra
journal, January 2013

  • Chylla, Roger A.; Van Acker, Rebecca; Kim, Hoon
  • Biotechnology for Biofuels, Vol. 6, Issue 1
  • DOI: 10.1186/1754-6834-6-45

Works referencing / citing this record:

Novel Synthesis of Immobilized Brønsted‐ Acidic Ionic Liquid: Application in Lignin Depolymerization
journal, May 2018


Opportunities of Ionic Liquids for Lignin Utilization from Biorefinery
journal, July 2018


Chemical and thermal properties of precipitates made from hydrolysate of spruce wood chips
journal, May 2019


Formic-Acid-Induced using Recyclable-Ionic Liquids as Catalysts for Lignin Conversion into Aromatic Co-Products
journal, November 2019


Ionic liquids catalyzed lignin liquefaction: mechanistic studies using TPO-MS, FT-IR, RAMAN and 1D, 2D-HSQC/NOSEY NMR
journal, January 2016

  • Singh, Sandip K.; Dhepe, Paresh L.
  • Green Chemistry, Vol. 18, Issue 14
  • DOI: 10.1039/c6gc00771f

Hyperpolarised NMR to follow water proton transport through membrane channels via exchange with biomolecules
journal, January 2018

  • Nastasa, Viorel; Stavarache, Cristina; Hanganu, Anamaria
  • Faraday Discussions, Vol. 209
  • DOI: 10.1039/c8fd00021b