Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics
Abstract
The deconstruction of cellulose is an essential step in the production of ethanol from lignocellulosic biomass. However, the presence of lignin hinders this process. Recently, a novel cosolvent based biomass pretreatment method called CELF (Cosolvent Enhanced Lignocellulosic Fractionation) which employs tetrahydrofuran (THF) in a single phase mixture with water, was found to be highly effective at solubilizing and extracting lignin from lignocellulosic biomass and achieving high yields of fermentable sugars. Here, using all-atom molecular-dynamics simulation, we find that THF preferentially solvates lignin, and in doing so, shifts the equilibrium configurational distribution of the biopolymer from a crumpled globule to coil, independent of temperature. Whereas pure water is a bad solvent for lignin, the THF : water cosolvent acts as a "theta" solvent, in which solvent : lignin and lignin : lignin interactions are approximately equivalent in strength. Furthermore, under these conditions, polymers do not aggregate, thus providing a mechanism for the observed lignin solubilization that facilitates unfettered access of celluloytic enzymes to cellulose.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Univ. of California, Riverside, CA (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). BioEnergy Science Center (BESC)
- Sponsoring Org.:
- USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1327653
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Green Chemistry
- Additional Journal Information:
- Journal Volume: 18; Journal Issue: 5; Journal ID: ISSN 1463-9262
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 09 BIOMASS FUELS
Citation Formats
Smith, Micholas Dean, Mostofian, Barmak, Cheng, Xiaolin, Petridis, Loukas, Cai, Charles M., Wyman, Charles E., and Smith, Jeremy C. Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics. United States: N. p., 2015.
Web. doi:10.1039/C5GC01952D.
Smith, Micholas Dean, Mostofian, Barmak, Cheng, Xiaolin, Petridis, Loukas, Cai, Charles M., Wyman, Charles E., & Smith, Jeremy C. Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics. United States. https://doi.org/10.1039/C5GC01952D
Smith, Micholas Dean, Mostofian, Barmak, Cheng, Xiaolin, Petridis, Loukas, Cai, Charles M., Wyman, Charles E., and Smith, Jeremy C. Mon .
"Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics". United States. https://doi.org/10.1039/C5GC01952D. https://www.osti.gov/servlets/purl/1327653.
@article{osti_1327653,
title = {Cosolvent pretreatment in cellulosic biofuel production: Effect of tetrahydrofuran-water on lignin structure and dynamics},
author = {Smith, Micholas Dean and Mostofian, Barmak and Cheng, Xiaolin and Petridis, Loukas and Cai, Charles M. and Wyman, Charles E. and Smith, Jeremy C.},
abstractNote = {The deconstruction of cellulose is an essential step in the production of ethanol from lignocellulosic biomass. However, the presence of lignin hinders this process. Recently, a novel cosolvent based biomass pretreatment method called CELF (Cosolvent Enhanced Lignocellulosic Fractionation) which employs tetrahydrofuran (THF) in a single phase mixture with water, was found to be highly effective at solubilizing and extracting lignin from lignocellulosic biomass and achieving high yields of fermentable sugars. Here, using all-atom molecular-dynamics simulation, we find that THF preferentially solvates lignin, and in doing so, shifts the equilibrium configurational distribution of the biopolymer from a crumpled globule to coil, independent of temperature. Whereas pure water is a bad solvent for lignin, the THF : water cosolvent acts as a "theta" solvent, in which solvent : lignin and lignin : lignin interactions are approximately equivalent in strength. Furthermore, under these conditions, polymers do not aggregate, thus providing a mechanism for the observed lignin solubilization that facilitates unfettered access of celluloytic enzymes to cellulose.},
doi = {10.1039/C5GC01952D},
journal = {Green Chemistry},
number = 5,
volume = 18,
place = {United States},
year = {Mon Oct 05 00:00:00 EDT 2015},
month = {Mon Oct 05 00:00:00 EDT 2015}
}
Web of Science
Works referenced in this record:
Bioenergy and Sustainable Development?
journal, November 2007
- Sagar, Ambuj D.; Kartha, Sivan
- Annual Review of Environment and Resources, Vol. 32, Issue 1
A review of cellulosic biofuel commercial-scale projects in the United States
journal, February 2013
- Brown, Tristan R.; Brown, Robert C.
- Biofuels, Bioproducts and Biorefining, Vol. 7, Issue 3
A techno-economic review of thermochemical cellulosic biofuel pathways
journal, February 2015
- Brown, Tristan R.
- Bioresource Technology, Vol. 178
Pretreatment: the key to unlocking low-cost cellulosic ethanol
journal, January 2008
- Yang, Bin; Wyman, Charles E.
- Biofuels, Bioproducts and Biorefining, Vol. 2, Issue 1
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
Hydrolysis of lignocellulosic materials for ethanol production: a review
journal, May 2002
- Sun, Ye; Cheng, Jiayang
- Bioresource Technology, Vol. 83, Issue 1, p. 1-11
Lignin Impact on Fiber Degradation. 3. Reversal of Inhibition of Enzymatic Hydrolysis by Chemical Modification of Lignin and by Additives
journal, May 1997
- Sewalt, V. J. H.; Glasser, W. G.; Beauchemin, K. A.
- Journal of Agricultural and Food Chemistry, Vol. 45, Issue 5
How Does Plant Cell Wall Nanoscale Architecture Correlate with Enzymatic Digestibility?
journal, November 2012
- Ding, S. -Y.; Liu, Y. -S.; Zeng, Y.
- Science, Vol. 338, Issue 6110
Integrated furfural production as a renewable fuel and chemical platform from lignocellulosic biomass: Furfural production from lignocellulosic biomass
journal, August 2013
- Cai, Charles M.; Zhang, Taiying; Kumar, Rajeev
- Journal of Chemical Technology & Biotechnology, Vol. 89, Issue 1
Lignin Valorization: Improving Lignin Processing in the Biorefinery
journal, May 2014
- Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.
- Science, Vol. 344, Issue 6185, p. 1246843-1246843
Enzymatic conversion of lignocellulose into fermentable sugars: challenges and opportunities
journal, October 2007
- Jørgensen, Henning; Kristensen, Jan Bach; Felby, Claus
- Biofuels, Bioproducts and Biorefining, Vol. 1, Issue 2
The lignin present in steam pretreated softwood binds enzymes and limits cellulose accessibility
journal, January 2012
- Kumar, Linoj; Arantes, Valdeir; Chandra, Richard
- Bioresource Technology, Vol. 103, Issue 1
Investigation of lignin deposition on cellulose during hydrothermal pretreatment, its effect on cellulose hydrolysis, and underlying mechanisms: Investigation of Lignin Deposition on Cellulose
journal, October 2013
- Li, Hongjia; Pu, Yunqiao; Kumar, Rajeev
- Biotechnology and Bioengineering, Vol. 111, Issue 3
Modifying plants for biofuel and biomaterial production
journal, November 2014
- Furtado, Agnelo; Lupoi, Jason S.; Hoang, Nam V.
- Plant Biotechnology Journal, Vol. 12, Issue 9
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
Coupling metal halides with a co-solvent to produce furfural and 5-HMF at high yields directly from lignocellulosic biomass as an integrated biofuels strategy
journal, January 2014
- Cai, Charles M.; Nagane, Nikhil; Kumar, Rajeev
- Green Chem., Vol. 16, Issue 8
Selective conversion of lignin in corncob residue to monophenols with high yield and selectivity
journal, January 2014
- Jiang, Zhicheng; He, Ting; Li, Jianmei
- Green Chem., Vol. 16, Issue 9
Co-solvent Pretreatment Reduces Costly Enzyme Requirements for High Sugar and Ethanol Yields from Lignocellulosic Biomass
journal, February 2015
- Nguyen, Thanh Yen; Cai, Charles M.; Kumar, Rajeev
- ChemSusChem, Vol. 8, Issue 10
Biopolymers: Lignin, Proteins, Bioactive Nanocomposites
book, January 2010
- Abe, Akihiro; Dusek, Karel; Kobayashi, Shiro
- Advances in Polymer Science
An efficient and economical process for lignin depolymerization in biomass-derived solvent tetrahydrofuran
journal, February 2014
- Long, Jinxing; Zhang, Qi; Wang, Tiejun
- Bioresource Technology, Vol. 154
Assessing the molecular structure basis for biomass recalcitrance during dilute acid and hydrothermal pretreatments
journal, January 2013
- Pu, Yunqiao; Hu, Fan; Huang, Fang
- Biotechnology for Biofuels, Vol. 6, Issue 1
Pseudo-lignin and pretreatment chemistry
journal, January 2011
- Sannigrahi, Poulomi; Kim, Dong Ho; Jung, Seokwon
- Energy Environ. Sci., Vol. 4, Issue 4
Characterization of Alkali Soluble Fraction of Steam Exploded Birch Wood
journal, January 1995
- Jakobsons, Juris; Hortling, Bo; Erins, Peteris
- Holzforschung, Vol. 49, Issue 1
Visualizing lignin coalescence and migration through maize cell walls following thermochemical pretreatment
journal, December 2008
- Donohoe, Bryon S.; Decker, Stephen R.; Tucker, Melvin P.
- Biotechnology and Bioengineering, Vol. 101, Issue 5
Mechanism of surfactant effect in enzymatic hydrolysis of lignocellulose
journal, August 2002
- Eriksson, Torny; Börjesson, Johan; Tjerneld, Folke
- Enzyme and Microbial Technology, Vol. 31, Issue 3
Inhibition of cellulase, xylanase and β-glucosidase activities by softwood lignin preparations
journal, September 2006
- Berlin, Alex; Balakshin, Mikhail; Gilkes, Neil
- Journal of Biotechnology, Vol. 125, Issue 2, p. 198-209
Predicting Enzyme Adsorption to Lignin Films by Calculating Enzyme Surface Hydrophobicity
journal, May 2014
- Sammond, Deanne W.; Yarbrough, John M.; Mansfield, Elisabeth
- Journal of Biological Chemistry, Vol. 289, Issue 30
Cellulase–lignin interactions—The role of carbohydrate-binding module and pH in non-productive binding
journal, October 2013
- Rahikainen, Jenni Liisa; Evans, James David; Mikander, Saara
- Enzyme and Microbial Technology, Vol. 53, Issue 5
Quantitative theory of the globule-to-coil transition. 4. Comparison of theoretical results with experimental data
journal, March 1992
- Grosberg, A. Yu.; Kuznetsov, D. V.
- Macromolecules, Vol. 25, Issue 7
The Configuration of Real Polymer Chains
journal, March 1949
- Flory, Paul J.
- The Journal of Chemical Physics, Vol. 17, Issue 3
Conformations of a polyelectrolyte chain
journal, September 1992
- Ha, Bae-Yeun; Thirumalai, D.
- Physical Review A, Vol. 46, Issue 6
Morphology of Dry Lignins and Size and Shape of Dissolved Kraft Lignin Particles by X-ray Scattering
journal, October 2004
- Vainio, Ulla; Maximova, Natalia; Hortling, Bo
- Langmuir, Vol. 20, Issue 22
Evidence for Complex Molecular Architectures for Solvent-Extracted Lignins
journal, April 2012
- Harton, Shane E.; Pingali, Sai Venkatesh; Nunnery, Grady A.
- ACS Macro Letters, Vol. 1, Issue 5
Supramolecular Interactions in Secondary Plant Cell Walls: Effect of Lignin Chemical Composition Revealed with the Molecular Theory of Solvation
journal, December 2014
- Silveira, Rodrigo L.; Stoyanov, Stanislav R.; Gusarov, Sergey
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 1
Simulation Analysis of the Temperature Dependence of Lignin Structure and Dynamics
journal, December 2011
- Petridis, Loukas; Schulz, Roland; Smith, Jeremy C.
- Journal of the American Chemical Society, Vol. 133, Issue 50
Interactions of Endoglucanases with Amorphous Cellulose Films Resolved by Neutron Reflectometry and Quartz Crystal Microbalance with Dissipation Monitoring
journal, May 2012
- Cheng, Gang; Datta, Supratim; Liu, Zelin
- Langmuir, Vol. 28, Issue 22
Effects of lengthscales and attractions on the collapse of hydrophobic polymers in water
journal, January 2007
- Athawale, Manoj V.; Goel, Gaurav; Ghosh, Tuhin
- Proceedings of the National Academy of Sciences, Vol. 104, Issue 3
Characterization and analysis of the molecular weight of lignin for biorefining studies
journal, June 2014
- Tolbert, Allison; Akinosho, Hannah; Khunsupat, Ratayakorn
- Biofuels, Bioproducts and Biorefining, Vol. 8, Issue 6
Molecular dynamics with coupling to an external bath
journal, October 1984
- Berendsen, H. J. C.; Postma, J. P. M.; van Gunsteren, W. F.
- The Journal of Chemical Physics, Vol. 81, Issue 8
Structural study of aqueous solutions of tetrahydrofuran and acetone mixtures using dielectric relaxation technique
journal, February 1996
- Kumbharkhane, A. C.; Helambe, S. N.; Lokhande, M. P.
- Pramana, Vol. 46, Issue 2
A molecular mechanics force field for lignin
journal, February 2009
- Petridis, Loukas; Smith, Jeremy C.
- Journal of Computational Chemistry, Vol. 30, Issue 3
Additive and Classical Drude Polarizable Force Fields for Linear and Cyclic Ethers
journal, March 2007
- Vorobyov, Igor; Anisimov, Victor M.; Greene, Shannon
- Journal of Chemical Theory and Computation, Vol. 3, Issue 3
Molecular Dynamics Studies of Polyethylene Oxide and Polyethylene Glycol: Hydrodynamic Radius and Shape Anisotropy
journal, August 2008
- Lee, Hwankyu; Venable, Richard M.; MacKerell, Alexander D.
- Biophysical Journal, Vol. 95, Issue 4
GROMACS 4: Algorithms for Highly Efficient, Load-Balanced, and Scalable Molecular Simulation
journal, February 2008
- Hess, Berk; Kutzner, Carsten; van der Spoel, David
- Journal of Chemical Theory and Computation, Vol. 4, Issue 3
GROMACS 4.5: a high-throughput and highly parallel open source molecular simulation toolkit
journal, February 2013
- Pronk, Sander; Páll, Szilárd; Schulz, Roland
- Bioinformatics, Vol. 29, Issue 7
GROMACS: Fast, flexible, and free
journal, January 2005
- Van Der Spoel, David; Lindahl, Erik; Hess, Berk
- Journal of Computational Chemistry, Vol. 26, Issue 16
VMD: Visual molecular dynamics
journal, February 1996
- Humphrey, William; Dalke, Andrew; Schulten, Klaus
- Journal of Molecular Graphics, Vol. 14, Issue 1
3V: cavity, channel and cleft volume calculator and extractor
journal, May 2010
- Voss, N. R.; Gerstein, M.
- Nucleic Acids Research, Vol. 38, Issue Web Server
Scaling law for the radius of gyration of proteins and its dependence on hydrophobicity
journal, January 2009
- Hong, Liu; Lei, Jinzhi
- Journal of Polymer Science Part B: Polymer Physics, Vol. 47, Issue 2
Computational Study of Bond Dissociation Enthalpies for a Large Range of Native and Modified Lignins
journal, October 2011
- Kim, Seonah; Chmely, Stephen C.; Nimlos, Mark R.
- The Journal of Physical Chemistry Letters, Vol. 2, Issue 22
Lignin Hydrolysis and Phosphorylation Mechanism during Phosphoric Acid–Acetone Pretreatment: A DFT Study
journal, December 2014
- Qin, Wu; Wu, Lingnan; Zheng, Zongming
- Molecules, Vol. 19, Issue 12
Works referencing / citing this record:
Solvent Liquefaction
book, March 2019
- Ghosh, Arpa; Haverly, Martin R.
- Thermochemical Processing of Biomass: Conversion into Fuels, Chemicals and Power (Second Edition)
Performances of Several Solvents on the Cleavage of Inter- and Intramolecular Linkages of Lignin in Corncob Residue
journal, April 2018
- Zhang, Hui; Liu, Xudong; Li, Jianmei
- ChemSusChem, Vol. 11, Issue 9
Atomic Force Microscopy and Molecular Dynamics Simulations for Study of Lignin Solution Self‐Assembly Mechanisms in Organic–Aqueous Solvent Mixtures
journal, February 2020
- Wang, Jingyu; Qian, Yong; Li, Libo
- ChemSusChem, Vol. 13, Issue 17
Bioethanol from Lignocellulosic Biomass
book, January 2017
- Wyman, Charles E.; Cai, Charles M.; Kumar, Rajeev
- Encyclopedia of Sustainability Science and Technology
Bioethanol from Lignocellulosic Biomass
book, July 2018
- Wyman, Charles E.; Cai, Charles M.; Kumar, Rajeev
- Energy from Organic Materials (Biomass)
Structures, intermolecular interactions, and chemical hardness of binary water–organic solvents: a molecular dynamics study
journal, September 2018
- Aguilera-Segura, Sonia M.; Di Renzo, Francesco; Mineva, Tzonka
- Journal of Molecular Modeling, Vol. 24, Issue 10
A simple fractionation method and GPC analysis of organosolv extracts obtained from lignocellulosic materials
journal, January 2020
- Andreo-Martínez, Pedro; Ortiz-Martínez, Víctor Manuel; García-Martínez, Nuria
- Biomass Conversion and Biorefinery
Molecular-level driving forces in lignocellulosic biomass deconstruction for bioenergy
journal, October 2018
- Petridis, Loukas; Smith, Jeremy C.
- Nature Reviews Chemistry, Vol. 2, Issue 11
Neutron scattering in the biological sciences: progress and prospects
journal, December 2018
- Ashkar, Rana; Bilheux, Hassina Z.; Bordallo, Heliosa
- Acta Crystallographica Section D Structural Biology, Vol. 74, Issue 12
Performance of three delignifying pretreatments on hardwoods: hydrolysis yields, comprehensive mass balances, and lignin properties
journal, September 2019
- Bhalla, Aditya; Cai, Charles M.; Xu, Feng
- Biotechnology for Biofuels, Vol. 12, Issue 1
Recent Trends in the Production, Combustion and Modeling of Furan-Based Fuels
journal, February 2018
- Eldeeb, Mazen; Akih-Kumgeh, Benjamin
- Energies, Vol. 11, Issue 3