skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Organosolv-Water Cosolvent Phase Separation on Cellulose and its Influence on the Physical Deconstruction of Cellulose: A Molecular Dynamics Analysis

Abstract

Deconstruction of cellulose is crucial for the chemical conversion of lignocellulose into fuel/bioproduct precursors. Recently, a water-organosolv cosolvent system (THF-water) has been shown to both phase-separate on cellulose surfaces and partially deconstruct Avicel (cellulose) in the absence of acid. Here we employ molecular dynamics simulations to determine whether other common water-organosolv cosolvent systems (acetone, ethanol, and γ-valerolactone) exhibit phase separation at cellulose surface and whether this alters a purely physical cellulose dissociation pathway. Despite finding varied degrees of phase-separation of organosolv on cellulose surfaces, physical dissociation is not enhanced. Interestingly, however, the total amount the median water-cellulose contact lifetimes increases for the cosolvent systems in the order of THF > acetone > ethanol > γ-valerolactone. Together our results indicate two points: a purely physical process for deconstruction of cellulose is unlikely for these cosolvents, and in THF-water, unlike γ-valerolactone- (and some concentrations of acetone and ethanol) water cosolvents, a significant fraction of surface water is slowed. As a result, this slowing may be of importance in enhancing chemical deconstruction of cellulose, as it permits an increase in potential THF-water-cellulose reactions, even while the amount of water near cellulose is decreased.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1435328
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Scientific Reports
Additional Journal Information:
Journal Volume: 7; Journal Issue: 1; Journal ID: ISSN 2045-2322
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; Biofuels; Biophysical chemistry; Computational biophysics

Citation Formats

Smith, Micholas Dean, Cheng, Xiaolin, Petridis, Loukas, Mostofian, Barmak, and Smith, Jeremy C. Organosolv-Water Cosolvent Phase Separation on Cellulose and its Influence on the Physical Deconstruction of Cellulose: A Molecular Dynamics Analysis. United States: N. p., 2017. Web. doi:10.1038/s41598-017-15048-7.
Smith, Micholas Dean, Cheng, Xiaolin, Petridis, Loukas, Mostofian, Barmak, & Smith, Jeremy C. Organosolv-Water Cosolvent Phase Separation on Cellulose and its Influence on the Physical Deconstruction of Cellulose: A Molecular Dynamics Analysis. United States. doi:10.1038/s41598-017-15048-7.
Smith, Micholas Dean, Cheng, Xiaolin, Petridis, Loukas, Mostofian, Barmak, and Smith, Jeremy C. Fri . "Organosolv-Water Cosolvent Phase Separation on Cellulose and its Influence on the Physical Deconstruction of Cellulose: A Molecular Dynamics Analysis". United States. doi:10.1038/s41598-017-15048-7. https://www.osti.gov/servlets/purl/1435328.
@article{osti_1435328,
title = {Organosolv-Water Cosolvent Phase Separation on Cellulose and its Influence on the Physical Deconstruction of Cellulose: A Molecular Dynamics Analysis},
author = {Smith, Micholas Dean and Cheng, Xiaolin and Petridis, Loukas and Mostofian, Barmak and Smith, Jeremy C.},
abstractNote = {Deconstruction of cellulose is crucial for the chemical conversion of lignocellulose into fuel/bioproduct precursors. Recently, a water-organosolv cosolvent system (THF-water) has been shown to both phase-separate on cellulose surfaces and partially deconstruct Avicel (cellulose) in the absence of acid. Here we employ molecular dynamics simulations to determine whether other common water-organosolv cosolvent systems (acetone, ethanol, and γ-valerolactone) exhibit phase separation at cellulose surface and whether this alters a purely physical cellulose dissociation pathway. Despite finding varied degrees of phase-separation of organosolv on cellulose surfaces, physical dissociation is not enhanced. Interestingly, however, the total amount the median water-cellulose contact lifetimes increases for the cosolvent systems in the order of THF > acetone > ethanol > γ-valerolactone. Together our results indicate two points: a purely physical process for deconstruction of cellulose is unlikely for these cosolvents, and in THF-water, unlike γ-valerolactone- (and some concentrations of acetone and ethanol) water cosolvents, a significant fraction of surface water is slowed. As a result, this slowing may be of importance in enhancing chemical deconstruction of cellulose, as it permits an increase in potential THF-water-cellulose reactions, even while the amount of water near cellulose is decreased.},
doi = {10.1038/s41598-017-15048-7},
journal = {Scientific Reports},
number = 1,
volume = 7,
place = {United States},
year = {2017},
month = {11}
}

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

Citation Metrics:
Cited by: 6 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

CHARMM-GUI Input Generator for NAMD, Gromacs, Amber, Openmm, and CHARMM/OpenMM Simulations using the CHARMM36 Additive Force Field
journal, February 2016


An engineered solvent system for sugar production from lignocellulosic biomass using biomass derived γ-valerolactone
journal, January 2016

  • Motagamwala, Ali Hussain; Won, Wangyun; Maravelias, Christos T.
  • Green Chemistry, Vol. 18, Issue 21
  • DOI: 10.1039/C6GC02297A

Valorization of bamboo by γ-valerolactone/acid/water to produce digestible cellulose, degraded sugars and lignin
journal, April 2017


Nonenzymatic Sugar Production from Biomass Using Biomass-Derived  -Valerolactone
journal, January 2014


CHARMM-GUI: A web-based graphical user interface for CHARMM
journal, March 2008

  • Jo, Sunhwan; Kim, Taehoon; Iyer, Vidyashankara G.
  • Journal of Computational Chemistry, Vol. 29, Issue 11
  • DOI: 10.1002/jcc.20945

Common processes drive the thermochemical pretreatment of lignocellulosic biomass
journal, January 2014

  • Langan, Paul; Petridis, Loukas; O'Neill, Hugh M.
  • Green Chem., Vol. 16, Issue 1
  • DOI: 10.1039/C3GC41962B

Canonical sampling through velocity rescaling
journal, January 2007

  • Bussi, Giovanni; Donadio, Davide; Parrinello, Michele
  • The Journal of Chemical Physics, Vol. 126, Issue 1
  • DOI: 10.1063/1.2408420

Organic amine catalytic organosolv pretreatment of corn stover for enzymatic saccharification and high-quality lignin
journal, May 2017


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
  • DOI: 10.1021/jf9608074

LINCS: A linear constraint solver for molecular simulations
journal, September 1997


Organosolvent pretreatment and enzymatic hydrolysis of rice straw for the production of bioethanol
journal, July 2011

  • Sindhu, Raveendran; Binod, Parameswaran; Janu, Kanakambaran Usha
  • World Journal of Microbiology and Biotechnology, Vol. 28, Issue 2
  • DOI: 10.1007/s11274-011-0838-8

CHARMM36 all-atom additive protein force field: Validation based on comparison to NMR data
journal, July 2013

  • Huang, Jing; MacKerell, Alexander D.
  • Journal of Computational Chemistry, Vol. 34, Issue 25
  • DOI: 10.1002/jcc.23354

Effects of organosolv pretreatment and enzymatic hydrolysis on cellulose structure and crystallinity in Loblolly pine
journal, May 2010


Hydrolysis of lignocellulosic materials for ethanol production: a review
journal, May 2002


Co-solvent Pretreatment Reduces Costly Enzyme Requirements for High Sugar and Ethanol Yields from Lignocellulosic Biomass
journal, February 2015


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
  • DOI: 10.1063/1.448118

Molecular-Level Origins of Biomass Recalcitrance: Decrystallization Free Energies for Four Common Cellulose Polymorphs
journal, April 2011

  • Beckham, Gregg T.; Matthews, James F.; Peters, Baron
  • The Journal of Physical Chemistry B, Vol. 115, Issue 14
  • DOI: 10.1021/jp1106394

Synergetic Effects of Alcohol/Water Mixing on the Catalytic Reductive Fractionation of Poplar Wood
journal, October 2016

  • Renders, Tom; Van den Bosch, Sander; Vangeel, Thijs
  • ACS Sustainable Chemistry & Engineering, Vol. 4, Issue 12
  • DOI: 10.1021/acssuschemeng.6b01844

THE weighted histogram analysis method for free-energy calculations on biomolecules. I. The method
journal, October 1992

  • Kumar, Shankar; Rosenberg, John M.; Bouzida, Djamal
  • Journal of Computational Chemistry, Vol. 13, Issue 8
  • DOI: 10.1002/jcc.540130812

The structural properties of alcohol–water mixtures
journal, January 1966


P-LINCS:  A Parallel Linear Constraint Solver for Molecular Simulation
journal, December 2007

  • Hess, Berk
  • Journal of Chemical Theory and Computation, Vol. 4, Issue 1
  • DOI: 10.1021/ct700200b

A mild biomass pretreatment using γ-valerolactone for concentrated sugar production
journal, January 2016

  • Shuai, Li; Questell-Santiago, Ydna M.; Luterbacher, Jeremy S.
  • Green Chemistry, Vol. 18, Issue 4
  • DOI: 10.1039/C5GC02489G

Force Pulling of Single Cellulose Chains at the Crystalline Cellulose−Liquid Interface: A Molecular Dynamics Study
journal, April 2009

  • Bergenstråhle, Malin; Thormann, Esben; Nordgren, Niklas
  • Langmuir, Vol. 25, Issue 8
  • DOI: 10.1021/la803915c

Molecular Driving Forces behind the Tetrahydrofuran–Water Miscibility Gap
journal, January 2016

  • Smith, Micholas Dean; Mostofian, Barmak; Petridis, Loukas
  • The Journal of Physical Chemistry B, Vol. 120, Issue 4
  • DOI: 10.1021/acs.jpcb.5b09770

Vapor–Liquid Equilibria, Excess Enthalpy, and Density of Aqueous γ-Valerolactone Solutions.
journal, January 2016

  • Zaitseva, Anna; Pokki, Juha-Pekka; Le, Huy Quang
  • Journal of Chemical & Engineering Data, Vol. 61, Issue 2
  • DOI: 10.1021/acs.jced.5b00724

Vapor-pressure Relations in Mixtures of Two Liquids, III.
journal, November 1900

  • Taylor, A. Ernest
  • The Journal of Physical Chemistry, Vol. 4, Issue 8
  • DOI: 10.1021/j150026a004

Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis
journal, February 2009

  • Zhao, Xuebing; Cheng, Keke; Liu, Dehua
  • Applied Microbiology and Biotechnology, Vol. 82, Issue 5
  • DOI: 10.1007/s00253-009-1883-1

g_wham—A Free Weighted Histogram Analysis Implementation Including Robust Error and Autocorrelation Estimates
journal, November 2010

  • Hub, Jochen S.; de Groot, Bert L.; van der Spoel, David
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 12
  • DOI: 10.1021/ct100494z

Extension of the CHARMM general force field to sulfonyl-containing compounds and its utility in biomolecular simulations
journal, July 2012

  • Yu, Wenbo; He, Xibing; Vanommeslaeghe, Kenno
  • Journal of Computational Chemistry, Vol. 33, Issue 31
  • DOI: 10.1002/jcc.23067

CELF pretreatment of corn stover boosts ethanol titers and yields from high solids SSF with low enzyme loadings
journal, January 2016

  • Nguyen, Thanh Yen; Cai, Charles M.; Osman, Omar
  • Green Chemistry, Vol. 18, Issue 6
  • DOI: 10.1039/C5GC01977J

Automation of the CHARMM General Force Field (CGenFF) II: Assignment of Bonded Parameters and Partial Atomic Charges
journal, November 2012

  • Vanommeslaeghe, K.; Raman, E. Prabhu; MacKerell, A. D.
  • Journal of Chemical Information and Modeling, Vol. 52, Issue 12
  • DOI: 10.1021/ci3003649

Enhanced sampling simulation analysis of the structure of lignin in the THF–water miscibility gap
journal, January 2016

  • Smith, Micholas Dean; Petridis, Loukas; Cheng, Xiaolin
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 9
  • DOI: 10.1039/C5CP07088K

Organosolv pretreatment of sorghum bagasse using a low concentration of hydrophobic solvents such as 1-butanol or 1-pentanol
journal, February 2016

  • Teramura, Hiroshi; Sasaki, Kengo; Oshima, Tomoko
  • Biotechnology for Biofuels, Vol. 9, Issue 1
  • DOI: 10.1186/s13068-016-0427-z

The Statistical Thermodynamics of Multicomponent Systems
journal, July 1945

  • McMillan, William G.; Mayer, Joseph E.
  • The Journal of Chemical Physics, Vol. 13, Issue 7
  • DOI: 10.1063/1.1724036

Phase equilibria in the system tetrahydrofuran(1)-water(2)
journal, January 1972

  • Matouš, J.; Novák, J. P.; Šobr, J.
  • Collection of Czechoslovak Chemical Communications, Vol. 37, Issue 8
  • DOI: 10.1135/cccc19722653

Organosolv pretreatment for enzymatic hydrolysis of poplars: I. Enzyme hydrolysis of cellulosic residues
journal, May 1988

  • Chum, H. L.; Johnson, D. K.; Black, S.
  • Biotechnology and Bioengineering, Vol. 31, Issue 7
  • DOI: 10.1002/bit.260310703

Current Pretreatment Technologies for the Development of Cellulosic Ethanol and Biorefineries
journal, September 2015

  • Silveira, Marcos Henrique Luciano; Morais, Ana Rita C.; da Costa Lopes, Andre M.
  • ChemSusChem, Vol. 8, Issue 20
  • DOI: 10.1002/cssc.201500282

Local Phase Separation of Co-solvents Enhances Pretreatment of Biomass for Bioenergy Applications
journal, August 2016

  • Mostofian, Barmak; Cai, Charles M.; Smith, Micholas Dean
  • Journal of the American Chemical Society, Vol. 138, Issue 34
  • DOI: 10.1021/jacs.6b03285

    Works referencing / citing this record:

    Systematic parameterization of lignin for the CHARMM force field
    journal, January 2019

    • Vermaas, Josh V.; Petridis, Loukas; Ralph, John
    • Green Chemistry, Vol. 21, Issue 1
    • DOI: 10.1039/c8gc03209b

    Lignin-based carbon fiber: a current overview
    journal, July 2018

    • Souto, Felipe; Calado, Veronica; Pereira, Nei
    • Materials Research Express, Vol. 5, Issue 7
    • DOI: 10.1088/2053-1591/aaba00