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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]
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  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 Laboratory (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.
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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. https://doi.org/10.1038/s41598-017-15048-7
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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. https://doi.org/10.1038/s41598-017-15048-7. https://www.osti.gov/servlets/purl/1435328.
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@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 = {Fri Nov 03 00:00:00 EDT 2017},
month = {Fri Nov 03 00:00:00 EDT 2017}
}
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https://doi.org/10.1038/s41598-017-15048-7
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