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Title: Simulation of a cellulose fiber in ionic liquid suggests a synergistic approach to dissolution

Abstract

Ionic liquids dissolve cellulose in a more efficient and environmentally acceptable way than conventional methods in aqueous solution. An understanding of how ionic liquids act on cellulose is essential for improving pretreatment conditions and thus detailed knowledge of the interactions between the cations, anions and cellulose is necessary. Here in this study, to explore ionic liquid effects, we perform all-atom molecular dynamics simulations of a cellulose microfibril in 1-butyl-3-methylimidazolium chloride and analyze site–site interactions and cation orientations at the solute–solvent interface. The results indicate that Cl- anions predominantly interact with cellulose surface hydroxyl groups but with differences between chains of neighboring cellulose layers, referred to as center and origin chains; Cl- binds to C3-hydroxyls on the origin chains but to C2- and C6-hydroxyls on the center chains, thus resulting in a distinct pattern along glucan chains of the hydrophilic fiber surfaces. In particular, Cl- binding disrupts intrachain O3H–O5 hydrogen bonds on the origin chains but not those on the center chains. In contrast, Bmim+ cations stack preferentially on the hydrophobic cellulose surface, governed by non-polar interactions with cellulose. Complementary to the polar interactions between Cl- and cellulose, the stacking interaction between solvent cation rings and cellulose pyranose rings can compensatemore » the interaction between stacked cellulose layers, thus stabilizing detached cellulose chains. Moreover, a frequently occurring intercalation of Bmim+ on the hydrophilic surface is observed, which by separating cellulose layers can also potentially facilitate the initiation of fiber disintegration. The results provide a molecular description why ionic liquids are ideal cellulose solvents, the concerted action of anions and cations on the hydrophobic and hydrophilic surfaces being key to the efficient dissolution of the amphiphilic carbohydrate.« less

Authors:
 [1];  [2];  [2]
+ Show Author Affiliations
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Molecular Biophysics; Univ. of Tennessee, Knoxville, TN (United States). Graduate School of Genome Science and Technology
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Center for Molecular Biophysics; Univ. of Tennessee, Knoxville, TN (United States). Dept. of Biochemistry, Cellular & Molecular Biology
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF)
OSTI Identifier:
1376299
Grant/Contract Number:  
AC05-00OR22725; TG-MCA08X032
Resource Type:
Accepted Manuscript
Journal Name:
Cellulose
Additional Journal Information:
Journal Volume: 21; Journal Issue: 2; Journal ID: ISSN 0969-0239
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Cellulose; Ionic liquids; Pretreatment; MD simulation

Citation Formats

Mostofian, Barmak, Smith, Jeremy C., and Cheng, Xiaolin. Simulation of a cellulose fiber in ionic liquid suggests a synergistic approach to dissolution. United States: N. p., 2013. Web. doi:10.1007/s10570-013-0018-0.
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Mostofian, Barmak, Smith, Jeremy C., & Cheng, Xiaolin. Simulation of a cellulose fiber in ionic liquid suggests a synergistic approach to dissolution. United States. https://doi.org/10.1007/s10570-013-0018-0
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Mostofian, Barmak, Smith, Jeremy C., and Cheng, Xiaolin. Sun . "Simulation of a cellulose fiber in ionic liquid suggests a synergistic approach to dissolution". United States. https://doi.org/10.1007/s10570-013-0018-0. https://www.osti.gov/servlets/purl/1376299.
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@article{osti_1376299,
title = {Simulation of a cellulose fiber in ionic liquid suggests a synergistic approach to dissolution},
author = {Mostofian, Barmak and Smith, Jeremy C. and Cheng, Xiaolin},
abstractNote = {Ionic liquids dissolve cellulose in a more efficient and environmentally acceptable way than conventional methods in aqueous solution. An understanding of how ionic liquids act on cellulose is essential for improving pretreatment conditions and thus detailed knowledge of the interactions between the cations, anions and cellulose is necessary. Here in this study, to explore ionic liquid effects, we perform all-atom molecular dynamics simulations of a cellulose microfibril in 1-butyl-3-methylimidazolium chloride and analyze site–site interactions and cation orientations at the solute–solvent interface. The results indicate that Cl- anions predominantly interact with cellulose surface hydroxyl groups but with differences between chains of neighboring cellulose layers, referred to as center and origin chains; Cl- binds to C3-hydroxyls on the origin chains but to C2- and C6-hydroxyls on the center chains, thus resulting in a distinct pattern along glucan chains of the hydrophilic fiber surfaces. In particular, Cl- binding disrupts intrachain O3H–O5 hydrogen bonds on the origin chains but not those on the center chains. In contrast, Bmim+ cations stack preferentially on the hydrophobic cellulose surface, governed by non-polar interactions with cellulose. Complementary to the polar interactions between Cl- and cellulose, the stacking interaction between solvent cation rings and cellulose pyranose rings can compensate the interaction between stacked cellulose layers, thus stabilizing detached cellulose chains. Moreover, a frequently occurring intercalation of Bmim+ on the hydrophilic surface is observed, which by separating cellulose layers can also potentially facilitate the initiation of fiber disintegration. The results provide a molecular description why ionic liquids are ideal cellulose solvents, the concerted action of anions and cations on the hydrophobic and hydrophilic surfaces being key to the efficient dissolution of the amphiphilic carbohydrate.},
doi = {10.1007/s10570-013-0018-0},
journal = {Cellulose},
number = 2,
volume = 21,
place = {United States},
year = {Sun Aug 11 00:00:00 EDT 2013},
month = {Sun Aug 11 00:00:00 EDT 2013}
}
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https://doi.org/10.1007/s10570-013-0018-0
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