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Title: Impact of hydration and temperature history on the structure and dynamics of lignin

Abstract

The full utilization of plant biomass for the production of energy and novel materials often involves high temperature treatment. Examples include melt spinning of lignin for manufacturing low-cost carbon fiber and the relocalization of lignin to increase the accessibility of cellulose for production of biofuels. These temperature-induced effects arise from poorly understood changes in lignin flexibility. Here, we combine molecular dynamics simulations with neutron scattering and dielectric spectroscopy experiments to probe the dependence of lignin dynamics on hydration and thermal history. We find a dynamical and structural hysteresis: at a given temperature, the lignin molecules are more expanded and their dynamics faster when the lignin is cooled than when heated. The structural hysteresis is more pronounced for dry lignin. The difference in dynamics, however, follows a different trend, it is found to be more significant at high temperatures and high hydration levels. The simulations also reveal syringyl units to be more dynamic than guiacyl. The results provide an atomic-detailed description of lignin dynamics, important for understanding lignin role in plant cell wall mechanics and for rationally improving lignin processing. The lignin glass transition, at which the polymer softens, is lower when lignin is cooled than when heated, therefore extending themore » cooling phase of processing and shortening the heating phase may offer ways to lower processing costs.« less

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [4];  [3];  [3]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [3]; ORCiD logo [3]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Giresun Univ. (Turkey); Univ. of Tennessee, Knoxville, TN (United States)
  2. Technische Univ. of Dortmund (Germany)
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  4. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  5. ORNL
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1435282
Alternate Identifier(s):
OSTI ID: 1434109
Grant/Contract Number:  
AC05-00OR22725; FWP ERKP752; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Green Chemistry
Additional Journal Information:
Journal Volume: 20; Journal Issue: 7; Journal ID: ISSN 1463-9262
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Vural, Derya, Gainaru, C., O'Neill, Hugh Michael, Pu, Yunqiao Joseph, Smith, Micholas D., Parks, Jerry M., Pingali, Sai Venkatesh, Mamontov, Eugene, Davison, Brian H., Sokolov, Alexei P., Ragauskas, Arthur J., Smith, Jeremy C., and Petridis, Loukas. Impact of hydration and temperature history on the structure and dynamics of lignin. United States: N. p., 2018. Web. doi:10.1039/C7GC03796A.
Vural, Derya, Gainaru, C., O'Neill, Hugh Michael, Pu, Yunqiao Joseph, Smith, Micholas D., Parks, Jerry M., Pingali, Sai Venkatesh, Mamontov, Eugene, Davison, Brian H., Sokolov, Alexei P., Ragauskas, Arthur J., Smith, Jeremy C., & Petridis, Loukas. Impact of hydration and temperature history on the structure and dynamics of lignin. United States. doi:10.1039/C7GC03796A.
Vural, Derya, Gainaru, C., O'Neill, Hugh Michael, Pu, Yunqiao Joseph, Smith, Micholas D., Parks, Jerry M., Pingali, Sai Venkatesh, Mamontov, Eugene, Davison, Brian H., Sokolov, Alexei P., Ragauskas, Arthur J., Smith, Jeremy C., and Petridis, Loukas. Fri . "Impact of hydration and temperature history on the structure and dynamics of lignin". United States. doi:10.1039/C7GC03796A. https://www.osti.gov/servlets/purl/1435282.
@article{osti_1435282,
title = {Impact of hydration and temperature history on the structure and dynamics of lignin},
author = {Vural, Derya and Gainaru, C. and O'Neill, Hugh Michael and Pu, Yunqiao Joseph and Smith, Micholas D. and Parks, Jerry M. and Pingali, Sai Venkatesh and Mamontov, Eugene and Davison, Brian H. and Sokolov, Alexei P. and Ragauskas, Arthur J. and Smith, Jeremy C. and Petridis, Loukas},
abstractNote = {The full utilization of plant biomass for the production of energy and novel materials often involves high temperature treatment. Examples include melt spinning of lignin for manufacturing low-cost carbon fiber and the relocalization of lignin to increase the accessibility of cellulose for production of biofuels. These temperature-induced effects arise from poorly understood changes in lignin flexibility. Here, we combine molecular dynamics simulations with neutron scattering and dielectric spectroscopy experiments to probe the dependence of lignin dynamics on hydration and thermal history. We find a dynamical and structural hysteresis: at a given temperature, the lignin molecules are more expanded and their dynamics faster when the lignin is cooled than when heated. The structural hysteresis is more pronounced for dry lignin. The difference in dynamics, however, follows a different trend, it is found to be more significant at high temperatures and high hydration levels. The simulations also reveal syringyl units to be more dynamic than guiacyl. The results provide an atomic-detailed description of lignin dynamics, important for understanding lignin role in plant cell wall mechanics and for rationally improving lignin processing. The lignin glass transition, at which the polymer softens, is lower when lignin is cooled than when heated, therefore extending the cooling phase of processing and shortening the heating phase may offer ways to lower processing costs.},
doi = {10.1039/C7GC03796A},
journal = {Green Chemistry},
number = 7,
volume = 20,
place = {United States},
year = {2018},
month = {3}
}

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Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Snapshot of the simulation system, with four lignin molecules (red, orange, grey and cyan) packed in a simulation box (blue) that employs periodic boundary conditions.

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