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Hydration Control of the Mechanical and Dynamical Properties of Cellulose

Journal Article · · Biomacromolecules
DOI:https://doi.org/10.1021/bm5011849· OSTI ID:1385998
; ;  [1];  [2];  [3]; ;  [2];  [4];  [3]
  1. Ripon College, Ripon, Wisconsin 54971, United States
  2. Department of Chemical Engineering, Pennsylvania State University, University Park, Pennsylvania 16802, United States
  3. Department of Biochemistry and Cellular and Molecular Biology, University of Tennessee, Knoxville, Tennessee 37996, United States
  4. Department of Chemistry, University of Toledo, Toledo, Ohio 43606, United States
The mechanical and dynamical properties of cellulose, the most abundant biomolecule on earth, are essential for its function in plant cell walls and advanced biomaterials. Cellulose is almost always found in a hydrated state, and it is therefore important to understand how hydration influences its dynamics and mechanics. Here, the nanosecond-time scale dynamics of cellulose is characterized using dynamic neutron scattering experiments and molecular dynamics (MD) simulation. The experiments reveal that hydrated samples exhibit a higher average mean-square displacement above ~240 K. The MD simulation reveals that the fluctuations of the surface hydroxymethyl atoms determine the experimental temperature and hydration dependence. The increase in the conformational disorder of the surface hydroxymethyl groups with temperature follows the cellulose persistence length, suggesting a coupling between structural and mechanical properties of the biopolymer. In the MD simulation, 20% hydrated cellulose is more rigid than the dry form, due to more closely packed cellulose chains and water molecules bridging cellulose monomers with hydrogen bonds. This finding may have implications for understanding the origin of strength and rigidity of secondary plant cell walls. The detailed characterization obtained here describes how hydration-dependent increased fluctuations and hydroxymethyl disorder at the cellulose surface lead to enhancement of the rigidity of this important biomolecule.
Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Center for Lignocellulose Structure and Formation (CLSF)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)
DOE Contract Number:
SC0001090
OSTI ID:
1385998
Journal Information:
Biomacromolecules, Journal Name: Biomacromolecules Journal Issue: 11 Vol. 15; ISSN 1525-7797
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English