Chirality and bound water in the hierarchical cellulose structure

Antti Paajanen, Sara Ceccherini, Thaddeus Maloney, Jukka A. Ketoja (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

Abstract

The origins of the unique properties of natural fibres have remained largely unresolved because of the complex interrelations between structural hierarchy, chirality and bound water. In this paper, analysis of the melting endotherms for bleached hardwood pulps indicates that the amount of non-freezing bound water (0.21 g/g) is roughly half of the amount of freezing bound water (0.42 g/g). We link this result to the two smallest constitutive units, microfibrils and their bundles, using molecular dynamics simulations at both hierarchical levels. The molecular water layers found in the simulations correspond quite accurately to the measured amount of non-freezing and freezing bound water. Disorder that results from the microfibril twist and amphiphilicity prevents co-crystallisation, leaving routes for water molecules to diffuse inside the microfibril bundle. Moreover, the simulations predict correctly the magnitude of the right-handed twist at different hierarchical levels. Significant changes in hydroxymethyl group conformations are seen during twisting that compare well with existing experimental data. Our findings go beyond earlier modelling studies in predicting the twist and structure of the microfibril bundle.
Original languageEnglish
Pages (from-to)5877-5892
Number of pages16
JournalCellulose
Volume26
Issue number10
Early online date2019
DOIs
Publication statusPublished - 1 Jan 2019
MoE publication typeA1 Journal article-refereed

Fingerprint

Chirality
Cellulose
Water
Freezing
Natural fibers
Hardwoods
Crystallization
Pulp
Conformations
Molecular dynamics
Melting
Molecules
Computer simulation

Keywords

  • Macrofibril
  • Twist
  • Cellulose
  • Microfibril
  • Molecular dynamics
  • Bound water

Cite this

Paajanen, Antti ; Ceccherini, Sara ; Maloney, Thaddeus ; Ketoja, Jukka A. / Chirality and bound water in the hierarchical cellulose structure. In: Cellulose. 2019 ; Vol. 26, No. 10. pp. 5877-5892.
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Chirality and bound water in the hierarchical cellulose structure. / Paajanen, Antti; Ceccherini, Sara; Maloney, Thaddeus; Ketoja, Jukka A. (Corresponding Author).

In: Cellulose, Vol. 26, No. 10, 01.01.2019, p. 5877-5892.

Research output: Contribution to journalArticleScientificpeer-review

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