Atomistic molecular dynamics simulations on the interaction of TEMPO-oxidized cellulose nanofibrils in water

Antti Paajanen (Corresponding Author), Yogesh Sonavane, Dominika Ignasiak, Jukka A. Ketoja, Thad C. Maloney, Sami Paavilainen

Research output: Contribution to journalArticleScientificpeer-review

5 Citations (Scopus)

Abstract

Atomistic molecular dynamics simulations were carried out to obtain information on the rheological, aggregation and disintegration properties of carboxylated (TEMPO-oxidized) cellulose nanofibrils with different functionalization levels. The magnitude of the inter-fibril interaction was quantified for parallel nanofibrils using the umbrella sampling method. The obtained potential of mean force was found highly sensitive to the charge configuration for intermediate functionalization levels. This feature was further studied with an electrostatic model for similar charge configurations and system periodicity as in the case of the molecular dynamics simulations. The electrostatic contribution of the charged surfaces varied from repulsive to attractive depending on the distribution of the carboxylate groups and nearby counter-ions, as well as the distance between the fibrils. The simulated deviations from average behavior for single fibrils in both models suggest heterogeneity in their aggregation and disintegration behavior. This was seen in disintegration experiments, where the differences in disintegration energy and in the structural variation qualitatively agreed with the model predictions. As to aggregation behavior, the studied case with parallel fibrils reflects the upper boundary of the repulsive interaction.
Original languageEnglish
Pages (from-to)3449-3462
JournalCellulose
Volume23
Issue number6
DOIs
Publication statusPublished - 2016
MoE publication typeA1 Journal article-refereed

Fingerprint

oxidized cellulose
Disintegration
Molecular dynamics
Cellulose
Agglomeration
Water
Computer simulation
Electrostatics
Radiation counters
Sampling
TEMPO
Experiments

Keywords

  • cellulose nanofibril
  • electrostatic interaction
  • functionalization
  • molecular dynamics
  • TEMPO-oxidation
  • ProperTune

Cite this

Paajanen, Antti ; Sonavane, Yogesh ; Ignasiak, Dominika ; Ketoja, Jukka A. ; Maloney, Thad C. ; Paavilainen, Sami. / Atomistic molecular dynamics simulations on the interaction of TEMPO-oxidized cellulose nanofibrils in water. In: Cellulose. 2016 ; Vol. 23, No. 6. pp. 3449-3462.
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abstract = "Atomistic molecular dynamics simulations were carried out to obtain information on the rheological, aggregation and disintegration properties of carboxylated (TEMPO-oxidized) cellulose nanofibrils with different functionalization levels. The magnitude of the inter-fibril interaction was quantified for parallel nanofibrils using the umbrella sampling method. The obtained potential of mean force was found highly sensitive to the charge configuration for intermediate functionalization levels. This feature was further studied with an electrostatic model for similar charge configurations and system periodicity as in the case of the molecular dynamics simulations. The electrostatic contribution of the charged surfaces varied from repulsive to attractive depending on the distribution of the carboxylate groups and nearby counter-ions, as well as the distance between the fibrils. The simulated deviations from average behavior for single fibrils in both models suggest heterogeneity in their aggregation and disintegration behavior. This was seen in disintegration experiments, where the differences in disintegration energy and in the structural variation qualitatively agreed with the model predictions. As to aggregation behavior, the studied case with parallel fibrils reflects the upper boundary of the repulsive interaction.",
keywords = "cellulose nanofibril, electrostatic interaction, functionalization, molecular dynamics, TEMPO-oxidation, ProperTune",
author = "Antti Paajanen and Yogesh Sonavane and Dominika Ignasiak and Ketoja, {Jukka A.} and Maloney, {Thad C.} and Sami Paavilainen",
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Atomistic molecular dynamics simulations on the interaction of TEMPO-oxidized cellulose nanofibrils in water. / Paajanen, Antti (Corresponding Author); Sonavane, Yogesh; Ignasiak, Dominika; Ketoja, Jukka A.; Maloney, Thad C.; Paavilainen, Sami.

In: Cellulose, Vol. 23, No. 6, 2016, p. 3449-3462.

Research output: Contribution to journalArticleScientificpeer-review

TY - JOUR

T1 - Atomistic molecular dynamics simulations on the interaction of TEMPO-oxidized cellulose nanofibrils in water

AU - Paajanen, Antti

AU - Sonavane, Yogesh

AU - Ignasiak, Dominika

AU - Ketoja, Jukka A.

AU - Maloney, Thad C.

AU - Paavilainen, Sami

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N2 - Atomistic molecular dynamics simulations were carried out to obtain information on the rheological, aggregation and disintegration properties of carboxylated (TEMPO-oxidized) cellulose nanofibrils with different functionalization levels. The magnitude of the inter-fibril interaction was quantified for parallel nanofibrils using the umbrella sampling method. The obtained potential of mean force was found highly sensitive to the charge configuration for intermediate functionalization levels. This feature was further studied with an electrostatic model for similar charge configurations and system periodicity as in the case of the molecular dynamics simulations. The electrostatic contribution of the charged surfaces varied from repulsive to attractive depending on the distribution of the carboxylate groups and nearby counter-ions, as well as the distance between the fibrils. The simulated deviations from average behavior for single fibrils in both models suggest heterogeneity in their aggregation and disintegration behavior. This was seen in disintegration experiments, where the differences in disintegration energy and in the structural variation qualitatively agreed with the model predictions. As to aggregation behavior, the studied case with parallel fibrils reflects the upper boundary of the repulsive interaction.

AB - Atomistic molecular dynamics simulations were carried out to obtain information on the rheological, aggregation and disintegration properties of carboxylated (TEMPO-oxidized) cellulose nanofibrils with different functionalization levels. The magnitude of the inter-fibril interaction was quantified for parallel nanofibrils using the umbrella sampling method. The obtained potential of mean force was found highly sensitive to the charge configuration for intermediate functionalization levels. This feature was further studied with an electrostatic model for similar charge configurations and system periodicity as in the case of the molecular dynamics simulations. The electrostatic contribution of the charged surfaces varied from repulsive to attractive depending on the distribution of the carboxylate groups and nearby counter-ions, as well as the distance between the fibrils. The simulated deviations from average behavior for single fibrils in both models suggest heterogeneity in their aggregation and disintegration behavior. This was seen in disintegration experiments, where the differences in disintegration energy and in the structural variation qualitatively agreed with the model predictions. As to aggregation behavior, the studied case with parallel fibrils reflects the upper boundary of the repulsive interaction.

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