Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.

Although cellulose derivatives are widely applied in high-tech materials, the relation between their force responses and their surface chemical properties in a biological environment as a function of pH is unknown. Here, interaction forces of surface modified cellulose nanocrystals (CNCs), lignin re...

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Main Authors: Jing Li, Aji P Mathew
Format: Article
Language:English
Published: Public Library of Science (PLoS) 2023-01-01
Series:PLoS ONE
Online Access:https://doi.org/10.1371/journal.pone.0279919
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author Jing Li
Aji P Mathew
author_facet Jing Li
Aji P Mathew
author_sort Jing Li
collection DOAJ
description Although cellulose derivatives are widely applied in high-tech materials, the relation between their force responses and their surface chemical properties in a biological environment as a function of pH is unknown. Here, interaction forces of surface modified cellulose nanocrystals (CNCs), lignin residual cellulose nanocrystals (LCNCs), and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibres (TCNFs) with OSO3-, COO- and lignin chemical groups were measured using in situ peak force quantitative nanomechanical mapping and force spectroscopy in salt solution at two pH values. We found that the forces acting between the tip and CNC or LCNC are steric dominated showing long range and slow decay as a result of their low surface charge density. High Mw lignin contributed to the increased repulsion range for LCNCs compared to CNCs. The repulsion measured for TCNFs at the very short range was electrostatic force dominating showing a steep decay attributed to its high surface charge density. In the case of TCNFs, electrostatic double layer force was also evidenced by the attraction measured at secondary minima. In all the three cases the electro steric interactions are pH dependent. Dissipation maps verified that the force behavior for each material was related to structural conformation restriction of the groups at compression. The slow decayed repulsion of CNCs or LCNCs is related to a weak restriction of conformational change due to small surface groups or high molecular weight bound polymers forming flat layers, whereas the steep repulsion of TCNFs is attributed to a strong conformation restriction of carboxylic groups occurred by forming extended structure. Our results suggest that the force responses of the materials were dominated by surface charges and structural differences. TCNFs showed superior nanomechanical and repulsion properties over CNCs or LCNCs at neutral pH.
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spelling doaj.art-08a8422fab304fe5a9395d9b38207aa02023-03-21T05:31:56ZengPublic Library of Science (PLoS)PLoS ONE1932-62032023-01-01181e027991910.1371/journal.pone.0279919Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.Jing LiAji P MathewAlthough cellulose derivatives are widely applied in high-tech materials, the relation between their force responses and their surface chemical properties in a biological environment as a function of pH is unknown. Here, interaction forces of surface modified cellulose nanocrystals (CNCs), lignin residual cellulose nanocrystals (LCNCs), and 2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)-oxidized cellulose nanofibres (TCNFs) with OSO3-, COO- and lignin chemical groups were measured using in situ peak force quantitative nanomechanical mapping and force spectroscopy in salt solution at two pH values. We found that the forces acting between the tip and CNC or LCNC are steric dominated showing long range and slow decay as a result of their low surface charge density. High Mw lignin contributed to the increased repulsion range for LCNCs compared to CNCs. The repulsion measured for TCNFs at the very short range was electrostatic force dominating showing a steep decay attributed to its high surface charge density. In the case of TCNFs, electrostatic double layer force was also evidenced by the attraction measured at secondary minima. In all the three cases the electro steric interactions are pH dependent. Dissipation maps verified that the force behavior for each material was related to structural conformation restriction of the groups at compression. The slow decayed repulsion of CNCs or LCNCs is related to a weak restriction of conformational change due to small surface groups or high molecular weight bound polymers forming flat layers, whereas the steep repulsion of TCNFs is attributed to a strong conformation restriction of carboxylic groups occurred by forming extended structure. Our results suggest that the force responses of the materials were dominated by surface charges and structural differences. TCNFs showed superior nanomechanical and repulsion properties over CNCs or LCNCs at neutral pH.https://doi.org/10.1371/journal.pone.0279919
spellingShingle Jing Li
Aji P Mathew
Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.
PLoS ONE
title Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.
title_full Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.
title_fullStr Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.
title_full_unstemmed Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.
title_short Effect of decoration route on the nanomechanical, adhesive, and force response of nanocelluloses-An in situ force spectroscopy study.
title_sort effect of decoration route on the nanomechanical adhesive and force response of nanocelluloses an in situ force spectroscopy study
url https://doi.org/10.1371/journal.pone.0279919
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