Investigating the interactions between a poloxamer and TEMPO-oxidised cellulose nanocrystals

Alessandra Lavoratti; Onajite Abafe Diejomaoh; Annela M. Seddon; Todor T. Koev; Yaroslav Z. Khimyak; Robert L. Harniman; Katri S. Kontturi; Tekla Tammelin; Stephen J. Eichhorn

doi:10.1016/j.carbpol.2024.123156

Investigating the interactions between a poloxamer and TEMPO-oxidised cellulose nanocrystals

Alessandra Lavoratti, Onajite Abafe Diejomaoh, Annela M. Seddon, Todor T. Koev, Yaroslav Z. Khimyak, Robert L. Harniman, Katri S. Kontturi, Tekla Tammelin, Stephen J. Eichhorn^*

^*Corresponding author for this work

Research output: Contribution to journal › Article › Scientific › peer-review

1 Citation (Scopus)

Abstract

Cellulose nanocrystals (CNCs) have emerged as promising, sustainable materials, with applications in sensors, coatings, pharmaceuticals, and composites. Their modification with block copolymers such as PEO-PPO-PEO triblock copolymers of the Pluronic family has been attempted many times in the literature, with claims that such modification would happen by an anchor(PEO)-buoy(PPO)-anchor(PEO) mechanism. However, there is much disagreement in the literature on this. We herein physically adsorbed Pluronic F127, a nontoxic triblock copolymer poloxamer, comprising hydrophilic polyethylene oxide (PEO) and hydrophobic polypropylene oxide (PPO) blocks, onto the surface of TEMPO oxidised CNCs by simple mixing in an aqueous medium. The adsorption of F127 onto the surface of these CNCs was successful and persistent even after solubilisation. The thermal stability of modified TOCNCs increased (by ∼19 °C) compared to their neat and oxidised counterparts. F127-TOCNC suspensions exhibited comparable viscosity to their neat and oxidised counterparts without premature gelation of F127. NOESY NMR observations showed that PPO blocks are more proximal to the TOCNC than the PEO blocks. AFM and QCM-D analyses supported the formation of a rigid, thin layer of block copolymer surrounding the TOCNC. A degree of modification (7 %) was achieved, even after washing, proving that adsorption is persistent and mainly irreversible.

Original language	English
Article number	123156
Journal	Carbohydrate Polymers
Volume	352
DOIs	https://doi.org/10.1016/j.carbpol.2024.123156
Publication status	Published - 15 Mar 2025
MoE publication type	A1 Journal article-refereed

Funding

S.J.E. A.L. and O.A.D. would like to thank the Engineering and Physical Sciences Research Council (EPSRC), Grant No. EP/V002651/1, for funding. Electron microscope studies were carried out in the Chemical Imaging Facility at the University of Bristol by Dr. Jean-Charles Eloi. The Ganesha X-ray scattering apparatus used for this research was purchased under EPSRC Grant \u2018Atoms to Applications\u2019 Grant ref. EP/K035746/1. This work benefited from SasView software, originally developed by the DANSE project under NSF award DMR-0520547. The authors also grateful to the University of East Anglia's Faculty of Science NMR facility and to the HH Wills Physics Laboratory for the SAXS experiments. T.K. is funded via a UKRI Future Leaders Fellowship awarded to Dr. Matthew Wallace (MR/T044020/1). K.S.K. acknowledges Research Council of Finland project PreDesign (no. 361951) for funding. T.T. acknowledges Research Council of Finland Flagship Program FinnCERES (no. 318890 and 318891) for funding.

Keywords

Adsorption
Cellulose nanocrystals
TEMPO oxidation
Triblock copolymer

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title = "Investigating the interactions between a poloxamer and TEMPO-oxidised cellulose nanocrystals",

abstract = "Cellulose nanocrystals (CNCs) have emerged as promising, sustainable materials, with applications in sensors, coatings, pharmaceuticals, and composites. Their modification with block copolymers such as PEO-PPO-PEO triblock copolymers of the Pluronic family has been attempted many times in the literature, with claims that such modification would happen by an anchor(PEO)-buoy(PPO)-anchor(PEO) mechanism. However, there is much disagreement in the literature on this. We herein physically adsorbed Pluronic F127, a nontoxic triblock copolymer poloxamer, comprising hydrophilic polyethylene oxide (PEO) and hydrophobic polypropylene oxide (PPO) blocks, onto the surface of TEMPO oxidised CNCs by simple mixing in an aqueous medium. The adsorption of F127 onto the surface of these CNCs was successful and persistent even after solubilisation. The thermal stability of modified TOCNCs increased (by ∼19 °C) compared to their neat and oxidised counterparts. F127-TOCNC suspensions exhibited comparable viscosity to their neat and oxidised counterparts without premature gelation of F127. NOESY NMR observations showed that PPO blocks are more proximal to the TOCNC than the PEO blocks. AFM and QCM-D analyses supported the formation of a rigid, thin layer of block copolymer surrounding the TOCNC. A degree of modification (7 %) was achieved, even after washing, proving that adsorption is persistent and mainly irreversible.",

keywords = "Adsorption, Cellulose nanocrystals, TEMPO oxidation, Triblock copolymer",

author = "Alessandra Lavoratti and Diejomaoh, {Onajite Abafe} and Seddon, {Annela M.} and Koev, {Todor T.} and Khimyak, {Yaroslav Z.} and Harniman, {Robert L.} and Kontturi, {Katri S.} and Tekla Tammelin and Eichhorn, {Stephen J.}",

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AU - Lavoratti, Alessandra

AU - Diejomaoh, Onajite Abafe

AU - Seddon, Annela M.

AU - Koev, Todor T.

AU - Khimyak, Yaroslav Z.

AU - Harniman, Robert L.

AU - Kontturi, Katri S.

AU - Tammelin, Tekla

AU - Eichhorn, Stephen J.

PY - 2025/3/15

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AB - Cellulose nanocrystals (CNCs) have emerged as promising, sustainable materials, with applications in sensors, coatings, pharmaceuticals, and composites. Their modification with block copolymers such as PEO-PPO-PEO triblock copolymers of the Pluronic family has been attempted many times in the literature, with claims that such modification would happen by an anchor(PEO)-buoy(PPO)-anchor(PEO) mechanism. However, there is much disagreement in the literature on this. We herein physically adsorbed Pluronic F127, a nontoxic triblock copolymer poloxamer, comprising hydrophilic polyethylene oxide (PEO) and hydrophobic polypropylene oxide (PPO) blocks, onto the surface of TEMPO oxidised CNCs by simple mixing in an aqueous medium. The adsorption of F127 onto the surface of these CNCs was successful and persistent even after solubilisation. The thermal stability of modified TOCNCs increased (by ∼19 °C) compared to their neat and oxidised counterparts. F127-TOCNC suspensions exhibited comparable viscosity to their neat and oxidised counterparts without premature gelation of F127. NOESY NMR observations showed that PPO blocks are more proximal to the TOCNC than the PEO blocks. AFM and QCM-D analyses supported the formation of a rigid, thin layer of block copolymer surrounding the TOCNC. A degree of modification (7 %) was achieved, even after washing, proving that adsorption is persistent and mainly irreversible.

KW - Adsorption

KW - Cellulose nanocrystals

KW - TEMPO oxidation

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JO - Carbohydrate Polymers

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Investigating the interactions between a poloxamer and TEMPO-oxidised cellulose nanocrystals

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