Challenges in Synthesis and Analysis of Asymmetrically Grafted Cellulose Nanocrystals via Atom Transfer Radical Polymerization

Gwendoline Delepierre; Katja Heise; Kiia Malinen; Tetyana Koso; Leena Pitkänen; Emily D. Cranston; Ilkka Kilpeläinen; Mauri A. Kostiainen; Eero Kontturi; Christoph Weder; Justin O. Zoppe; Alistair W.T. King

doi:10.1021/acs.biomac.1c00392

Challenges in Synthesis and Analysis of Asymmetrically Grafted Cellulose Nanocrystals via Atom Transfer Radical Polymerization

Gwendoline Delepierre
, Katja Heise
, Kiia Malinen
, Tetyana Koso
, Leena Pitkänen
, Emily D. Cranston
, Ilkka Kilpeläinen
, Mauri A. Kostiainen
, Eero Kontturi
, Christoph Weder
, Justin O. Zoppe
, Alistair W.T. King^*

^*Corresponding author for this work

Not published at VTT

Aalto University
University of Helsinki
University of British Columbia
Polytechnic University of Catalonia (UPC)
University of Freiburg
Adolphe Merkle Institute

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

22 Citations (Scopus)

Abstract

When cellulose nanocrystals (CNCs) are isolated from cellulose microfibrils, the parallel arrangement of the cellulose chains in the crystalline domains is retained so that all reducing end-groups (REGs) point to one crystallite end. This permits the selective chemical modification of one end of the CNCs. In this study, two reaction pathways are compared to selectively attach atom-transfer radical polymerization (ATRP) initiators to the REGs of CNCs, using reductive amination. This modification further enabled the site-specific grafting of the anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS) from the CNCs. Different analytical methods, including colorimetry and solution-state NMR analysis, were combined to confirm the REG-modification with ATRP-initiators and PSS. The achieved grafting yield was low due to either a limited conversion of the CNC REGs or side reactions on the polymerization initiator during the reductive amination. The end-tethered CNCs were easy to redisperse in water after freeze-drying, and the shear birefringence of colloidal suspensions is maintained after this process.

Original language	English
Pages (from-to)	2702-2717
Number of pages	16
Journal	Biomacromolecules
Volume	22
Issue number	6
DOIs	https://doi.org/10.1021/acs.biomac.1c00392
Publication status	Published - 14 Jun 2021
MoE publication type	A1 Journal article-refereed

Funding

This work was part of the Academy of Finland’s Flagship Program (Project Numbers 318890 and 318891, Competence Center for Materials Bioeconomy, FinnCERES). K.H. acknowledges postdoc funding provided by the Academy of Finland (Project Number 333905). A.K. and T.K. would like to acknowledge the Academy of Finland for funding under the project “WTF-Click-Nano” (Project #311255). G.D. and J.Z. acknowledge funding provided by the Swiss National Science Foundation (SNSF; Ambizione Grant No. PZ00P2_167900), and G.D., C.W., and J.Z. thank the Adolphe Merkle Foundation for support. J.Z. gratefully acknowledges the Serra Hunter Fellowship from the Generalitat de Catalunya. This work was part of the Academy of Finland's Flagship Program (Project Numbers 318890 and 318891, Competence Center for Materials Bioeconomy FinnCERES). K.H. acknowledges postdoc funding provided by the Academy of Finland (Project Number 333905). A.K. and T.K. would like to acknowledge the Academy of Finland for funding under the project "WTF-Click-Nano" (Project #311255). G.D. and J.Z. acknowledge funding provided by the Swiss National Science Foundation (SNSF; Ambizione Grant No. PZ00P2_167900) and G.D., C.W., and J.Z. thank the Adolphe Merkle Foundation for support. J.Z. gratefully acknowledges the Serra Hunter Fellowship from the Generalitat de Catalunya.

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Delepierre, G., Heise, K., Malinen, K., Koso, T., Pitkänen, L., Cranston, E. D., Kilpeläinen, I., Kostiainen, M. A., Kontturi, E., Weder, C., Zoppe, J. O., & King, A. W. T. (2021). Challenges in Synthesis and Analysis of Asymmetrically Grafted Cellulose Nanocrystals via Atom Transfer Radical Polymerization. Biomacromolecules, 22(6), 2702-2717. https://doi.org/10.1021/acs.biomac.1c00392

@article{9e31f6e74a5a4ff0b89d77786dda634d,

title = "Challenges in Synthesis and Analysis of Asymmetrically Grafted Cellulose Nanocrystals via Atom Transfer Radical Polymerization",

abstract = "When cellulose nanocrystals (CNCs) are isolated from cellulose microfibrils, the parallel arrangement of the cellulose chains in the crystalline domains is retained so that all reducing end-groups (REGs) point to one crystallite end. This permits the selective chemical modification of one end of the CNCs. In this study, two reaction pathways are compared to selectively attach atom-transfer radical polymerization (ATRP) initiators to the REGs of CNCs, using reductive amination. This modification further enabled the site-specific grafting of the anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS) from the CNCs. Different analytical methods, including colorimetry and solution-state NMR analysis, were combined to confirm the REG-modification with ATRP-initiators and PSS. The achieved grafting yield was low due to either a limited conversion of the CNC REGs or side reactions on the polymerization initiator during the reductive amination. The end-tethered CNCs were easy to redisperse in water after freeze-drying, and the shear birefringence of colloidal suspensions is maintained after this process.",

author = "Gwendoline Delepierre and Katja Heise and Kiia Malinen and Tetyana Koso and Leena Pitk{\"a}nen and Cranston, \{Emily D.\} and Ilkka Kilpel{\"a}inen and Kostiainen, \{Mauri A.\} and Eero Kontturi and Christoph Weder and Zoppe, \{Justin O.\} and King, \{Alistair W.T.\}",

note = "Funding Information: This work was part of the Academy of Finland{\textquoteright}s Flagship Program (Project Numbers 318890 and 318891, Competence Center for Materials Bioeconomy, FinnCERES). K.H. acknowledges postdoc funding provided by the Academy of Finland (Project Number 333905). A.K. and T.K. would like to acknowledge the Academy of Finland for funding under the project “WTF-Click-Nano” (Project \#311255). G.D. and J.Z. acknowledge funding provided by the Swiss National Science Foundation (SNSF; Ambizione Grant No. PZ00P2\_167900), and G.D., C.W., and J.Z. thank the Adolphe Merkle Foundation for support. J.Z. gratefully acknowledges the Serra Hunter Fellowship from the Generalitat de Catalunya. Funding Information: This work was part of the Academy of Finland's Flagship Program (Project Numbers 318890 and 318891, Competence Center for Materials Bioeconomy FinnCERES). K.H. acknowledges postdoc funding provided by the Academy of Finland (Project Number 333905). A.K. and T.K. would like to acknowledge the Academy of Finland for funding under the project {"}WTF-Click-Nano{"} (Project \#311255). G.D. and J.Z. acknowledge funding provided by the Swiss National Science Foundation (SNSF; Ambizione Grant No. PZ00P2\_167900) and G.D., C.W., and J.Z. thank the Adolphe Merkle Foundation for support. J.Z. gratefully acknowledges the Serra Hunter Fellowship from the Generalitat de Catalunya. Publisher Copyright: {\textcopyright} 2021 The Authors. Published by American Chemical Society.",

year = "2021",

month = jun,

day = "14",

doi = "10.1021/acs.biomac.1c00392",

language = "English",

volume = "22",

pages = "2702--2717",

journal = "Biomacromolecules",

issn = "1525-7797",

publisher = "American Chemical Society ACS",

number = "6",

}

Delepierre, G, Heise, K, Malinen, K, Koso, T, Pitkänen, L, Cranston, ED, Kilpeläinen, I, Kostiainen, MA, Kontturi, E, Weder, C, Zoppe, JO & King, AWT 2021, 'Challenges in Synthesis and Analysis of Asymmetrically Grafted Cellulose Nanocrystals via Atom Transfer Radical Polymerization', Biomacromolecules, vol. 22, no. 6, pp. 2702-2717. https://doi.org/10.1021/acs.biomac.1c00392

TY - JOUR

T1 - Challenges in Synthesis and Analysis of Asymmetrically Grafted Cellulose Nanocrystals via Atom Transfer Radical Polymerization

AU - Delepierre, Gwendoline

AU - Heise, Katja

AU - Malinen, Kiia

AU - Koso, Tetyana

AU - Pitkänen, Leena

AU - Cranston, Emily D.

AU - Kilpeläinen, Ilkka

AU - Kostiainen, Mauri A.

AU - Kontturi, Eero

AU - Weder, Christoph

AU - Zoppe, Justin O.

AU - King, Alistair W.T.

N1 - Funding Information: This work was part of the Academy of Finland’s Flagship Program (Project Numbers 318890 and 318891, Competence Center for Materials Bioeconomy, FinnCERES). K.H. acknowledges postdoc funding provided by the Academy of Finland (Project Number 333905). A.K. and T.K. would like to acknowledge the Academy of Finland for funding under the project “WTF-Click-Nano” (Project #311255). G.D. and J.Z. acknowledge funding provided by the Swiss National Science Foundation (SNSF; Ambizione Grant No. PZ00P2_167900), and G.D., C.W., and J.Z. thank the Adolphe Merkle Foundation for support. J.Z. gratefully acknowledges the Serra Hunter Fellowship from the Generalitat de Catalunya. Funding Information: This work was part of the Academy of Finland's Flagship Program (Project Numbers 318890 and 318891, Competence Center for Materials Bioeconomy FinnCERES). K.H. acknowledges postdoc funding provided by the Academy of Finland (Project Number 333905). A.K. and T.K. would like to acknowledge the Academy of Finland for funding under the project "WTF-Click-Nano" (Project #311255). G.D. and J.Z. acknowledge funding provided by the Swiss National Science Foundation (SNSF; Ambizione Grant No. PZ00P2_167900) and G.D., C.W., and J.Z. thank the Adolphe Merkle Foundation for support. J.Z. gratefully acknowledges the Serra Hunter Fellowship from the Generalitat de Catalunya. Publisher Copyright: © 2021 The Authors. Published by American Chemical Society.

PY - 2021/6/14

Y1 - 2021/6/14

N2 - When cellulose nanocrystals (CNCs) are isolated from cellulose microfibrils, the parallel arrangement of the cellulose chains in the crystalline domains is retained so that all reducing end-groups (REGs) point to one crystallite end. This permits the selective chemical modification of one end of the CNCs. In this study, two reaction pathways are compared to selectively attach atom-transfer radical polymerization (ATRP) initiators to the REGs of CNCs, using reductive amination. This modification further enabled the site-specific grafting of the anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS) from the CNCs. Different analytical methods, including colorimetry and solution-state NMR analysis, were combined to confirm the REG-modification with ATRP-initiators and PSS. The achieved grafting yield was low due to either a limited conversion of the CNC REGs or side reactions on the polymerization initiator during the reductive amination. The end-tethered CNCs were easy to redisperse in water after freeze-drying, and the shear birefringence of colloidal suspensions is maintained after this process.

AB - When cellulose nanocrystals (CNCs) are isolated from cellulose microfibrils, the parallel arrangement of the cellulose chains in the crystalline domains is retained so that all reducing end-groups (REGs) point to one crystallite end. This permits the selective chemical modification of one end of the CNCs. In this study, two reaction pathways are compared to selectively attach atom-transfer radical polymerization (ATRP) initiators to the REGs of CNCs, using reductive amination. This modification further enabled the site-specific grafting of the anionic polyelectrolyte poly(sodium 4-styrenesulfonate) (PSS) from the CNCs. Different analytical methods, including colorimetry and solution-state NMR analysis, were combined to confirm the REG-modification with ATRP-initiators and PSS. The achieved grafting yield was low due to either a limited conversion of the CNC REGs or side reactions on the polymerization initiator during the reductive amination. The end-tethered CNCs were easy to redisperse in water after freeze-drying, and the shear birefringence of colloidal suspensions is maintained after this process.

UR - https://www.scopus.com/pages/publications/85108303230

U2 - 10.1021/acs.biomac.1c00392

DO - 10.1021/acs.biomac.1c00392

M3 - Article

C2 - 34060815

AN - SCOPUS:85108303230

SN - 1525-7797

VL - 22

SP - 2702

EP - 2717

JO - Biomacromolecules

JF - Biomacromolecules

IS - 6

ER -

Challenges in Synthesis and Analysis of Asymmetrically Grafted Cellulose Nanocrystals via Atom Transfer Radical Polymerization

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