Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water

Marco Beaumont; Paul Jusner; Notburga Gierlinger; Alistair W.T. King; Antje Potthast; Orlando J. Rojas; Thomas Rosenau

doi:10.1038/s41467-021-22682-3

Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water

Marco Beaumont^*
, Paul Jusner
, Notburga Gierlinger
, Alistair W.T. King
, Antje Potthast
, Orlando J. Rojas
, Thomas Rosenau^*

^*Corresponding author for this work

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

98 Citations (Scopus)

85 Downloads (Pure)

Abstract

The remarkable efficiency of chemical reactions is the result of biological evolution, often involving confined water. Meanwhile, developments of bio-inspired systems, which exploit the potential of such water, have been so far rather complex and cumbersome. Here we show that surface-confined water, inherently present in widely abundant and renewable cellulosic fibres can be utilised as nanomedium to endow a singular chemical reactivity. Compared to surface acetylation in the dry state, confined water increases the reaction rate and efficiency by 8 times and 30%, respectively. Moreover, confined water enables control over chemical accessibility of selected hydroxyl groups through the extent of hydration, allowing regioselective reactions, a major challenge in cellulose modification. The reactions mediated by surface-confined water are sustainable and largely outperform those occurring in organic solvents in terms of efficiency and environmental compatibility. Our results demonstrate the unexploited potential of water bound to cellulosic nanostructures in surface esterifications, which can be extended to a wide range of other nanoporous polymeric structures and reactions.

Original language	English
Article number	2513
Number of pages	8
Journal	Nature Communications
Volume	12
Issue number	1
Early online date	4 May 2021
DOIs	https://doi.org/10.1038/s41467-021-22682-3
Publication status	Published - Dec 2021
MoE publication type	A1 Journal article-refereed

Funding

We wish to acknowledge CSC—IT Centre for Science, Finland, and Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533) for computational resources. We thank Dr. Markus Bacher, Dr. Sonja Schiehser and Dr. Caio G. Otoni for their support with NMR, GPC and DVS measurements, respectively. Dr. Blaise L. Tardy is acknowledged for helpful discussions and SEM measurement. This research was funded in whole, or in part, by the Austrian Science Fund (FWF) (J4356). For the purpose of open access, the author has applied a CC BY public copyright license to any Author Accepted Manuscript version arising from this submission. The authors thank the financial support from the Austrian Biorefinery Centre Tulln (ABCT), the Academy of Finland (Project # 311255, ‘WTF-Click-Nano’) and the H2020-ERC-2017-Advanced Grant ‘BioELCell’ (788489).

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy

Access to Document

10.1038/s41467-021-22682-3Licence: CC BY

CHEM_Beaumont_et_al_Unique_reactivity_of_nanoporous_2021_Nature_CommunicationsFinal published version, 1.34 MBLicence: CC BY

Cite this

@article{11ac2b280a804a3487388bb08426e430,

title = "Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water",

abstract = "The remarkable efficiency of chemical reactions is the result of biological evolution, often involving confined water. Meanwhile, developments of bio-inspired systems, which exploit the potential of such water, have been so far rather complex and cumbersome. Here we show that surface-confined water, inherently present in widely abundant and renewable cellulosic fibres can be utilised as nanomedium to endow a singular chemical reactivity. Compared to surface acetylation in the dry state, confined water increases the reaction rate and efficiency by 8 times and 30\%, respectively. Moreover, confined water enables control over chemical accessibility of selected hydroxyl groups through the extent of hydration, allowing regioselective reactions, a major challenge in cellulose modification. The reactions mediated by surface-confined water are sustainable and largely outperform those occurring in organic solvents in terms of efficiency and environmental compatibility. Our results demonstrate the unexploited potential of water bound to cellulosic nanostructures in surface esterifications, which can be extended to a wide range of other nanoporous polymeric structures and reactions.",

author = "Marco Beaumont and Paul Jusner and Notburga Gierlinger and King, \{Alistair W.T.\} and Antje Potthast and Rojas, \{Orlando J.\} and Thomas Rosenau",

note = "| openaire: EC/H2020/788489/EU//BioELCell Funding Information: We wish to acknowledge CSC—IT Centre for Science, Finland, and Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533) for computational resources. We thank Dr. Markus Bacher, Dr. Sonja Schiehser and Dr. Caio G. Otoni for their support with NMR, GPC and DVS measurements, respectively. Dr. Blaise L. Tardy is acknowledged for helpful discussions and SEM measurement. This research was funded in whole, or in part, by the Austrian Science Fund (FWF) (J4356). For the purpose of open access, the author has applied a CC BY public copyright license to any Author Accepted Manuscript version arising from this submission. The authors thank the financial support from the Austrian Biorefinery Centre Tulln (ABCT), the Academy of Finland (Project \# 311255, {\textquoteleft}WTF-Click-Nano{\textquoteright}) and the H2020-ERC-2017-Advanced Grant {\textquoteleft}BioELCell{\textquoteright} (788489). Publisher Copyright: {\textcopyright} 2021, The Author(s). Copyright: Copyright 2021 Elsevier B.V., All rights reserved.",

year = "2021",

month = dec,

doi = "10.1038/s41467-021-22682-3",

language = "English",

volume = "12",

journal = "Nature Communications",

issn = "2041-1723",

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AU - Beaumont, Marco

AU - Jusner, Paul

AU - Gierlinger, Notburga

AU - King, Alistair W.T.

AU - Potthast, Antje

AU - Rojas, Orlando J.

AU - Rosenau, Thomas

N1 - | openaire: EC/H2020/788489/EU//BioELCell Funding Information: We wish to acknowledge CSC—IT Centre for Science, Finland, and Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533) for computational resources. We thank Dr. Markus Bacher, Dr. Sonja Schiehser and Dr. Caio G. Otoni for their support with NMR, GPC and DVS measurements, respectively. Dr. Blaise L. Tardy is acknowledged for helpful discussions and SEM measurement. This research was funded in whole, or in part, by the Austrian Science Fund (FWF) (J4356). For the purpose of open access, the author has applied a CC BY public copyright license to any Author Accepted Manuscript version arising from this submission. The authors thank the financial support from the Austrian Biorefinery Centre Tulln (ABCT), the Academy of Finland (Project # 311255, ‘WTF-Click-Nano’) and the H2020-ERC-2017-Advanced Grant ‘BioELCell’ (788489). Publisher Copyright: © 2021, The Author(s). Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

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Y1 - 2021/12

N2 - The remarkable efficiency of chemical reactions is the result of biological evolution, often involving confined water. Meanwhile, developments of bio-inspired systems, which exploit the potential of such water, have been so far rather complex and cumbersome. Here we show that surface-confined water, inherently present in widely abundant and renewable cellulosic fibres can be utilised as nanomedium to endow a singular chemical reactivity. Compared to surface acetylation in the dry state, confined water increases the reaction rate and efficiency by 8 times and 30%, respectively. Moreover, confined water enables control over chemical accessibility of selected hydroxyl groups through the extent of hydration, allowing regioselective reactions, a major challenge in cellulose modification. The reactions mediated by surface-confined water are sustainable and largely outperform those occurring in organic solvents in terms of efficiency and environmental compatibility. Our results demonstrate the unexploited potential of water bound to cellulosic nanostructures in surface esterifications, which can be extended to a wide range of other nanoporous polymeric structures and reactions.

AB - The remarkable efficiency of chemical reactions is the result of biological evolution, often involving confined water. Meanwhile, developments of bio-inspired systems, which exploit the potential of such water, have been so far rather complex and cumbersome. Here we show that surface-confined water, inherently present in widely abundant and renewable cellulosic fibres can be utilised as nanomedium to endow a singular chemical reactivity. Compared to surface acetylation in the dry state, confined water increases the reaction rate and efficiency by 8 times and 30%, respectively. Moreover, confined water enables control over chemical accessibility of selected hydroxyl groups through the extent of hydration, allowing regioselective reactions, a major challenge in cellulose modification. The reactions mediated by surface-confined water are sustainable and largely outperform those occurring in organic solvents in terms of efficiency and environmental compatibility. Our results demonstrate the unexploited potential of water bound to cellulosic nanostructures in surface esterifications, which can be extended to a wide range of other nanoporous polymeric structures and reactions.

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ER -

Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water

Abstract

Funding

UN SDGs

Access to Document

Other files and links

Fingerprint

Confined water-mediated surface-acetylation of cellulose: figure raw data, calibration curve and regioselectivty

BioELCell: Bioproducts Engineered from Lignocelluloses: from plants and upcycling to next generation materials

Nano: Water-free, Low-Cost Click Modification and Oxidative Regeneration of (Nano)Celluloses

Cite this

Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water

Abstract

Funding

UN SDGs

Access to Document

Other files and links

Fingerprint

Datasets

Confined water-mediated surface-acetylation of cellulose: figure raw data, calibration curve and regioselectivty

Projects

BioELCell: Bioproducts Engineered from Lignocelluloses: from plants and upcycling to next generation materials

Nano: Water-free, Low-Cost Click Modification and Oxidative Regeneration of (Nano)Celluloses

Cite this