TY - JOUR
T1 - Unique reactivity of nanoporous cellulosic materials mediated by surface-confined water
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 - 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).
PY - 2021/5/4
Y1 - 2021/5/4
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.
UR - http://www.scopus.com/inward/record.url?scp=85105261072&partnerID=8YFLogxK
U2 - 10.1038/s41467-021-22682-3
DO - 10.1038/s41467-021-22682-3
M3 - Article
C2 - 33947852
AN - SCOPUS:85105261072
SN - 2041-1723
VL - 12
SP - 2513
JO - Nature Communications
JF - Nature Communications
IS - 1
M1 - 2513
ER -