Highly regioselective surface acetylation of cellulose and shaped cellulose constructs in the gas-phase

Tetyana Koso (Corresponding Author), Marco Beaumont, Blaise L. Tardy, Daniel Rico del Cerro, Samuel Eyley, Wim Thielemans, Orlando J. Rojas, Ilkka Kilpeläinen, Alistair W.T. King (Corresponding Author)

Research output: Contribution to journalArticleScientificpeer-review

12 Citations (Scopus)

Abstract

Gas-phase acylation is an attractive and sustainable method for modifying the surface properties of cellulosics. However, little is known concerning the regioselectivity of the chemistry, i.e., which cellulose hydroxyls are preferentially acylated and if acylation can be restricted to the surface, preserving crystallinities/morphologies. Consequently, we reexplore simple gas-phase acetylation of modern-day cellulosic building blocks - cellulose nanocrystals, pulps, dry-jet wet spun (regenerated cellulose) fibres and a nanocellulose-based aerogel. Using advanced analytics, we show that the gas-phase acetylation is highly regioselective for the C6-OH, a finding also supported by DFT-based transition-state modelling on a crystalloid surface. This contrasts with acid- and base-catalysed liquid-phase acetylation methods, highlighting that gas-phase chemistry is much more controllable, yet with similar kinetics, to the uncatalyzed liquid-phase reactions. Furthermore, this method preserves both the native (or regenerated) crystalline structure of the cellulose and the supramolecular morphology of even delicate cellulosic constructs (nanocellulose aerogel exhibiting chiral cholesteric liquid crystalline phases). Due to the soft nature of this chemistry and an ability to finely control the kinetics, yielding highly regioselective low degree of substitution products, we are convinced this method will facilitate the rapid adoption of precisely tailored and biodegradable cellulosic materials.

Original languageEnglish
Pages (from-to)5604-5613
JournalGreen Chemistry
Volume24
Issue number14
DOIs
Publication statusPublished - 21 Jun 2022
MoE publication typeA1 Journal article-refereed

Funding

T. K. & A. K. would like to acknowledge the Academy of Finland for funding under the project “WTF-Click-Nano” (project #311255). M. B., B. L. T. and O. J. R. acknowledge funding support from the European Research Council (ERC) under the European Union's Horizon 2020 research and innovation program (grant agreement no. 788489, BioElCell). We are also grateful to the University of Melbourne Materials Characterisation and Fabrication Platform (MCFP), and Prof. Raymond Dagastine for his support in obtaining the AFM data. W. T. and S. E. thank KU Leuven (grant C14/18/061) as well as EU Interreg Vlaanderen-Nederland, Flanders Innovation and Trade and the Province of West Flanders (Accelerate3 project) for funding. The authors would also like to acknowledge the CSC – IT Centre for Science, Finland, and Finnish Grid and Cloud Infrastructure (persistent identifier urn:nbn:fi:research-infras-2016072533) for computational resources. Finally, the authors would like to thank Prof. Herbert Sixta (Aalto University) for his many advices concerning cellulose chemistry and structure.

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