Cellulose modified to host functionalities via facile cation exchange approach

Panagiotis Spiliopoulos; Saül Llàcer Navarro; Eliott Orzan; Reza Ghanbari; Rudolf Pietschnig; Clemens Stilianu; Stefan Spirk; Andreas Schaefer; Roland Kádár; Tiina Nypelö

doi:10.1016/j.carbpol.2024.121857

Cellulose modified to host functionalities via facile cation exchange approach

Carbohydr Polym. 2024 May 15:332:121857. doi: 10.1016/j.carbpol.2024.121857. Epub 2024 Jan 22.

Authors

Affiliations

¹ Department of Chemistry and Chemical Engineering, Chalmers University of Technology, Gothenburg, Sweden; Wallenberg Wood Science Center (WWSC), Chalmers University of Technology, Gothenburg, Sweden.
² Department of Chemistry and Chemical Engineering, Chalmers University of Technology, Gothenburg, Sweden.
³ Department of Industrial and Materials Science, Chalmers University of Technology, Gothenburg, Sweden.
⁴ Institute of Chemistry and CINSaT, University of Kassel, Kassel, Germany.
⁵ Institute of Biomedical Imaging, Graz University of Technology, Graz, Austria.
⁶ Institute of Bioproducts and Paper Technology, Graz University of Technology, Graz, Austria.
⁷ Wallenberg Wood Science Center (WWSC), Chalmers University of Technology, Gothenburg, Sweden; Department of Industrial and Materials Science, Chalmers University of Technology, Gothenburg, Sweden.
⁸ Department of Chemistry and Chemical Engineering, Chalmers University of Technology, Gothenburg, Sweden; Wallenberg Wood Science Center (WWSC), Chalmers University of Technology, Gothenburg, Sweden; Department of Bioproducts and Biosystems, Aalto University, Espoo, Finland. Electronic address: tiina.nypelo@aalto.fi.

PMID: 38431387
DOI: 10.1016/j.carbpol.2024.121857

Abstract

Properties of cellulose are typically functionalized by organic chemistry means. We progress an alternative facile way to functionalize cellulose by functional group counter-cation exchange. While ion-exchange is established for cellulose, it is far from exploited and understood beyond the most common cation, sodium. We build on our work that established the cation exchange for go-to alkali metal cations. We expand and further demonstrate the introduction of functional cations, namely, lanthanides. We show that cellulose nanocrystals (CNCs) carrying sulfate-half ester groups can acquire properties through the counter-cation exchange. Trivalent lanthanide cations europium (Eu³⁺), dysprosium (Dy³⁺) and gadolinium (Gd³⁺) were employed. The respective ions showed distinct differences in their ability of being coordinated by the sulfate groups; with Eu³⁺ fully saturating the sulfate groups while for Gd³⁺ and Dy³⁺, values of 82 and 41 % were determined by compositional analysis. CNCs functionalized with Eu³⁺ displayed red emission, those containing Dy³⁺ exhibited no optical functionality, while those with Gd³⁺ revealed significantly altered magnetic relaxation times. Using cation exchange to alter cellulose properties in various ways is a tremendous opportunity for modification of the abundant cellulose raw materials for a renewable future.

Keywords: Lanthanides; Luminescence; Rheology.