Allyl-Functionalized Polysaccharides for 3D Printable Hydrogels Through Thiol–Ene Click Chemistry

This study presents the synthesis of allyl-functionalized polysaccharide carbamates (AFCs) with tailored water solubility designed for use in responsive hydrogels and 3D printing applications. A modular one-pot approach was employed to produce cellulose- and xylan-based AFCs, utilizing polysaccharid...

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Main Authors: Zakaria Atmani, Tobias Steindorfer, Rupert Kargl, Karin Stana Kleinschek, Thomas Heinze, Martin Gericke
Format: Article
Language:English
Published: MDPI AG 2025-02-01
Series:Polysaccharides
Subjects:
Online Access:https://www.mdpi.com/2673-4176/6/1/13
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author Zakaria Atmani
Tobias Steindorfer
Rupert Kargl
Karin Stana Kleinschek
Thomas Heinze
Martin Gericke
author_facet Zakaria Atmani
Tobias Steindorfer
Rupert Kargl
Karin Stana Kleinschek
Thomas Heinze
Martin Gericke
author_sort Zakaria Atmani
collection DOAJ
description This study presents the synthesis of allyl-functionalized polysaccharide carbamates (AFCs) with tailored water solubility designed for use in responsive hydrogels and 3D printing applications. A modular one-pot approach was employed to produce cellulose- and xylan-based AFCs, utilizing polysaccharide phenyl carbonates as activated compounds. By fine-tuning the degree of substitution (DS) of functional groups, the water solubility and shear-thinning properties of AFCs were controlled to enhance the gelation and printability. AFC-based hydrogels could be obtained by rapid gelation induced without harmful catalysts through UV irradiation at 365 nm. The materials displayed highly porous and interconnected microstructures, as well as mechanical resilience and high swelling ratios. The hydrogel formation was characterized, and its crosslinking degree was calculated using HR-MAS NMR. The study demonstrated that gelation behavior was sensitive to the pH value, with optimal results under neutral or acidic conditions. Initial 3D printing trials confirmed the material’s rapid shaping capabilities, which is beneficial for biomedical applications and advanced manufacturing of stimuli-responsive materials.
format Article
id doaj-art-cb4749c51d4341ffbd8badcc8479419c
institution OA Journals
issn 2673-4176
language English
publishDate 2025-02-01
publisher MDPI AG
record_format Article
series Polysaccharides
spelling doaj-art-cb4749c51d4341ffbd8badcc8479419c2025-08-20T01:49:01ZengMDPI AGPolysaccharides2673-41762025-02-01611310.3390/polysaccharides6010013Allyl-Functionalized Polysaccharides for 3D Printable Hydrogels Through Thiol–Ene Click ChemistryZakaria Atmani0Tobias Steindorfer1Rupert Kargl2Karin Stana Kleinschek3Thomas Heinze4Martin Gericke5Centre of Excellence for Polysaccharide Research, Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstraße 10, 07743 Jena, GermanyInstitute for Chemistry and Technology of Biobased Systems (IBIOSYS), Graz University of Technology, Stremayrgasse 9, 8010 Graz, AustriaInstitute for Chemistry and Technology of Biobased Systems (IBIOSYS), Graz University of Technology, Stremayrgasse 9, 8010 Graz, AustriaInstitute for Chemistry and Technology of Biobased Systems (IBIOSYS), Graz University of Technology, Stremayrgasse 9, 8010 Graz, AustriaCentre of Excellence for Polysaccharide Research, Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstraße 10, 07743 Jena, GermanyCentre of Excellence for Polysaccharide Research, Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University Jena, Humboldtstraße 10, 07743 Jena, GermanyThis study presents the synthesis of allyl-functionalized polysaccharide carbamates (AFCs) with tailored water solubility designed for use in responsive hydrogels and 3D printing applications. A modular one-pot approach was employed to produce cellulose- and xylan-based AFCs, utilizing polysaccharide phenyl carbonates as activated compounds. By fine-tuning the degree of substitution (DS) of functional groups, the water solubility and shear-thinning properties of AFCs were controlled to enhance the gelation and printability. AFC-based hydrogels could be obtained by rapid gelation induced without harmful catalysts through UV irradiation at 365 nm. The materials displayed highly porous and interconnected microstructures, as well as mechanical resilience and high swelling ratios. The hydrogel formation was characterized, and its crosslinking degree was calculated using HR-MAS NMR. The study demonstrated that gelation behavior was sensitive to the pH value, with optimal results under neutral or acidic conditions. Initial 3D printing trials confirmed the material’s rapid shaping capabilities, which is beneficial for biomedical applications and advanced manufacturing of stimuli-responsive materials.https://www.mdpi.com/2673-4176/6/1/13polysaccharideschemical derivatizationhydrogelsthiol–ene click chemistry3D printing
spellingShingle Zakaria Atmani
Tobias Steindorfer
Rupert Kargl
Karin Stana Kleinschek
Thomas Heinze
Martin Gericke
Allyl-Functionalized Polysaccharides for 3D Printable Hydrogels Through Thiol–Ene Click Chemistry
Polysaccharides
polysaccharides
chemical derivatization
hydrogels
thiol–ene click chemistry
3D printing
title Allyl-Functionalized Polysaccharides for 3D Printable Hydrogels Through Thiol–Ene Click Chemistry
title_full Allyl-Functionalized Polysaccharides for 3D Printable Hydrogels Through Thiol–Ene Click Chemistry
title_fullStr Allyl-Functionalized Polysaccharides for 3D Printable Hydrogels Through Thiol–Ene Click Chemistry
title_full_unstemmed Allyl-Functionalized Polysaccharides for 3D Printable Hydrogels Through Thiol–Ene Click Chemistry
title_short Allyl-Functionalized Polysaccharides for 3D Printable Hydrogels Through Thiol–Ene Click Chemistry
title_sort allyl functionalized polysaccharides for 3d printable hydrogels through thiol ene click chemistry
topic polysaccharides
chemical derivatization
hydrogels
thiol–ene click chemistry
3D printing
url https://www.mdpi.com/2673-4176/6/1/13
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AT rupertkargl allylfunctionalizedpolysaccharidesfor3dprintablehydrogelsthroughthioleneclickchemistry
AT karinstanakleinschek allylfunctionalizedpolysaccharidesfor3dprintablehydrogelsthroughthioleneclickchemistry
AT thomasheinze allylfunctionalizedpolysaccharidesfor3dprintablehydrogelsthroughthioleneclickchemistry
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