Conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high-fidelity 3D printing

While 3D printing has enabled the fabrication of hydrogels with complex structures, high fidelity techniques (vat polymerization) that enable precisely engineered design of hydrogels require stiff structures to withstand the forces of printing. This is a pressing research gap in hydrogel vat-polymer...

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Main Authors: Lukas A. Bauman, Boxin Zhao
Format: Article
Language:English
Published: Elsevier 2025-03-01
Series:Carbohydrate Polymer Technologies and Applications
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Online Access:http://www.sciencedirect.com/science/article/pii/S2666893925000416
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author Lukas A. Bauman
Boxin Zhao
author_facet Lukas A. Bauman
Boxin Zhao
author_sort Lukas A. Bauman
collection DOAJ
description While 3D printing has enabled the fabrication of hydrogels with complex structures, high fidelity techniques (vat polymerization) that enable precisely engineered design of hydrogels require stiff structures to withstand the forces of printing. This is a pressing research gap in hydrogel vat-polymerization 3D printing. To address this limitation, a novel ionic crosslinker consisting of quaternized chitosan complexed with 3-sulfopropyl acrylate was used to form supramolecular 2-hydroxyethyl acrylate organogel precursors. The Cyrene organogel enhanced mechanical properties enabling the printing of high-fidelity structures; the final compliant hydrogels were then obtained through solvent exchange with water. This yielded high-fidelity 3D-printed conductive supramolecular hydrogels with tensile properties of 288±29 kPa at 516±37 % elongation and compressive properties of 572±34 kPa at 65±4 % strain with uniform swelling (320–350 %). Nuclear magnetic resonance and conductivity measurements confirmed SPA-rich blocks within the hydrogel network and the solvent-dependent copolymer structure. Furthermore, through varying the anionic acrylate concentration, ultimate strain between 222 % and 516 % was achieved at a constant elastic modulus. Additionally, electrical properties were tunable with conductivity reaching 156 mS/m at 7 MH in ultrapure water. This work advances applications of quaternized chitosan as an ionic crosslinker in printable conductive hydrogels, opening new applications in medical and technological fields.
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spelling doaj-art-0e7d820be45f4a6998f8f0b49952e0b32025-02-10T04:35:02ZengElsevierCarbohydrate Polymer Technologies and Applications2666-89392025-03-019100702Conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high-fidelity 3D printingLukas A. Bauman0Boxin Zhao1Surface Science and Bio-nanomaterials Laboratory, Waterloo Institute for Nanotechnology, Institute for Polymer Research, Centre for Bioengineering and Biotechnology, Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2 L 3G1, CanadaCorresponding author.; Surface Science and Bio-nanomaterials Laboratory, Waterloo Institute for Nanotechnology, Institute for Polymer Research, Centre for Bioengineering and Biotechnology, Department of Chemical Engineering, University of Waterloo, 200 University Avenue West, Waterloo, Ontario N2 L 3G1, CanadaWhile 3D printing has enabled the fabrication of hydrogels with complex structures, high fidelity techniques (vat polymerization) that enable precisely engineered design of hydrogels require stiff structures to withstand the forces of printing. This is a pressing research gap in hydrogel vat-polymerization 3D printing. To address this limitation, a novel ionic crosslinker consisting of quaternized chitosan complexed with 3-sulfopropyl acrylate was used to form supramolecular 2-hydroxyethyl acrylate organogel precursors. The Cyrene organogel enhanced mechanical properties enabling the printing of high-fidelity structures; the final compliant hydrogels were then obtained through solvent exchange with water. This yielded high-fidelity 3D-printed conductive supramolecular hydrogels with tensile properties of 288±29 kPa at 516±37 % elongation and compressive properties of 572±34 kPa at 65±4 % strain with uniform swelling (320–350 %). Nuclear magnetic resonance and conductivity measurements confirmed SPA-rich blocks within the hydrogel network and the solvent-dependent copolymer structure. Furthermore, through varying the anionic acrylate concentration, ultimate strain between 222 % and 516 % was achieved at a constant elastic modulus. Additionally, electrical properties were tunable with conductivity reaching 156 mS/m at 7 MH in ultrapure water. This work advances applications of quaternized chitosan as an ionic crosslinker in printable conductive hydrogels, opening new applications in medical and technological fields.http://www.sciencedirect.com/science/article/pii/S26668939250004163D printingPhoto-polymerizationQuaternized chitosanChitosanConductive polymersSupramolecular hydrogel
spellingShingle Lukas A. Bauman
Boxin Zhao
Conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high-fidelity 3D printing
Carbohydrate Polymer Technologies and Applications
3D printing
Photo-polymerization
Quaternized chitosan
Chitosan
Conductive polymers
Supramolecular hydrogel
title Conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high-fidelity 3D printing
title_full Conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high-fidelity 3D printing
title_fullStr Conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high-fidelity 3D printing
title_full_unstemmed Conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high-fidelity 3D printing
title_short Conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high-fidelity 3D printing
title_sort conductive supramolecular acrylate hydrogels enabled by quaternized chitosan ionic crosslinking for high fidelity 3d printing
topic 3D printing
Photo-polymerization
Quaternized chitosan
Chitosan
Conductive polymers
Supramolecular hydrogel
url http://www.sciencedirect.com/science/article/pii/S2666893925000416
work_keys_str_mv AT lukasabauman conductivesupramolecularacrylatehydrogelsenabledbyquaternizedchitosanioniccrosslinkingforhighfidelity3dprinting
AT boxinzhao conductivesupramolecularacrylatehydrogelsenabledbyquaternizedchitosanioniccrosslinkingforhighfidelity3dprinting