Extrusion-Based 3D Printing of Photocrosslinkable Chitosan Inks

Photocuring of chitosan has shown great promise in the extrusion-based 3D printing of scaffolds for advanced biomedical and tissue engineering applications. However, the poor mechanical stability of methacrylated chitosan photocuring ink restricts its applicability. The inclusion of co-networks by m...

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Main Authors: Ane García-García, Leyre Pérez-Álvarez, Leire Ruiz-Rubio, Asier Larrea-Sebal, Cesar Martin, José Luis Vilas-Vilela
Format: Article
Language:English
Published: MDPI AG 2024-02-01
Series:Gels
Subjects:
Online Access:https://www.mdpi.com/2310-2861/10/2/126
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author Ane García-García
Leyre Pérez-Álvarez
Leire Ruiz-Rubio
Asier Larrea-Sebal
Cesar Martin
José Luis Vilas-Vilela
author_facet Ane García-García
Leyre Pérez-Álvarez
Leire Ruiz-Rubio
Asier Larrea-Sebal
Cesar Martin
José Luis Vilas-Vilela
author_sort Ane García-García
collection DOAJ
description Photocuring of chitosan has shown great promise in the extrusion-based 3D printing of scaffolds for advanced biomedical and tissue engineering applications. However, the poor mechanical stability of methacrylated chitosan photocuring ink restricts its applicability. The inclusion of co-networks by means of simultaneous polycomplex formation is an effective method by which to solve this drawback, but the formed hydrogel inks are not printable. This work aims to develop new photocurable chitosan inks based on the simultaneous photocrosslinking of methacrylated chitosan (CHIMe) with N,N′-methylenebisacrylamide, polyethylene glycol diacrylate, and acrylic acid to be applied in extrusion 3D printing. Interestingly, the polycomplex co-network corresponding to the acrylic-acid-based ink could be successfully printed by the here-presented simultaneous photocuring strategy. Further, the conversion of photocrosslinking was studied via photo-DSC analyses that revealed a clear dependence on the chemical structure of the employed crosslinking agents (from 40 to ~100%). In addition, the mechanical and rheological properties of the photocured hydrogels were comparatively studied, as well as the printing quality of the extruded scaffolds. The newly developed chitosan photocurable inks demonstrated extrusion printability (squareness ~0.90; uniformity factor ~0.95) and tunable mechanical properties (Young modulus 14–1068 Pa) by means of different crosslinking approaches according to the chemical architecture of the reactive molecules employed. This work shows the great potential of photocrosslinkable chitosan inks.
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spelling doaj.art-5e34e776963342139a3df47edaf23ce42024-02-23T15:17:32ZengMDPI AGGels2310-28612024-02-0110212610.3390/gels10020126Extrusion-Based 3D Printing of Photocrosslinkable Chitosan InksAne García-García0Leyre Pérez-Álvarez1Leire Ruiz-Rubio2Asier Larrea-Sebal3Cesar Martin4José Luis Vilas-Vilela5Grupo de Química Macromolecular (LABQUIMAC), Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), 48940 Leioa, SpainGrupo de Química Macromolecular (LABQUIMAC), Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), 48940 Leioa, SpainGrupo de Química Macromolecular (LABQUIMAC), Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), 48940 Leioa, SpainBiofisika Institute (UPV/EHU, CSIC), UPV/EHU Science Park, 48940 Leioa, SpainBiofisika Institute (UPV/EHU, CSIC), UPV/EHU Science Park, 48940 Leioa, SpainGrupo de Química Macromolecular (LABQUIMAC), Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco (UPV/EHU), 48940 Leioa, SpainPhotocuring of chitosan has shown great promise in the extrusion-based 3D printing of scaffolds for advanced biomedical and tissue engineering applications. However, the poor mechanical stability of methacrylated chitosan photocuring ink restricts its applicability. The inclusion of co-networks by means of simultaneous polycomplex formation is an effective method by which to solve this drawback, but the formed hydrogel inks are not printable. This work aims to develop new photocurable chitosan inks based on the simultaneous photocrosslinking of methacrylated chitosan (CHIMe) with N,N′-methylenebisacrylamide, polyethylene glycol diacrylate, and acrylic acid to be applied in extrusion 3D printing. Interestingly, the polycomplex co-network corresponding to the acrylic-acid-based ink could be successfully printed by the here-presented simultaneous photocuring strategy. Further, the conversion of photocrosslinking was studied via photo-DSC analyses that revealed a clear dependence on the chemical structure of the employed crosslinking agents (from 40 to ~100%). In addition, the mechanical and rheological properties of the photocured hydrogels were comparatively studied, as well as the printing quality of the extruded scaffolds. The newly developed chitosan photocurable inks demonstrated extrusion printability (squareness ~0.90; uniformity factor ~0.95) and tunable mechanical properties (Young modulus 14–1068 Pa) by means of different crosslinking approaches according to the chemical architecture of the reactive molecules employed. This work shows the great potential of photocrosslinkable chitosan inks.https://www.mdpi.com/2310-2861/10/2/126methacrylated chitosanphotocrosslinkingextrusion printing
spellingShingle Ane García-García
Leyre Pérez-Álvarez
Leire Ruiz-Rubio
Asier Larrea-Sebal
Cesar Martin
José Luis Vilas-Vilela
Extrusion-Based 3D Printing of Photocrosslinkable Chitosan Inks
Gels
methacrylated chitosan
photocrosslinking
extrusion printing
title Extrusion-Based 3D Printing of Photocrosslinkable Chitosan Inks
title_full Extrusion-Based 3D Printing of Photocrosslinkable Chitosan Inks
title_fullStr Extrusion-Based 3D Printing of Photocrosslinkable Chitosan Inks
title_full_unstemmed Extrusion-Based 3D Printing of Photocrosslinkable Chitosan Inks
title_short Extrusion-Based 3D Printing of Photocrosslinkable Chitosan Inks
title_sort extrusion based 3d printing of photocrosslinkable chitosan inks
topic methacrylated chitosan
photocrosslinking
extrusion printing
url https://www.mdpi.com/2310-2861/10/2/126
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AT asierlarreasebal extrusionbased3dprintingofphotocrosslinkablechitosaninks
AT cesarmartin extrusionbased3dprintingofphotocrosslinkablechitosaninks
AT joseluisvilasvilela extrusionbased3dprintingofphotocrosslinkablechitosaninks