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Volumetric printing of thiol‐ene photo‐cross‐linkable poly(ε‐caprolactone) : a tunable material platform serving biomedical applications

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Abstract
Current thoroughly described biodegradable and cross-linkable polymers mainly rely on acrylate cross-linking. However, despite the swift cross-linking kinetics of acrylates, the concomitant brittleness of the resulting materials limits their applicability. Here, photo-cross-linkable poly(e-caprolactone) networks through orthogonal thiol-ene chemistry are introduced. The step-growth polymerized networks are tunable, predictable by means of the rubber elasticity theory and it is shown that their mechanical properties are significantly improved over their acrylate cross-linked counterparts. Tunability is introduced to the materials, by altering M-c (or the molar mass between cross-links), and its effect on the thermal properties, mechanical strength and degradability of the materials is evaluated. Moreover, excellent volumetric printability is illustrated and the smallest features obtained via volumetric 3D-printing to date are reported, for thiol-ene systems. Finally, by means of in vitro and in vivo characterization of 3D-printed constructs, it is illustrated that the volumetrically 3D-printed materials are biocompatible. This combination of mechanical stability, tunability, biocompatibility, and rapid fabrication by volumetric 3D-printing charts a new path toward bedside manufacturing of biodegradable patient-specific implants.
Keywords
Mechanical Engineering, Mechanics of Materials, General Materials Science, volumetric 3D-printing, tissue engineering, thiol-ene, poly(epsilon-caprolactone), computed axial lithography

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MLA
Thijssen, Quinten, et al. “Volumetric Printing of Thiol‐ene Photo‐cross‐linkable Poly(Ε‐caprolactone) : A Tunable Material Platform Serving Biomedical Applications.” ADVANCED MATERIALS, vol. 35, no. 19, Wiley, 2023, doi:10.1002/adma.202210136.
APA
Thijssen, Q., Quaak, A., Toombs, J., De Vlieghere, E., Parmentier, L., Taylor, H., & Van Vlierberghe, S. (2023). Volumetric printing of thiol‐ene photo‐cross‐linkable poly(ε‐caprolactone) : a tunable material platform serving biomedical applications. ADVANCED MATERIALS, 35(19). https://doi.org/10.1002/adma.202210136
Chicago author-date
Thijssen, Quinten, Astrid Quaak, Joseph Toombs, Elly De Vlieghere, Laurens Parmentier, Hayden Taylor, and Sandra Van Vlierberghe. 2023. “Volumetric Printing of Thiol‐ene Photo‐cross‐linkable Poly(Ε‐caprolactone) : A Tunable Material Platform Serving Biomedical Applications.” ADVANCED MATERIALS 35 (19). https://doi.org/10.1002/adma.202210136.
Chicago author-date (all authors)
Thijssen, Quinten, Astrid Quaak, Joseph Toombs, Elly De Vlieghere, Laurens Parmentier, Hayden Taylor, and Sandra Van Vlierberghe. 2023. “Volumetric Printing of Thiol‐ene Photo‐cross‐linkable Poly(Ε‐caprolactone) : A Tunable Material Platform Serving Biomedical Applications.” ADVANCED MATERIALS 35 (19). doi:10.1002/adma.202210136.
Vancouver
1.
Thijssen Q, Quaak A, Toombs J, De Vlieghere E, Parmentier L, Taylor H, et al. Volumetric printing of thiol‐ene photo‐cross‐linkable poly(ε‐caprolactone) : a tunable material platform serving biomedical applications. ADVANCED MATERIALS. 2023;35(19).
IEEE
[1]
Q. Thijssen et al., “Volumetric printing of thiol‐ene photo‐cross‐linkable poly(ε‐caprolactone) : a tunable material platform serving biomedical applications,” ADVANCED MATERIALS, vol. 35, no. 19, 2023.
@article{01GW6ZP1ZR7EZMWXMPGGQQETYG,
  abstract     = {{Current thoroughly described biodegradable and cross-linkable polymers mainly rely on acrylate cross-linking. However, despite the swift cross-linking kinetics of acrylates, the concomitant brittleness of the resulting materials limits their applicability. Here, photo-cross-linkable poly(e-caprolactone) networks through orthogonal thiol-ene chemistry are introduced. The step-growth polymerized networks are tunable, predictable by means of the rubber elasticity theory and it is shown that their mechanical properties are significantly improved over their acrylate cross-linked counterparts. Tunability is introduced to the materials, by altering M-c (or the molar mass between cross-links), and its effect on the thermal properties, mechanical strength and degradability of the materials is evaluated. Moreover, excellent volumetric printability is illustrated and the smallest features obtained via volumetric 3D-printing to date are reported, for thiol-ene systems. Finally, by means of in vitro and in vivo characterization of 3D-printed constructs, it is illustrated that the volumetrically 3D-printed materials are biocompatible. This combination of mechanical stability, tunability, biocompatibility, and rapid fabrication by volumetric 3D-printing charts a new path toward bedside manufacturing of biodegradable patient-specific implants.}},
  articleno    = {{2210136}},
  author       = {{Thijssen, Quinten and Quaak, Astrid and Toombs, Joseph and De Vlieghere, Elly and Parmentier, Laurens and Taylor, Hayden and Van Vlierberghe, Sandra}},
  issn         = {{0935-9648}},
  journal      = {{ADVANCED MATERIALS}},
  keywords     = {{Mechanical Engineering,Mechanics of Materials,General Materials Science,volumetric 3D-printing,tissue engineering,thiol-ene,poly(epsilon-caprolactone),computed axial lithography}},
  language     = {{eng}},
  number       = {{19}},
  pages        = {{16}},
  publisher    = {{Wiley}},
  title        = {{Volumetric printing of thiol‐ene photo‐cross‐linkable poly(ε‐caprolactone) : a tunable material platform serving biomedical applications}},
  url          = {{http://doi.org/10.1002/adma.202210136}},
  volume       = {{35}},
  year         = {{2023}},
}

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