Exploiting the network architecture of thiol–ene photo-crosslinked poly(ε-caprolactone) towards tailorable materials for light-based 3D-printing

Quaak, Astrid; Thijssen, Quinten; Vlierberghe, Sandra Van

doi:10.1039/d3py00381g

Cited by 4 publications

(5 citation statements)

References 51 publications

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“…Several of the photo-cross-linked hydrogels developed cracks during deformation. We hypothesize that the potential of homophotopolymerization of the PEG-Alkyne chains and the possibility of double addition of thiol to alkyne in the photo-cross-linked gels leads to excess/unreacted thiol chains and less regularity/homogeneity in the cross-linking process . This translates into a reduction of the mechanical integrity (see Figure ).…”

Section: Resultsmentioning

confidence: 99%

“…We hypothesize that the potential of homophotopolymerization of the PEG-Alkyne chains and the possibility of double addition of thiol to alkyne in the photocross-linked gels leads to excess/unreacted thiol chains and less regularity/homogeneity in the cross-linking process. 52 This translates into a reduction of the mechanical integrity (see Figure 1). Premature collapse may result from these inhomogeneities acting as stress concentration zones.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…In contrast, the reaction between the thiol and alkyne functionalities is the most viable reaction pathway during gelation in PBS. Although side reactions like disulfide formation can contribute to nonuniformity (stoichiometric imbalance would leave unreacted chains), 52 improved mechanical properties suggest a more uniformly cross-linked network.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Tailoring Network Topology in Mechanically Robust Hydrogels for 3D Printing and Injection

Ebrahimi,

Arreguín-Campos,

Dookhith

et al. 2024

ACS Appl. Mater. Interfaces

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Tissue engineering and regenerative medicine are confronted with a persistent challenge: the urgent demand for robust, load-bearing, and biocompatible scaffolds that can effectively endure substantial deformation. Given that inadequate mechanical performance is typically rooted in structural deficiencies�specifically, the absence of energy dissipation mechanisms and network uniformity�a crucial step toward solving this problem is generating synthetic approaches that enable exquisite control over network architecture. This work systematically explores structure−property relationships in poly(ethylene glycol)-based hydrogels constructed utilizing thiol−yne chemistry. We systematically vary polymer concentration, constituent molar mass, and cross-linking protocols to understand the impact of architecture on hydrogel mechanical properties. The network architecture was resolved within the molecular model of Rubinstein−Panyukov to obtain the densities of chemical cross-links and entanglements. We employed both nucleophilic and radical pathways, uncovering notable differences in mechanical response, which highlight a remarkable degree of versatility achievable by tuning readily accessible parameters. Our approach yielded hydrogels with good cell viability and remarkably robust tensile and compression profiles. Finally, the hydrogels are shown to be amenable to advanced processing techniques by demonstrating injection-and extrusion-based 3D printing. Tuning the mechanism and network regularity during the cell-compatible formation of hydrogels is an emerging strategy to control the properties and processability of hydrogel biomaterials by making simple and rational design choices.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

Section: ■ Experimental Sectionmentioning

confidence: 99%

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Tailoring Network Topology in Mechanically Robust Hydrogels for 3D Printing and Injection

Ebrahimi,

Arreguín-Campos,

Dookhith

et al. 2024

ACS Appl. Mater. Interfaces

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“…22 Quaak et al studied tunable thiol− ene networks with telechelic, trifunctional, and tetra-functional PCL, which were degradable with sodium hydroxide (NaOH) aqueous solutions. 23 Takasu et al reported several linear thiol− ene polymers synthesized from malic acid, tartaric acid, and dianhydro sugars, which showed varied degrees of biodegradation through biochemical oxygen demand (BOD) tests. 24−26 It is worth noting that biodegradable hydrogels and nanoparticles have also been demonstrated, for which the biodegradation is conducted in enzymatic aqueous solutions.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Thijssen et al utilized dialkene functionalized poly(ε-caprolactone) to create biocompatible 3D-printed materials and demonstrated their degradation in PBS . Quaak et al studied tunable thiol–ene networks with telechelic, trifunctional, and tetra-functional PCL, which were degradable with sodium hydroxide (NaOH) aqueous solutions . Takasu et al reported several linear thiol–ene polymers synthesized from malic acid, tartaric acid, and dianhydro sugars, which showed varied degrees of biodegradation through biochemical oxygen demand (BOD) tests. − It is worth noting that biodegradable hydrogels and nanoparticles have also been demonstrated, for which the biodegradation is conducted in enzymatic aqueous solutions. , These works demonstrate the effectiveness of thiol–ene systems in incorporating degradable linkages to design degradable polymers, but studies on soil compostability of thiol–ene cross-linked, network photopolymers have not been conducted.…”

Section: Introductionmentioning

confidence: 99%

Soil Compostability of Ester-based Thiol–ene Photopolymer Networks

Heiner,

Bishop,

Musgrave

et al. 2024

ACS Sustainable Chem. Eng.

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Photopolymer materials are used in many commodity applications, including adhesives, overprint varnishes, packaging materials, and disposable medical devices such as contact lenses. The vast majority of photopolymer materials directly contribute to landfill waste, as they are not recyclable or capable of biodegradation. To address this problem, we design a series of photopolymers leveraging thiol−ene click chemistry to incorporate ester groups into the backbone, including the ones found in biodegradable polymers, such as oligo-caprolactone and adipate. We investigated the degradability of these photopolymer networks and found that over 28 days, thiol−ene photopolymers containing oligo-caprolactone groups were susceptible to 55−83% biodegradation through biochemical oxygen demand (BOD) testing with activated sludge. We were able to completely disintegrate these polymers in compost at 58 °C and 76 ± 1% humidity through soil disintegration testing adapted from international standards (e.g., ISO 14851, ISO 20200, and OECD 301D). Our work demonstrates for the first time that ester-based thiol−ene photopolymers are biodegradable alternative materials for photopolymer applications.

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The importance of mechanical and biological cues of tympanic membrane grafts to ensure optimal regeneration

Nobus,

Parmentier,

Livens

et al. 2024

Biomaterials Advances

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Exploiting the network architecture of thiol–ene photo-crosslinked poly(ε-caprolactone) towards tailorable materials for light-based 3D-printing

Abstract: Thiol–ene photo-crosslinked poly-ε-caprolactone networks, exhibiting varying network architectures, were employed to fine-tune physico-chemical characteristics, while simultaneously exploring their potential application in digital light processing.

Cited by 4 publications

References 51 publications

Tailoring Network Topology in Mechanically Robust Hydrogels for 3D Printing and Injection

Tailoring Network Topology in Mechanically Robust Hydrogels for 3D Printing and Injection

Soil Compostability of Ester-based Thiol–ene Photopolymer Networks

The importance of mechanical and biological cues of tympanic membrane grafts to ensure optimal regeneration

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