Tailorable acrylate-endcapped urethane-based polymers for precision in digital light processing: Versatile solutions for biomedical applications

Pien, Nele; Deroose, Nicolas; Meeremans, Marguerite; Perneel, Charlotte; Popovici, Cezar-Ştefan; Dubruel, Peter; De Schauwer, Catharina; Van Vlierberghe, Sandra

doi:10.1016/j.bioadv.2024.213923

Biomaterials Advances

2024

DOI: 10.1016/j.bioadv.2024.213923

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Tailorable acrylate-endcapped urethane-based polymers for precision in digital light processing: Versatile solutions for biomedical applications

Nele Pien,

Nicolas Deroose,

Marguerite Meeremans

et al.

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2024

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Cited by 2 publications

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Toward In Vitro Vascular Wall Models: Digital Light Processing of Acrylate‐Endcapped Urethane‐Based Polymers into Tubular Constructs

Pien,

Pokholenko,

Deroose

et al. 2024

Macro Chemistry & Physics

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Digital light processing (DLP) is emerging as a powerful tool for fabricating tissue engineering (TE) scaffolds, particularly for vascular TE and the development of representative in vitro vascular wall models. For the latter, biomaterials should mimick the biological and mechanical properties of native blood vessels. To fabricate tubular constructs, the DLP‐printing process is optimized by exploiting acrylate‐endcapped urethane‐based (AUP) polymers as the presence of the acrylate end groups render them suitable for DLP printing and desirable mechanical properties arise from the urethane segments. Four AUP variants are synthesized, exploring polyethylene glycol (PEG) and polypropylene glycol (PPG) backbones with varying acrylate functionalities (di‐acrylate versus hexa‐acrylate), namely UPEG2, UPEG6, UPPG2, and UPPG6. Tubular constructs with precise dimensions and morphology are fabricated. PPG‐based AUP polymers exhibit superior computer‐aided design/manufacturing (CAD/CAM) mimicry compared to PEG‐based derivatives. Construct characterization reveals tunable mechanical properties, with elastic moduli ranging from 45 to 259 kPa, reaching values of the human blood vessels. In particular, UPPG6 shows a two‐fold higher elastic modulus compared to UPPG2. All materials show excellent biocompatibility. Additionally, surface modification with gelatin‐methacryloyl (GELMA) significantly enhances the cytocompatibility of UPPG2 scaffolds. This study demonstrates the feasibility of fabricating tubular constructs with tunable properties using DLP and AUP polymers.

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Toward In Vitro Vascular Wall Models: Digital Light Processing of Acrylate‐Endcapped Urethane‐Based Polymers into Tubular Constructs

Pien,

Pokholenko,

Deroose

et al. 2024

Macro Chemistry & Physics

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Design and Depolymerization of Bis(2‐hydroxyethyl) Terephthalate‐Containing Polyurethanes for Vat Photopolymerization

Westover,

Nayyar,

Long

2024

Macro Chemistry & Physics

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Vat photopolymerization (VPP) of highly aromatic polyurethanes (PUs) expands the library of additive manufacturing (AM) materials and enables a vast array of ductile thermoplastics, rigid and flexible thermosets, and elastomers. Aromatic diisocyanates and various diols enable printing of rigid, highly aromatic cross‐linked parts, which offer high glass transition temperatures and tunable thermomechanical performance. The judicious control of molecular weight of the photo‐reactive telechelic oligomers allows for a fundamental study of the influence of cross‐link density in highly aromatic 3D PU printed objects. VPP AM produces objects with high resolution, smooth surface finish, and isotropic mechanical properties. Thermal post‐processing is critical in maintaining excellent thermomechanical properties with semi‐crystallinity as a function of cross‐link density. Due to the presence of two ester carbonyls in the bis(2‐hydroxyethyl) terephthalate chain extender, the printed parts are readily amenable to depolymerization with methanolysis to produce difunctional dimethyl dicarbamates under modest reaction conditions. Dimethyl dicarbamates serve as suitable monomers for subsequent polycondensation.

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Tailorable acrylate-endcapped urethane-based polymers for precision in digital light processing: Versatile solutions for biomedical applications

Cited by 2 publications

References 46 publications

Toward In Vitro Vascular Wall Models: Digital Light Processing of Acrylate‐Endcapped Urethane‐Based Polymers into Tubular Constructs

Toward In Vitro Vascular Wall Models: Digital Light Processing of Acrylate‐Endcapped Urethane‐Based Polymers into Tubular Constructs

Design and Depolymerization of Bis(2‐hydroxyethyl) Terephthalate‐Containing Polyurethanes for Vat Photopolymerization

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