Control of the network topology by selection of an appropriate cross‐linking chemistry is introduced as a new strategy to improve the elasticity and toughness of bioresorbable networks. The development of novel photocross‐linkable and bioresorbable oligomers is essential for the application of light‐based 3D‐printing techniques in the context of tissue engineering. Although light‐based 3D‐printing techniques are characterized by an increased resolution and manufacturing speed as compared to extrusion‐based 3D‐printing, their application remains limited. Via chemical modification, poly‐ε‐caprolactone (PCL) is functionalized with photoreactive end groups such as acrylates, alkenes, and alkynes. Based on these precursors, networks with different topologies are designed via chain growth polymerization, step growth polymerization, or a combination thereof. The influence of the network topology and the concomitant cross‐linking chemistry on the thermal, mechanical, and biological properties are elucidated together with their applicability in digital light processing (DLP). Photocross‐linkable PCL with an elongation at break of 736.3 ± 47% and an ultimate strength of 21.3 ± 0.8 MPa is realized, which is approximately tenfold higher compared to the current state‐of‐the‐art. Finally, extremely elastic DLP‐printed dog bones are developed which can fully retrieve their initial length upon stress relieve at an elongation of 1000%.
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(ε‐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 Mc (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.
Melt electrowriting (MEW) is an additive manufacturing process that produces highly defined constructs with elements in the micrometer range. A specific configuration of MEW enables printing tubular constructs to create small‐diameter tubular structures. The small pool of processable materials poses a bottleneck for wider application in biomedicine. To alleviate this obstacle, an acrylate‐endcapped urethane‐based polymer (AUP), using a poly(ε‐caprolactone) (PCL) (molar mass: 20 000 g mol−1) (AUP PCL20k) as backbone material, is synthesized and utilized for MEW. Spectroscopic analysis confirms the successful modification of the PCL backbone with photo‐crosslinkable acrylate endgroups. Printing experiments of AUP PCL20k reveal limited printability but the photo‐crosslinking ability is preserved post‐printing. To improve printability and to tune the mechanical properties of printed constructs, the AUP‐material is blended with commercially available PCL (AUP PCL20k:PCL in ratios 80:20, 60:40, 50:50). Print fidelity improves for 60:40 and 50:50 blends. Blending enables modification of the constructs' mechanical properties to approximate the range of blood vessels for transplantation surgeries. The crosslinking‐ability of the material allows pure AUP to be manipulated post‐printing and illustrates significant differences in mechanical properties of 80:20 blends after crosslinking. An in vitro cell compatibility assay using human umbilical vein endothelial cells also demonstrates the material's non‐cytotoxicity.
Many bone defects arising due to traumatic injury, disease, or surgery are unable to regenerate, requiring intervention. More than four million graft procedures are performed each year to treat these defects making bone the second most commonly transplanted tissue worldwide. However, these types of graft suffer from a limited supply, a second surgical site, donor site morbidity, and pain. Due to the unmet clinical need for new materials to promote skeletal repair, this study aimed to produce novel biomimetic materials to enhance stem/stromal cell osteogenesis and bone repair by recapitulating aspects of the biophysical and biochemical cues found within the bone microenvironment. Utilizing a collagen type I–alginate interpenetrating polymer network we fabricated a material which mirrors the mechanical and structural properties of unmineralized bone, consisting of a porous fibrous matrix with a young’s modulus of 64 kPa, both of which have been shown to enhance mesenchymal stromal/stem cell (MSC) osteogenesis. Moreover, by combining this material with biochemical paracrine factors released by statically cultured and mechanically stimulated osteocytes, we further mirrored the biochemical environment of the bone niche, enhancing stromal/stem cell viability, differentiation, and matrix deposition. Therefore, this biomimetic material represents a novel approach to promote skeletal repair.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
customersupport@researchsolutions.com
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.