Fabrication of Biomedical Scaffolds Using Biodegradable Polymers.

Degradable polymers are used widely in tissue engineering and regenerative medicine. Maturing capabilities in additive manufacturing coupled with advances in orthogonal chemical functionalization methodologies have enabled a rapid evolution of defect-specific form factors and strategies for designing and creating bioactive scaffolds. However, these defect-specific scaffolds, especially when utilizing degradable polymers as the base material, present processing challenges that are distinct and unique from other classes of materials. The goal of this review is to provide a guide for the fabrication of biodegradable polymer-based scaffolds that includes the complete pathway starting from selecting materials, choosing the correct fabrication method, and considering the requirements for tissue specific applications of the scaffold.

Degradable, Photochemically Printable Poly(propylene fumarate)-Based ABA Triblock Elastomers.

Additive manufacturing is rapidly advancing tissue engineering, but the scope of its clinical translation is limited by a lack of materials designed to meet specific mechanical properties and resorption timelines. Materials that are printable via photochemical cross-linking, fully degradable, and elastomeric have proven to be particularly challenging to develop. Herein, we report the synthesis of a series of poly(propylene fumarate-b-γ-methyl-ε-caprolactone-b-propylene fumarate) ABA triblock polymers using sequential ring-opening polymerization and ring-opening copolymerization. When cross-linked photochemically using a continuous liquid interface production digital light processing Carbon M2 printer, these ABA-type triblock copolymers are durable elastomers with tunable degradation and elastic properties. The polymers are shown to undergo slow, hydrolytic degradation in vitro with minimal loss of mechanical performance during degradation.

Advancing Toward 3D Printing of Bioresorbable Shape Memory Polymer Stents.

Stents have evolved significantly since their introduction to the medical field in the early 1980s, becoming widely used in percutaneous coronary interventions and following nephrological procedures. However, the current commercially available stents do not degrade and remain in the body forever, leading to problems like restenosis in cardiovascular applications or requiring removal procedures in ureteral applications. Efforts to replace metal with resorbable materials have largely been halted after the commercial failure of and safety concerns elicited by Abbott's Absorb stent in 2017. Industry continues to use common polymers such as poly(l-lactide) (PLLA) and polycaprolactone (PCL) for biomedical products, but due to the weak mechanical properties of these bioresorbable materials in comparison to metals, these devices have struggled to accomplish the goals set, increasing risk of thrombosis. 3D printing stents using bioresorbable and shape memory materials could provide a method of patient-personalized production, remove the need for balloon expansion, and limit stent migration, thus bringing a new age of stent technology. The investigation of a range of 3D-printable and bioresorbable shape-memory polymers can provide solutions to the shortcomings of previously explored bioresorbable stents and revitalize the medical device industry efforts into advancing stent technology.

Thiol-Based Three-Dimensional Printing of Fully Degradable Poly(propylene fumarate) Star Polymers.

Poly(propylene fumarate) star polymers photochemically 3D printed with degradable thiol cross-linkers yielded highly tunable biodegradable polymeric materials. Tailoring the alkene:thiol ratio (5:1, 10:1, 20:1 and 30:1) and thus the cross-link density within the PPF star systems yielded a wide variation of both the mechanical and degradation properties of the printed materials. Fundamental trends were established between the polymer network cross-link density, glass transition temperature, and tensile and thermomechanical properties of the materials. The tensile properties of the PPF star-based systems were compared to commercial state-of-the-art non-degradable polymer resins. The thiolene-cross-linked materials are fully degradable and possess properties over a wide range of mechanical properties relevant to regenerative medicine applications.