Tyrosol-Derived Biodegradable Inks with Tunable Properties for 3D Printing.

Three-dimensional (3D) printing has emerged as a valuable tool in medicine over the past few decades. With a growing number of applications using this advanced processing technique, new polymer libraries with varied properties are required. Herein, we investigate tyrosol-based poly(ester-arylate)s as biodegradable inks in fused deposition modeling (FDM). Tyrosol-based polycarbonates and polyesters have proven to be useful biomaterials due to their excellent tunability, nonacidic degradation components, and the ability to be functionalized. Polymers are synthesized by polycondensation between a custom diphenol and commercially available diacids. Thermal properties, degradation rates, and mechanical properties are all tunable based on the diphenol and diacid chosen. Evaluation of material print as it relates to chemical structure, molecular weight, and thermal properties was explored. Higher-molecular-weight polymers greater than 50 kDa exhibit thermal degradation during printing and at some points are too viscous to print. It was determined that polymers with lower processing temperatures and molecular weights were printable regardless of the structure. An exception to this was pHTy6 that was printed at 65 kDa with minimal degradation. This is most likely due to its low melting temperature and, as a result, lower printing temperatures. Additionally, chemical improvements were made to incorporate thiol-alkene click chemistry as a means for postprint curing. Low-molecular-weight pHTy6 was end-capped with alkene functionality. This material was then formulated with either a dithiol for chain extension or tetrathiol for cross-linking. Scaffolds were cured after printing for 5, 15, 30 and 60 min intervals where longer cure times resulted in a tougher material. This design builds on the library of biologically active materials previously explored and aims to bring new biomaterials to the field of 3D-printed personal medicine.

Reversibly Softening and Stiffening Organogels Using a Wavelength-Controlled Disulfide-Diselenide Exchange.

Wavelength-dependent light-responsive seleno-sulfide dynamic covalent bonds were used to prepare organogels with reversible changes in stiffness. The disulfide cross-link organogels prepared from norbornene-terminated poly(ethylene glycol) (PEG-diNB) and poly(2-hydroxypropyl methacrylate-stat-mercaptoethyl acrylate) (PEG-diNB-poly(HPMA-stat-MEMA)) polymers underwent exchange reactions with 5,5'-diselenide-bis(2-aminobenzoic acid) upon irradiation with UV light. Following irradiation with visible light, the seleno-sulfide bonds were cleaved, reforming disulfide cross-links and the 5,5'-diselenide-bis(2-aminobenzoic acid). Reduction in G' with disulfide-diselenide exchange was consistent with that observed following a thiol-disulfide exchange reaction. Recovery of G' upon disulfide bond formation was 85-95% of the initial value in the as-prepared gel over five cycles of bond cleaving and reformation. This initial study shows the potential of the wavelength-controlled disulfide-diselenide chemistry to develop light-responsive reversible organogels. These organogels have the potential to be used in functional materials such as polymeric actuators or biomimetic soft robotics.