Suitability of EtO Sterilization for Polydopamine-coated, Self-fitting Bone Scaffolds.

Irregularly shaped craniomaxillofacial (CMF) defects may be advantageously treated by "self-fitting" shape memory polymer (SMP) scaffolds, namely those prepared from poly(ε-caprolactone)diacrylate (PCL-DA) networks and PCL-DA/poly(L-lactic acid) (PLLA) (75:25 wt%) semi-interpenetrating polymer networks (semi-IPNs). In addition to achieving good scaffold-tissue contact, a polydopamine (PD) coating can be leveraged to enhance bioactivity for improved osseointegration. Sterilization with ethylene oxide (EtO) represents a logical choice due to its low operating temperature and humidity. Herein, for the first time, the impact of EtO sterilization on the material properties of PD-coated SMP scaffolds was systematically assessed. Morphological features (i.e., pore size and pore interconnectivity), and in vitro bioactivity were preserved as were PCL crystallinity, PLLA crystallinity, and crosslinking. These latter features led to sustained shape memory properties, and compressive modulus. EtO-sterilized, PD-coated scaffolds displayed similar in vitro degradation behaviors versus analogous non-sterilized scaffolds. This included maintenance of compression modulus following 28 days of exposure to non-accelerated degradation conditions.

Bioactive Siloxane-Containing Shape-Memory Polymer (SMP) Scaffolds with Tunable Degradation Rates.

A material-guided, regenerative approach to heal cranial defects requires a scaffold that cannot only achieve conformal fit into irregular geometries but also has bioactivity and suitable resorption rates. We have previously reported "self-fitting" shape-memory polymer (SMP) scaffolds based on poly(ε-caprolactone) diacrylate (PCL-DA) that shape recover to fill irregular defect geometries. However, PCL-DA scaffolds lack innate bioactivity and degrade very slowly. Polydimethylsiloxane (PDMS) has been shown to impart innate bioactivity and modify degradation rates when combined with organic cross-linked networks. Thus, this work reports the introduction of PDMS segments to form PCL/PDMS SMP scaffolds. These were prepared as co-matrices with three types of macromers to systematically alter PDMS content and cross-link density. Specifically, PCL90-DA was combined with linear-PDMS66-dimethacrylate (DMA) or 4-armed star-PDMS66-tetramethacrylate (TMA) macromers at 90:10, 75:25, and 60:40 wt % ratios. Additionally, a triblock macromer (AcO-PCL45-b-PDMS66-b-PCL45-OAc), having a 65:35 wt % ratio PCL/PDMS, was used. Scaffolds exhibited pore interconnectivity and uniform pore sizes and further maintained excellent shape-memory behavior. Degradation rates increased with PDMS content and reduced cross-link density, with phase separation contributing to this effect. Irrespective of PDMS content, all PCL/PDMS scaffolds exhibited the formation of carbonated hydroxyapatite (HAp) following exposure to simulated body fluid (SBF). While inclusion of PDMS expectedly reduced scaffold modulus and strength, mineralization increased these properties and, in some cases, to values exceeding or similar to the PCL-DA, which did not mineralize.