Preparation of Flexible and Elastic Poly(trimethylene carbonate) Structures by Stereolithography

3D porous and non-porous structures are designed and prepared by stereolithography using resins based on PTMC macromers. Tough, flexible network films prepared in this manner show E moduli of approximate to 3.8MPa and high elongations at break >900% tensile strengths are approximate to 4.2MPa. These values increase with increasing PTMC macromer molecular weight. To reach suitable viscosities for processing, up to 45 wt% propylene carbonate is added as non-reactive diluent. The solid specimens have compression moduli of 3.14.2 MPa, similar to the values determined in tensile testing. The built porous structures show porosities of 53-66% and average pore sizes of 309-407 mu m. The compression moduli of the porous structures are significantly lower than those of the solid structures

Poly(trimethylene carbonate) and nano-hydroxyapatite porous scaffolds manufactured by stereolithography

Designing calcium phosphate-loaded polymeric porous scaffolds with controlled architecture using stereolithography (SLA) has great potential in the field of bone tissue engineering. However, the use of poly(ester)s with suboptimal degradation property has mainly been reported. In the present work, we introduced a poly(trimethylene carbonate) (PTMC) and nano-hydroxyapatite (HA) resin suitable for SLA manufacturing and created cytocompatible 3D porous structure. First, the resin formulation and HA content were optimized for photo-crosslink-based SLA fabrication process. Subsequently, we evaluated the influence of the resin composition on physico-chemical characteristics of fabricated films and scaffolds. Then, the influence of the biomaterial composition on human bone marrow mesenchymal stem cell viability, adhesion and proliferation was assessed. Films and macroporous scaffolds were successfully produced by photo-crosslinking with up to 40 wt% of HA (relative to PTMC). We demonstrated that addition of HA in PTMC matrices induced a direct effect on the surface properties, in terms of wettability and topography. Additionally, mechanical tests revealed a correlation between the amounts of HA loaded in PTMC and the stiffness of the SLA-fabricated scaffolds. Importantly, the different photo-crosslinked biomaterials exhibited in vitro cytocompatibility, similar to tissue culture polystyrene. Those data suggest the possibility to fabricate highly tunable HA-loaded PTMC 3D porous structures for bone tissue engineering application

Micro-porous composite scaffolds of photo-crosslinked poly(trimethylene carbonate) and nano-hydroxyapatite prepared by low-temperature extrusion-based additive manufacturing

Complex bony defects such as those of the orbital floor are challenging to repair. Additive manufacturing techniques open up possibilities for the fabrication of implants with a designed macro-porosity for the reconstruction of such defects. Apart from a designed macro-porosity for tissue ingrowth, a micro-porosity in the implant struts will be beneficial for nutrient diffusion, protein adsorption and drug loading and release. In this work, we report on a low-temperature extrusion-based additive manufacturing method for the preparation of composite photo-crosslinked structures of poly(trimethylene carbonate) with bone-forming nano-hydroxyapatite and noricaritin (derived from bone growth stimulating icariin). In this method, we extrude a dispersion of nano-hydroxyapatite and noricaritin particles in a solution of photo-crosslinkable poly(trimethylene carbonate) in ethylene carbonate into defined three-dimensional structures. The ethylene carbonate is subsequently crystallized and extracted after photo-crosslinking. We show that this results in designed macro-porous structures with micro-pores in the struts. The dispersion used to fabricate these structures shows favorable properties for extrusion-based processing, such as a sharp crystallization response and shear thinning. The formed photo-crosslinked materials have a micro-porosity of up to 48%, and the E modulus, ultimate tensile strength and toughness are in excess of 24 MPa, 2.0 N/mm2 and 113 N/mm2 respectively. A sustained release of noricaritin from these materials was also achieved. The results show that the technique described here is promising for the fabrication of micro-porous photo-crosslinked composite structures of poly(trimethylene carbonate) with nano-hydroxyapatite and that these may be applied in the reconstruction of orbital floor defect

Degradation behavior of, and tissue response to photo-crosslinked poly(trimethylene carbonate) networks

Item does not contain fulltextPhoto-crosslinked networks prepared from three-armed methacrylate functionalized PTMC oligomers (PTMC-tMA macromers) are attractive materials for developing an anatomically correct meniscus scaffold. In this study, we evaluated cell specific biocompatibility, in vitro and in vivo degradation behavior of, and tissue response to, such PTMC networks. By evaluating PTMC networks prepared from PTMC-tMA macromers of different molecular weights, we were able to assess the effect of macromer molecular weight on the degradation rate of the PTMC network obtained after photo-crosslinking. Three photo-crosslinked networks with different crosslinking densities were prepared using PTMC-tMA macromers with molecular weights 13.3, 17.8, and 26.7 kg/mol. Good cell biocompatibility was demonstrated in a proliferation assay with synovium derived cells. PTMC networks degraded slowly, but statistically significant, both in vitro as well as subcutaneously in rats. Networks prepared from macromers with higher molecular weights demonstrated increased degradation rates compared to networks prepared from initial macromers of lowest molecular weight. The degradation process took place via surface erosion. The PTMC networks showed good tissue tolerance during subcutaneous implantation, to which the tissue response was characterized by the presence of fibrous tissue and encapsulation of the implants. Concluding, we developed cell and tissue biocompatible, photo-crosslinked PTMC networks using PTMC-tMA macromers with relatively high molecular weights. These photo-crosslinked PTMC networks slowly degrade by a surface erosion process. Increasing the crosslinking density of these networks decreases the rate of surface degradation. (c) 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 2823-2832, 2016