Ring-opening polymerization (ROP) of cyclic esters/lactones by efficient catalysts is a powerful method for synthesis of biodegradable and biocompatible polyesters with well-defined structures. To develop catalytic systems that are fast, selective and controlled is a persistent effort of chemists. In this contribution, we report a binary urea/alkoxide catalytic system that could catalyze ROP of rac-LA in a fast (over 90% conversion within 1–2 min), stereoselective (Pi up to 0.93) and controlled manner, indicated by narrow MW distributions, linear relationship between the monomer conversions and Mns, end-group fidelity, and chain extension experiments. Remarkably, the catalytic system described here is simple, easily prepared, and structurally tunable and thus has versatile catalytic performances.
The
synthetic biodegradable polyester-based rigid porous scaffolds
and cell-laden hydrogels have been separately employed as therapeutic
modality for cartilage repair. However, the synthetic rigid scaffolds
alone may be limited due to the inherent lack of bioactivity for cartilage
regeneration, while the hydrogels have insufficient mechanical properties
that are not ideal for load-bearing cartilage applications. In the
present study, a hybrid construct was designed to merge the advantage
of 3D-printed rigid poly(lactic-co-glycolic acid) (PLGA) scaffolds
with cell-laden platelet-rich plasma (PRP) hydrogels that can release
growth factors to regulate the tissue healing process. PRP hydrogels
potentially achieved the effective delivery of mesenchymal stem cells
(MSCs) into PLGA scaffolds. This hybrid construct could obtain adequate
mechanical properties and independently provide MSCs with appropriate
clues for proliferation and differentiation. Real-time gene expression
analysis showed that PRP stimulated both chondrogenic and osteogenic
differentiation of MSC seeding into PLGA scaffolds. Finally, the hybrid
constructs were implanted into rabbits to simultaneously regenerate
both articular cartilage and subchondral bone within osteochondral
defects. Our findings suggest that this unique hybrid system could
be practically applied for osteochondral regeneration due to its capacity
for cell transportation, growth factors release, and excellent mechanical
strength, which would greatly contribute to the progress of cartilage
tissue engineering.
Bioresorbable poly(4-hydroxybutyrate) (P4HB) may fulfill the specific requirements that are necessary for a dural substitute, including its high elasticity, long-term strength retention properties, and the biocompatibility without significant accumulation of acidic degradation products. However, commercial P4HB can only be produced by the bacterial fermentation, which limits its applications in the cerebrospinal system due to higher endotoxin restriction. Meanwhile, P4HB can be prepared via the ring-opening polymerization of -butyrolactone. In this contribution, high molecular weight P4HB from chemosynthesis is electrospun into fibrous membrane, showing good mechanical properties that match the natural dura mater. Such P4HB membrane induces fast cellular migration, adhesion, and proliferation of fibroblasts in vitro. Subcutaneous implantation in rats demonstrates excellent biocompatibility of the P4HB membrane with proper biodegradation behaviors. After implantation in the rabbit dural defect model as an onlay graft, the P4HB membranes prevent cerebrospinal fluid leakage and regenerate dura tissue without detecting any local or systematic infections or foreign body responses. Thus, the electrospun P4HB membranes may be particularly useful as artificial dural substitutes to induce wound closure and tissue regeneration, which will be of great benefit to neurosurgery in the future.
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