Biodegradable Polyurethane Scaffolds in Regeneration Therapy: Characterization and In Vivo Real-Time Degradation Monitoring by Grafted Fluorescent Tracer

There is an urgent need to assess material degradation in situ and in real time for their promising application in regeneration therapy. However, traditional monitoring methods in vitro cannot always profile the complicated behavior in vivo. This study designed and synthesized a new biodegradable polyurethane (PU-P) scaffold with polycaprolactone glycol, isophorone diisocyanate, and l-lysine ethyl ester dihydrochloride. To monitor the degradation process of PU-P, calcein was introduced into the backbone (PU-5) as a chromophore tracing in different sites of the body and undegradable fluorescent scaffold (CPU-5) as the control group. Both PU-P and PU-5 can be enzymatically degraded, and the degradation products are molecularly small and biosafe. Meanwhile, by virtue of calcein anchoring with urethane, polymer chains of PU-5 have maintained the conformational stability and extended the system conjugation, raising a structure-induced emission effect that successfully achieved a significant enhancement in the fluorescence intensity better than pristine calcein. Evidently, unlike the weak fluorescent response of CPU-5, PU-5 and its degradation can be clearly imaged and monitored in real time after implantation in the subcutaneous tissue of nude mice. Meanwhile, the in situ osteogeneration has also been promoted after the two degradable scaffolds have been implanted in the rabbit femoral condyles and degraded with time. To sum up, the strategy of underpinning tracers into degradable polymer chains provides a possible and effective way for real-time monitoring of the degradation process of implants in vivo.