Engineering Degradation Rate of Polyphosphazene-Based Layer-by-Layer Polymer Coatings.

Degradable layer-by-layer (LbL) polymeric coatings have distinct advantages over traditional biomedical coatings due to their precision of assembly, versatile inclusion of bioactive molecules, and conformality to the complex architectures of implantable devices. However, controlling the degradation rate while achieving biocompatibility has remained a challenge. This work employs polyphosphazenes as promising candidates for film assembly due to their inherent biocompatibility, tunability of chemical composition, and the buffering capability of degradation products. The degradation of pyrrolidone-functionalized polyphosphazenes was monitored in solution, complexes and LbL coatings (with tannic acid), providing the first to our knowledge comparison of solution-state degradation to solid-state LbL degradation. In all cases, the rate of degradation accelerated in acidic conditions. Importantly, the tunability of the degradation rate of polyphosphazene-based LbL films was achieved by varying film assembly conditions. Specifically, by slightly increasing the ionization of tannic acid (near neutral pH), we introduce electrostatic "defects" to the hydrogen-bonded pairs that accelerate film degradation. Finally, we show that replacing the pyrrolidone side group with a carboxylic acid moiety greatly reduces the degradation rate of the LbL coatings. In practical applications, these coatings have the versatility to serve as biocompatible platforms for various biomedical applications and controlled release systems.