Synthesis of new biodegradable polysulfenamides for applications in medicine

The first polysulfenamides were synthesized with S-N and N-S-N bonds along the backbone. We demonstrated that sulfenamides were stable in polar protic and aprotic solvents, but degraded rapidly when exposed to acidic conditions. Microparticles were fabricated from polysulfenamides with S-N bonds, their surfaces were readily functionalized, and they were internalized by cells allowing for intracellular delivery of their cargo. These microparticles were also stable at physiological pH, degraded under acidic conditions, and possessed minimal toxicity towards cells. This work demonstrated that polysulfenamides form the basis for a new set of polymers for drug delivery that greatly differ from prior work in this field. New biodegradable polymers with N-S-N bonds along the backbone were synthesized. These were the first polymers with these bonds and possessed many of the same characteristics as polymers synthesized with S-N bonds. The synthesis and characterization of comb block copolymers with arms composed of poly(lactic acid), poly(butyl acrylate), and poly(styrene-b-vinylpyridine) were described. The self-assembled morphologies in the solid state of comb triand tetrablock copolymers with poly(styrene) were also described. These assemblies demonstrated that well-ordered and complex morphologies were assembled from these polymers. The steric effect of substitutions on oxanorbornenes in ring-opening metathesis polymerization (ROMP) was investigated. Oxanorbornenes substituted with methyls at the bridgehead positions showed limited reactivity with the Grubbs first and second generation catalysts and the Grubbs first generation methylidene catalyst.