Poly tyrosine-derived monomer

Tyrosine-containing poly(DTR-PEG ethers) (Fig. 1.25) these polymers are synthesized by copolymerization of tyrosine-derived monomers and methylsulfone-activated PEG. 

The thermal properties of tyrosine-derived poly(iminocarbonates) were also investigated. Based on analysis by DSC and thermogravi-metric analysis, all poly(iminocarbonates) decompose between 140 and 220 C. The thermal decomposition is due to the inherent instability of the iminocarbonate bond above 150°C and is not related to the presence of tyrosine derivatives in the polymer backbone. The molecular structure of the monomer has no significant influence on the degradation temperature as indicated by the fact that poly(BPA.-iminocarbonate) also decomposed at about 170 C, while the structurally analogous poly(BPA-carbonate) is thermally stable up to 350 C. 

In an attempt to identify new, biocompatible diphenols for the synthesis of polyiminocarbonates and polycarbonates, we considered derivatives of tyrosine dipeptide as potential monomers. Our experimental rationale was based on the assumption that a diphenol derived from natural amino acids may be less toxic than many of the industrial diphenols. After protection of the amino and carboxylic acid groups, we expected the dipeptide to be chemically equivalent to conventional diphenols. In preliminary studies (14) this hypothesis was confirmed by the successful preparation of poly(Z-Tyr-Tyr-Et iminocarbonate) from the protected tyrosine dipeptide Z-Tyr-Tyr-Et (Figure 3). Unfortunately, poly (Z-Tyr-Tyr-Et iminocarbonate) was an insoluble, nonprocessible material for which no practical applications could be identified. This result illustrated the difficulty of balancing the requirement for biocompatibility with the need to obtain a material with suitable "engineering" properties. 

---