Structure and Thermal Transitions in a Biomedically Relevant Liquid Crystalline Poly(ester amide)

There is still a need to develop bioresorbable polymers with high strength and high modulus for load-bearing biomedical applications. Here we investigate the liquid crystalline structural features of poly­(desaminotyrosyl-tyrosine dodecyl dodecanedioate), poly­(DTD DD), a new bioresorbable poly­(ester amide) that is currently studied in vivo as a slow-degrading implantable biomaterial for load bearing applications. Thermally induced structural changes in poly­(DTD DD) were studied using simultaneously differential scanning calorimetry (DSC) and X-ray scattering. The hexatic SmB organization of the polymer chains that exists at room temperature becomes progressively disordered upon heating, changing into a SmF phase and then into a smectic C phase at 60 °C before turning into a free-flowing melt at 130 °C. X-ray scattering data and thermal analysis indicate the presence of a 2D ordered structure in the polymer melt. A structural model with an interesting 3-fold symmetry in the packing of the side chains around the rigid aromatic main chain, and the packing of these chains into fibrils is proposed. The liquid crystalline behavior of poly­(DTD DD) makes it possible to melt process it at low temperatures without thermal degradation. This is a noteworthy advantage for the use of poly­(DTD DD) as a high strength, readily processable, yet biodegradable polymer.