Synthesis, Characterization, and Electrospinning of a Functionalizable, Polycaprolactone-Based Polyurethane for Soft Tissue Engineering

Abstract

We synthesized a biodegradable, elastomeric, and functionalizable polyurethane (PU) that can be electrospun for use as a scaffold in soft tissue engineering. The PU was synthesized from polycaprolactone diol, hexamethylene diisocyanate, and dimethylolpropionic acid (DMPA) chain extender using two-step polymerization and designated as PU-DMPA. A control PU using 1,4-butanediol (1,4-BDO) as a chain extender was synthesized similarly and designated as PU-BDO. The chemical structure of the two PUs was verified by FT-IR and 1H-NMR. The PU-DMPA had a lower molecular weight than the PU-BDO (~16,700 Da vs. ~78,600 Da). The melting enthalpy of the PU-DMPA was greater than that of the PU-BDO. Both the PUs exhibited elastomeric behaviors with a comparable elongation at break (λ=L/L0= 13.2). The PU-DMPA had a higher initial modulus (19.8 MPa vs. 8.7 MPa) and a lower linear modulus (0.7 MPa vs. 1.2 MPa) and ultimate strength (9.5 MPa vs. 13.8 MPa) than the PU-BDO. The PU-DMPA had better hydrophilicity than the PU-BDO. Both the PUs displayed no cytotoxicity, although the adhesion of human umbilical artery smooth muscle cells on the PU-DMPA surface was better. Bead free electrospun PU-DMPA membranes with a narrow fiber diameter distribution were successfully fabricated. As a demonstration of its functionalizability, gelatin was conjugated to the electrospun PU-DMPA membrane using carbodiimide chemistry. Moreover, hyaluronic acid was immobilized on the amino-functionalized PU-DMPA. In conclusion, the PU-DMPA has the potential to be used as a scaffold material for soft tissue engineering.

Keywords

• polyurethanes
• two-step reaction
• elastomer
• functionalization
• electrospinning
• 2,2-bis(hydroxymethyl)propionic acid