title: Synthesis, characterization, and in vitro degradation of a biodegradable photo-cross-linked film from liquid poly(epsilon-caprolactone-co-lactide-co-glycolide) diacrylate.
abstract: There has been little study on the effect of composition or molecular weight on the biodegradation rate of photo-cross-linked biodegradable aliphatic polyesters though such information is important for tissue engineering scaffolds. We have synthesized a new series of photopolymerizable linear poly(epsilon-caprolactone-co-lactide-co-glycolide) diacrylates with different molecular weights (Mn = 1800, 4800, and 9300 Da) and compositions (20%, 40%, and 60% epsilon-CL) and studied their biodegradation rates. The resultant oligomers were amorphous and appeared as viscous liquids at room temperature. Liquid-to-solid polymerization was carried out by UV irradiation in the presence of a photoinitiator. The photocuring yield was high (greater than 95%), and the photo-cross-linked polymers were amorphous and rubbery. Mechanical measurements showed that the polymers can be stretchable or rigid; the high molecular weight/low epsilon-CL network has a strain of 176% and a modulus of 1.66 MPa while the low molecular weight/high epsilon-CL network has a strain of 21% and a modulus of 12.3 MPa. In a 10 week in vitro biodegradation study, the polymers exhibited a two-stage degradation behavior. In the first stage, the polymer weight and strain remained almost constant, but a linear decrease in the Young's modulus (E) and ultimate stress (sigma) were observed. Lower oligomer molecular weight or epsilon-CL content correlated with a faster decrease in Young's modulus. In the second stage, which began when the Young's modulus dropped below 1 MPa, there was rapid weight loss and strain increase. The lower the epsilon-CL content, the earlier the second stage happened. Low molecular weight and high epsilon-CL content correlated with a longer modulus half-life (time for the modulus to degrade to 50% of its initial value). The degradation results suggest principles that may be helpful in predicting the biodegradation behavior of similar polymeric cross-linked networks. Films formed from these new polymers have excellent biocompatibility with smooth muscle cells.
authors.affiliation: The Biological and Chemical Process Engineering Laboratory, School of Mechanical and Aerospace Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798.
authors.forename: Jin Y
authors.initials: JY
authors.lastname: Shen
authors.forename: Xiao Y
authors.initials: XY
authors.lastname: Pan
authors.forename: Chin H
authors.initials: CH
authors.lastname: Lim
authors.forename: Mary B
authors.initials: MB
authors.lastname: Chan-Park
authors.forename: Xiao
authors.initials: X
authors.lastname: Zhu
authors.forename: Roger W
authors.initials: RW
authors.lastname: Beuerman
mesh_terms: D000179:Acrylates / Q000138:chemical synthesis*; D000818:Animals; D001672:Biocompatible Materials / Q000138:chemical synthesis*; D001673:Biodegradation, Environmental; D003432:Cross-Linking Reagents; D006801:Humans; D032389:Myocytes, Smooth Muscle; D010777:Photochemistry; D011091:Polyesters / Q000138:chemical synthesis*; D023822:Tissue Engineering
chemical_list: D000179:Acrylates; D001672:Biocompatible Materials; D003432:Cross-Linking Reagents; D011091:Polyesters; C507868:poly(glycolide-co-lactide-co-caprolactone)