title: Oxidative biodegradation mechanisms of biaxially strained poly(etherurethane urea) elastomers.
abstract: As part of ongoing studies in polyurethane biostability and biodegradation, we have investigated an in vitro system to test strained poly(etherurethane urea) (PEUU). Recently, we utilized this system to reproduce in vivo stress cracking in strained Pellethane. In this study, strained PEUU was tested to determine whether it degrades through a common mechanism with Pellethane and to further examine the steps involved in this degradation. Biaxially strained PEUU elastomers were treated with an alpha 2-macroglobulin (alpha 2-Mac) protein solution followed by an oxidative H2O2/CoCl2 treatment. Characterization of the strained PEUU specimens was performed with attenuated total reflectance-Fourier transform infrared spectroscopy, scanning electron microscopy (SEM), electron spectroscopy for chemical analysis, and contact angle analysis. The results from these characterization techniques provide conclusive evidence that biodegradation of PEUU and Pellethane occurs through a common mechanism. Chemical changes to the PEUU include cleavage of the polyether soft segments and urethane linkages, leaving the hard segment domains unaffected. SEM analysis shows that this chain cleavage leads to the development of severe pitting and cracking of the PEUU surface. In addition, the in vitro degradation accurately reproduces the in vivo degradation chemically and physically. This result verifies that the primary species responsible for biodegradation of PEUUs, in vivo, are hydroxyl and/or hydroperoxide radicals. alpha 2-Mac pretreatment increases the rate of degradation compared to direct treatment in H2O2/CoCl2. As the PEUU soft segment chains are cleaved, the degradation products are extracted into the treatment solution or environment. Finally, a new biodegradation mechanism of PEUUs is presented that involves crosslinking of the polyether soft segments.
authors.affiliation: Department of Macromolecular Science, Case Western Reserve University, Cleveland, Ohio 44106, USA.
authors.forename: M A
authors.initials: MA
authors.lastname: Schubert
authors.forename: M J
authors.initials: MJ
authors.lastname: Wiggins
authors.forename: M P
authors.initials: MP
authors.lastname: Schaefer
authors.forename: A
authors.initials: A
authors.lastname: Hiltner
authors.forename: J M
authors.initials: JM
authors.lastname: Anderson
mesh_terms: D000327:Adsorption; D000818:Animals; D001672:Biocompatible Materials; D001673:Biodegradation, Environmental; D005782:Gels; D006801:Humans; D008855:Microscopy, Electron, Scanning; D010084:Oxidation-Reduction; D011108:Polymers; D011140:Polyurethanes; D051381:Rats; D012995:Solubility; D017550:Spectroscopy, Fourier Transform Infrared; D013314:Stress, Mechanical; D013499:Surface Properties; D000511:alpha-Macroglobulins / Q000737:chemistry*
chemical_list: D001672:Biocompatible Materials; D005782:Gels; D011108:Polymers; D011140:Polyurethanes; D000511:alpha-Macroglobulins; C044690:polyetherurethane urea