Novel phosphate-grafted ePTFE copolymers for optimum in vitro mineralization

Surface modification via graft copolymerization is an attractive method for optimizing polymers used in biomedical applications. We developed a novel method using a mixed solvent system (either water and dichloromethane (DCM) or water, methanol and DCM) consisting of two solvent phases for grafting 2-(methacryloyloxy) ethyl phosphate onto expanded polytetrafluoroethylene (ePTFE). This new method resulted in the fabrication of grafted membranes with greater grafting extents (GEs) (as evaluated from x-ray photoelectron spectroscopy (XPS)) in the organic phase than those obtained when grafting was carried out in a single phase. It also made it possible to graft in the aqueous phase, a process that is otherwise inhibited by the concomitant formation of large amounts of highly crystalline homopolymer. Thorough characterization of the grafted membranes using gravimetric, XPS and attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) not only permitted evaluation of the grafting outcomes but also made it possible to analyze their dependence on monomer concentration and solvent composition. A selection of membranes was tested for their in vitro mineralization capacity using simulated body fluid. It was found that an 'ideal' mineralization outcome, i.e. a uniform coating of carbonated hydroxyapatite (cHAP) formed on the sample grafted in the aqueous phase of the water/DCM two-phase solvent system. A detailed discussion bringing together these results, as well as results from a series of earlier studies, allows conclusions regarding polymer chemistry and the topology necessary for cHAP mineralization