Poly(methyl methacrylate)-based terpolymers bearing sulfonate and carboxylate groups have been synthesized by radical copolymerization leading to polymers with random distributions of ionic monomer units. Fibroblast cells were seeded on terpolymers of various molar compositions of ionic groups. Kinetics of the cell proliferation were examined and systematically compared to the nonfunctionalized control polymer, poly(methyl methacrylate). Modulation of cell proliferation was observed on 15% ionic monomer content copolymers of various compositions (R = COO(-)/(COO(-) + SO(3)(-)) and varies from 0 to 1). The inhibition percentage of cell proliferation calculated for each polymer by comparison to the cell proliferation on the control was plotted against R and gave a maximum value for R close to 0.55. Copolymers with ionic group contents higher or lower than 15% exhibit inhibition percentages fitting with those previously observed for the same R values, showing that the hydrophilic properties are not sufficient to explain the modulation effect of this material toward cells. Moreover, for each polymer tested, cells, even if inhibited in growth, were shown to be viable, indicating that the synthesized terpolymers exhibit cytostatic properties excluding any cytotoxic effect. Such polymers may be used for the fabrication of biocompatible intraocular lenses and prevent secondary cataract.
Bioactive polymers bearing sulfonate (styrene sodium sulfonate, NaSS) and carboxylate (methylacrylic acid, MA) groups were grafted onto Ti6Al4V alloy surfaces by a two-step procedure. The Ti alloy surfaces were first chemically oxidized in a piranha solution and then directly subjected to radical polymerization at 70°C in absence of oxygen. The grafted surfaces were characterized by X-ray photoelectron spectroscopy (XPS), time-of-flight secondary ion mass spectrometry (ToF-SIMS) and the Toluidin blue colorimetric method. Toluidin blue results showed 1 to 5 g/cm 2 of polymer was grafted onto the oxidized Ti surfaces. Grafting resulted in a decrease in the XPS Ti and O signals from the underlying Ti substrate and a corresponding increase in the XPS C and S signals from the polymer layer. The ToF-SIMS intensities of the S − and SO − ions correlated linearly with the XPS atomic percent S concentrations and the ToF-SIMS intensity of the TiO 3 H 2 − ion correlated linearly with the XPS atomic percent Ti concentration. Thus, the ToF-SIMS S − , SO − and TiO 3 H 2 − intensities can be used to quantify composition and amount of grafted polymer. ToF-SIMS also detected ions that were more characteristic of the polymer molecular structure (C 6 H 4 SO 3 − and C 8 H 7 SO 3 − from NaSS, C 4 H 5 O 2 − from MA), but the intensity of these peaks depended on the polymer thickness and composition. An in vitro cell culture test was carried out with human osteoblast-like cells to assess the influence of the grafted polymers on cell response. Cell adhesion after 30 min of incubation showed significant differences between the grafted and un-grafted surfaces. The NaSS grafted surfaces showed the highest degree of cell adhesion while the MA-NaSS grafted surfaces showed the lowest degree of cell adhesion. After 4 weeks in vivo in rabbit femoral bones bone was observed to be in direct contact with all implants. The percent of mineralized tissue around the implants was similar for NaSS grafted and non-grafted implants (59 and 57%). The MA-NaSS grafted implant exhibited a lower amount of mineralized tissue (47%).
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