[Inhibition of Staphylococcus epidermidis adhesion on titanium surface with bioactive water-soluble copolymers bearing sulfonate, phosphate or carboxylate functions]. / Inhibition de l'adhérence de Staphylococcus epidermidis sur des surfaces en titane par des polymères hydrosolubles bioactifs comportant des fonctions sulfonate, phosphate ou carboxylate.

Implanted prostheses are sometimes subject to bacterial infections, which can threat their benefit rule on a long-term basis. Various methods are studied to fight against these infections. Among them, the grafting of bioactive polymers onto the prosthesis surface shows up as a promising way to the problem of infections. This work presents the influence of various water-soluble bioactive polymers on the inhibition of the Staphylococcus epidermidis adhesion on the titanium samples surfaces initially preadsorbed with various proteins. Whatever the studied protein is, it is shown that the bioactive polymer containing sulfonate functions generates an inhibition of the adhesion of Staphylococcus epidermidis. For a plasma preadsorption, the inhibition rate rises up to 68% when the concentration of sulfonate function is 2.5µmol/L. Titanium surfaces grafted with the bioactive polymer were also tested. We find an inhibitive activity of the adhesion close to that of the previous case. These preliminary results can point up a clinical interest in the fight against the medical devices infection, because they highlight a clear local effect of S. epidermidis adhesion inhibition. Copolymers containing other functional groups (phosphate or carboxylate) were dissolved in a bacterial suspension to monitor the influence of the composition on the adhesion inhibition. Their inhibition rates are not significantly lower than those of pNaSS homopolymers, as much as the sulfonate function proportion remains higher than 50%. Thus, the sulfonate function is the main responsible for the inhibition of the S. epidermidis adhesion.

The influence of isocyanurate content on the bioperformance of hydrocarbon-based polyurethanes.

Bulk, surface and bioactivity of newly synthesized hydroxy telechelic polyisoprene-based (H-HTPI) polyurethane were investigated by means of ATR-FT-IR, contact-angle measurements, cell viability, calcification, and platelet and fibrinogen quantification. The influence of isophorone diisocyanates isocyanurate (I-IPDI) content on these properties was determined. Results generally showed a non-significant difference in these properties when they were compared with a commercially available biomedical polyurethane (PU), such as Tecoflex. Unexpectedly, where the increase of isocyanate content for commercial diisocyanate-based biocompatible PU significantly increases the surface contact angle, the new hydroxy telechelic polyisoprene-based PU showed a decrease of water contact angle with increasing I-IPDI content in the polymer. Nevertheless, the overall surface exhibited hydrophobic properties, i.e., theta > 85. Polymer cytotoxicity, assessed with L929 cell line in direct contact with the surface of the samples, showed no toxic effects on the cells. Interestingly, regardless of the I-IPDI content, platelet adhesion and fibrinogen adsorption, as well as the mineral deposition were fairly similar for all synthesized PUs. Our findings revealed that replacing diisocyanates by their isocyanurate homologues is a very relevant approach for preparation of polyurethanes with different mechanical properties while maintaining similar surface properties.

In vitro thrombogenicity investigation of new water-dispersible polyurethane anionomers bearing carboxylate groups.

New segmented polyurethane (PU) anionomers based on hydroxytelechelic polybutadiene were synthesized via an aqueous dispersion process. Incorporation of carboxylic groups was achieved using thioacids of different length. Surface properties were investigated by mean of water absorption analysis and static contact-angle measurements using water, diiodomethane, formamide and ethylene glycol. Blood compatibility of the PUs was evaluated by in vitro adhesion assays using 111In-radiolabeled platelet-rich plasma and [125I]fibrinogen. Morphology of the adhered platelets was examined by scanning electron microscopy (SEM). Results were compared to two biomedical-grade PUs, namely Pellethane and Tecoflex. Insertion of carboxylic groups increased surface hydrophilicity and limited water uptake ( < 8% for an ion content of 5% by weight). Surface energy of all synthesized PUs was between 40 and 45 mJ/m2. Platelet adhesion and fibrinogen adsorption on the PU anionomer surfaces were affected as a function to the increase of graft length; thiopropionic was the most haemocompatible, followed by thiosuccinic and then thioglycolic acid. SEM analyses of all ionic PU samples exhibited low platelet adhesion to surfaces with no morphological modification. In conclusion, increased hydrophily, dynamic mobility and charge repulsion are synergistic key factors for enhanced haemocompatibility.

Hemocompatibilty of new ionic polyurethanes: influence of carboxylic group insertion modes.

New segmented polyurethane (PU) anionomers based on hydroxytelechelic polybutadiene (HTPB) were synthesized via two environment-friendly chemical routes. The effects of carboxylic content and ion incorporation mode on the surface properties were investigated by mean of water absorption analysis and static contact angle measurements using water, diiodomethane, formamide and ethylene glycol. Blood compatibility of the PUs was evaluated by in vitro adhesion assay using 111In-radiolabeled platelet rich plasma and 125I-fibrinogen. The morphology of platelet adhesion was also observed by scanning electron microscopy (SEM). Results were compared with a biomedical-grade PU, Pellethane. Insertion of the carboxylic groups on the soft segments (S-alpha series), using thioglycolic acid (TGA), increases surface hydrophilicity, limits water uptake (5%, for an ion content of 3.6 wt%), and reduces platelet adhesion and fibrinogen adsorption on the PUs' surfaces. In contrast, the classical insertion onto the hard segment (H-alpha series), using dimethylolpropionate (DMPA) as chain extender, leads to high water uptake (18%, for an ion content of 3.6 wt%) and promotes platelet and fibrinogen adhesion. SEM analyses of the non-ionic PUs exhibited surfaces with adhered platelets which underwent morphological modification. Similarly, the H-alpha ionic PUs show adherent and activated platelets. On the contrary, no platelet morphology changes were observed on the S-alpha ionic surfaces. In conclusion, insertion of carboxyl groups on the soft segments of PUs reduces their thrombogenicity.