Polycaprolactone (PCL) is a biodegradable polymer which is used in tissue engineering applications thanks to its many favorable characteristics. However, PCL surfaces are known as hydrophobic leading to a lack of favorable cell response. To overcome this problem, PCL surfaces will undergo a surface functionalization by grafting bioactive polymers bearing ionic groups.

Our laboratory has demonstrated that the grafting of bioactive polymers onto biomaterials can improve cell and antibacterial response. The objective of this work is to functionalize PCL surfaces by the grafting of a bioactive polymer.

The grafting of an ionic polymer poly(sodium styrene sulfonate) (polyNaSS), using UV irradiation on PCL surfaces was carried out in a two-steps reaction process. PCL surfaces were (1) chemically oxidized in order to allow the formation of (hydro)peroxide species. (2) Then immersed in a sodium styrene sulfonate (NaSS) solution and placed under UV irradiation to induce the decomposition of (hydro)peroxides to form radicals able to initiate the polymerization of the NaSS monomer. Various parameters, such as polymerization time, the effect of the surface activation, lamp power and monomer concentration were investigated in order to optimize the yield of polyNaSS grafting. The amount of polyNaSS grafted onto PCL surfaces was first determined by toluidine blue colorimetric method and characterized by contact angle measurement, Fourier-transform infrared spectra recorded in attenuated total reflection mode (ATR-FTIR), scanning electron microscopy with Oxford energy dispersive spectroscopy (SEM-EDS).

Various techniques showed that the grafting of ionic polymer polyNaSS bearing sulfonate groups was successful by using radicals from (hydro)peroxides able to initiate the radical polymerization of ionic monomers onto PCL surfaces.

We developed a new approach of radical grafting which allows us to successfully graft bioactive polymer polyNaSS covalently to PCL surfaces using UV irradiation.