Physicochemical and biological properties of nanohydroxyapatite grafted with star-shaped poly(ε-caprolactone)

To overcome the disadvantages generated by the lack of interfacial bonding between hydroxyapatite nanocrystals (HAPN) and agglomeration of particles in the development of biodegradable nanocomposites a chemical grafting method was applied to modify the surface of HAPN through grafting of the three-arms star-shaped poly(ε-caprolactone) (SPCL) onto the nanoparticles. The chemical grafting of SPCL onto HAPN (SPCL-g-HAPN) has been investigated using Fourier transform infrared spectroscopy, thermogravimetric analysis, transmission electron microscopy (TEM), photoelectron spectroscopy, X-ray diffraction, zeta potential (ZP) and contact angle (CA). TEM micrographs of the SPCL-g-HAPN revealed the existence of hybrid organic/inorganic (O/I) nanoscale domains. The results of albumin (HSA) and fibrinogen (HFb) adsorption indicate resistance to HFb adsorption by SPCL-g-HAPN relatively to unmodified HAPN. The ZP and CA measurement suggest a heterogeneous topology for SPCL-g-HAPN likely due to the existence of hydrophobic-hydrophilic regions on the nanocomposite surface. The enzyme degradation by cholesterol esterase and lipase indicates that the rates of hydrolysis for SPCL-g-HAPN were very slow relative to the SPCL/HAPN blends. The in vitro biological studies showed that the human osteoblast-like cells (MG-63) cells had normal morphology and they were able to attach and spread out on SPCL-g-HAPN surfaces. A higher overall cellular proliferation was observed on SPCL-g-HAPN scaffolds compared to pure HAPN or SPCL materials.