Surface modifications and oxidative degradation in MPC-grafted highly cross-linked polyethylene liners retrieved from short-term total hip arthroplasty

Highly cross-linked polyethylene (HXLPE) hip liners grafted with 2-methacryloyloxyethyl phosphorylcholine (MPC) on their bearing surfaces have recently been commercialized as components of a new generation of artificial hip joints, while improvements in wear resistance and biocompatibility were reported based on in vitro studies. The present study aimed at evaluating the surface modification and oxidative degradation in short-term retrieved MPC-grafted liners by X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared spectroscopy (FT-IR) with attenuated total reflection (ATR) equipment and Raman spectroscopy. In none of 3 samples of retrieved MPC-grafted liners, detectable MPC graft remained on the bearing surfaces although 2 samples yet contained remains of MPC polymer in their rim zone. These results revealed that the MPC polymer might have quickly disappeared from the bearing surface under in vivo loading, which is more severe than the in vitro one. Furthermore, a detectable oxidation index (OI) value (>0.1) was not only observed in any zone of any sample investigated, but also in the rim zones of Samples 1 and 2, which surprisingly experienced the most remarkable increase in OI value detected in this study. We thus confirmed that: (i) annealing of HXLPE cannot completely remove free radicals; (ii) the MPC graft has no beneficial effect in protecting HXLPE against oxidation and wear; and, (iii) lipid absorption occurred even in the rim zone where the MPC layer remained. Based on these evidences we consider that the declaimed advanced MPC technology is not a suitable one to elongate the in vivo lifetime of hip joints. Statement of significance Several studies reported that highly crosslinked polyethylene (HXLPE) have resulted in reduced wear in total hip arthroplasty. Beyond those studies, HXLPE hip liners grafted with 2-methacryloyloxyethyl phosphorylcholine (MPC) on their bearing surface were extensively studied in vitro and then commercialized as a new generation of artificial hip joints. The present study reports for the first time results about the evaluation of surface modification and oxidative degradation in retrieved the MPC grafted liners. The findings of this investigation clearly show that the MPC layer has been peeled off on the bearing surface of the liner main wear zone although the MPC layer remained on the surface of the rim zones. Furthermore, we assessed the microstructural modifications and the oxidation drifts that occurred in vivo in the hip joints despite the presence of the MPC layer.