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Manipulating the surface and substrate of cross-linked polyethylene (CLPE) is an essential approach for obtaining life-long orthopedic bearings. We therefore proposed a bearing material comprised of an antioxidative substrate generated by vitamin E blending (HD-CLPE[VE]) with a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC)-grafted surface, and investigated its wear resistance and oxidative stability under accelerated aging and load bearing conditions. Neither the hydration nor friction kinetics of the molecular network structure of the PMPC-grafted surface or the HD-CLPE(VE) substrate were influenced by accelerated aging but rather exhibited high stability even under high oxidation conditions. The characteristics of the PMPC-grafted surface improved the wear and impact fatigue resistance of the HD-CLPE(VE) liner regardless of accelerated aging. Notably, the PMPC-grafted surface was found to affect the potential oxidative stability at the rim part of the acetabular liner. PMPC chains serve several important functions on the surface regardless of load bearing, such as high lubricity or low lipophilicity attributed to phosphorylcholine groups and/or surrounding water-fluid film, and suppression of lipid diffusion attributed to methacrylate main chains on the surface. Together, these results provide preliminary evidence that the PMPC graft layer and vitamin E-blended substrate might positively affect the extent of orthopedic implant durability., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

The surface and substrate of a cross-linked polyethylene (CLPE) liner are designed to achieve resistance against oxidative degradation in the construction of hip joint replacements. In this study, we aimed to evaluate the oxidative degradation caused by lipid absorption of a highly hydrophilic nanometer-scaled thickness layer prepared by grafting a poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer and a high-dose gamma-ray irradiated CLPE with vitamin E blending (HD-CLPE[VE]). The HD-CLPE(VE) and PMPC-grafted HD-CLPE(VE) exhibited extremely high oxidation resistance regardless of lipid absorption, even though residual-free radical levels were detectable. The water wettability of the PMPC-grafted CLPE and PMPC-grafted HD-CLPE(VE) surfaces was considerably greater than that of untreated surfaces. The hydrated PMPC-grafted layer also exhibited extremely low solubility for squalene. Lipids such as squalene and cholesterol esters diminished the oxidation resistance of CLPE despite the vitamin E improvement. Notably, the PMPC-grafted surface was resistant to lipid absorption and diffusion as well as subsequent lipid-related oxidative degradation, likely because of the presence of the hydrated PMPC-grafted layer. Together, these results provide preliminary evidence that the resistance against lipid absorption and diffusion of a hydrated PMPC-grafted layer might positively affect the extent of resistance to the in vivo oxidation of orthopedic implants., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Surface modification by grafting of biocompatible phospholipid polymer onto the surface of artificial joint material has been proposed to reduce the risk of aseptic loosening and improve the durability. Poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC)-grafted cross-linked polyethylene (CLPE) has shown promising results for reducing wear of CLPE. The main lubrication mechanism for the PMPC layer is considered to be the hydration lubrication. In this study, the lubrication properties of PMPC-grafted CLPE were evaluated in reciprocating friction test with rehydration process by unloading in various lubricants. The start-up friction of PMPC-grafted CLPE was reduced, and the damage of PMPC layer was suppressed by rehydration in water or hyaluronic acid solutions. In contrast, the start-up friction of PMPC-grafted CLPE increased in fetal bovine serum solution, and the damage for PMPC layer was quite noticeable. Interestingly, the start-up friction of PMPC-grafted CLPE was reduced in fetal bovine serum solution containing hyaluronic acid, and the damage of the PMPC layer was suppressed. These results indicate that the rehydration by unloading and hyaluronic acid are elemental in maximizing the lubrication effect of hydrated PMPC layer., (© IMechE 2015.)

Background: Modifying the surface and substrate of a crosslinked polyethylene (CLPE) liner may be beneficial for high wear resistance as well as high oxidative stability and excellent mechanical properties, which would be useful in contributing to the long-term performance of orthopaedic bearings. A grafted poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) layer on a vitamin E-blended crosslinked PE (HD-CLPE[VE]) surface may provide hydrophilicity and lubricity without compromising the oxidative stability or mechanical properties., Questions/purposes: (1) Will the modifications (PMPC grafting and vitamin E blending) affect the lubrication characteristics of the CLPE surface? (2) Will the modifications affect wear resistance? (3) Will the modifications affect fatigue resistance?, Methods: We investigated the effects of surface and substrate modifications (PMPC grafting and vitamin E blending) on the wear and fatigue fracture of thin CLPE samples. For each of the untreated and PMPC-grafted CLPE surfaces with and without vitamin E blended (four groups), wettability and lubricity surface analyses were conducted as well as multidirectional wear and impact-to-wear tests using a pin-on-disk testing machine., Results: The water wettability and lubricity (CLPE [mean ± 95% confidence interval]: 23.2° ± 1.8°, 0.005 ± 0.001; HD-CLPE[VE]: 26.0° ± 2.3°, 0.009 ± 0.003) of the PMPC-grafted surfaces were greater (p < 0.001) than that (CLPE: 90.3° ± 1.2°, 0.067 ± 0.015; HD-CLPE[VE]: 90.8° ± 2.0°, 0.063 ± 0.008) of the untreated surface regardless of vitamin E additives. It was observed that the PMPC grafting (CLPE: 0.23 ± 0.06 mg; HD-CLPE[VE]: 0.05 ± 0.10 mg) was associated with reduced gravimetric wear (CLPE: 0.53 ± 0.08 mg, p = 0.004 HD-CLPE[VE]: 0.23 ± 0.07 mg, p = 0.038) in the multidirectional wear test. The PMPC-grafted surface characteristics did not appear to affect the impact fatigue resistance regardless of vitamin E blending., Conclusions: PMPC grafting improved the surface hydrophilicity and lubricity, and it reduced the gravimetric wear in terms of multidirectional sliding. It did not result in differences in terms of the impact-to-unidirectional sliding regardless of vitamin E blending. Further research is needed to evaluate the wear resistance of PMPC-grafted HD-CLPE(VE) in long-term hip simulator tests under normal and severe conditions, which may offer useful clues to the possible performance of these materials in vivo., Clinical Relevance: Our preliminary in vitro findings suggest that some improvement in the wear performance of crosslinked polyethylene acetabular liners in total hip arthroplasty could be obtained using PMPC grafting. Further research is needed to evaluate the wear resistance of PMPC-grafted HD-CLPE(VE) in long-term hip simulator tests under normal and severe conditions, which may offer useful clues to the possible performance of these materials in vivo.

The wear and creep deformation resistances of polymeric orthopedic bearing materials are both important for extending their longevity. In this study, we evaluated the wear and creep deformation resistances, including backside damage, of different polyethylene (PE) materials, namely, conventional PE, cross-linked PE (CLPE), and poly(2-methacryloyloxyethyl phosphorylcholine)- (PMPC-) grafted CLPE, through wear tests and finite element analysis. The gravimetric and volumetric degrees of wear of disks (3 or 6 mm in thickness) of these materials against a cobalt-chromium-molybdenum alloy pin were examined using a multidirectional pin-on-disk tester. Cross-linking and PMPC grafting decreased the gravimetric wear of the PE disks significantly. The volumetric wear at the bearing surface and the volumetric penetration in the backside of the 3-mm thick PE disk were higher than those of the 6-mm thick PE disk, regardless of the bearing material. The geometrical changes induced in the PE disks consisted of creep, because the calculated internal von Mises stress at the bearing side of all disks and that at the backside of the 3-mm thick disks exceeded their actual yield strengths. A highly hydrated bearing surface layer, formed by PMPC grafting, and a cross-linking-strengthened substrate of adequate thickness are essential for increasing the wear and creep deformation resistances.

Photoinduced grafting of 2-methacryloyloxyethyl phosphorylcholine (MPC) onto cross-linked polyethylene (CLPE) was investigated for its ability to reduce the wear of orthopedic bearings. We investigated the effect of UV-irradiation intensity on the extent of poly(MPC) (PMPC) grafting, and found that it increased with increasing intensity up to 7.5 mW/cm(2), and the remained fairly constant. It was found to be extremely important to carefully control the UV intensity, as at higher values, a PMPC gel formed via homopolymerization of the MPC, resulting in the formation of cracks at the interface of the PMPC layer and the CLPE substrate. When the CLPE was exposed to UV-irradiation during the graft polymerization process, some of its physical and mechanical properties were slightly changed due to cross-linking and scission effects in the surface region; however, the results of all of the tests exceed the lower limits of the ASTM standards. Modification of the CLPE surface with the hydrophilic PMPC layer increased lubrication to levels that match articular cartilage. The highly hydrated thin PMPC films mimicked the native cartilage extracellular matrix that covers synovial joint surface, acting as an extremely efficient lubricant, and providing high-wear resistance., (© 2013 Wiley Periodicals, Inc.)

The ultimate goal in manipulating the surface and substrate of a cross-linked polyethylene (CLPE) liner is to obtain not only high wear resistance but also high oxidative stability and high-mechanical properties for life-long orthopedic bearings. We have demonstrated the fabrication of highly hydrophilic and lubricious poly(2-methacryloyloxyethyl phosphorylcholine) (PMPC) grafting layer onto the antioxidant vitamin E-blended CLPE (HD-CLPE(VE)) surface. The PMPC grafting layer with a thickness of 100 nm was successfully fabricated on the vitamin E-blended CLPE surface by using photoinduced-radical graft polymerization. Since PMPC has a highly hydrophilic nature, the water wettability and lubricity of the PMPC-grafted CLPE and HD-CLPE(VE) surfaces were greater than that of the untreated CLPE surface. The PMPC grafting contributed significantly to wear reduction in a hip-joint simulator wear test. Despite high-dose gamma-ray irradiation for cross-linking and further UV irradiation for PMPC grafting, the substrate modified by vitamin E blending maintained high-oxidative stability because vitamin E is an extremely efficient radical scavenger. Furthermore, the mechanical properties of the substrate remained almost unchanged even after PMPC grafting or vitamin E blending, or both PMPC grafting and vitamin E blending. In conclusion, the PMPC-grafted HD-CLPE(VE) provided simultaneously high-wear resistance, oxidative stability, and mechanical properties., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

Natural joints rely on fluid thin-film lubrication by the hydrated polyelectrolyte layer of cartilage. However, current artificial joints with polyethylene (PE) surfaces have considerably less efficient lubrication and thus much greater wear, leading to osteolysis and aseptic loosening. This is considered a common factor limiting prosthetic longevity in total hip arthroplasty (THA). However, such wear could be mitigated by surface modification to mimic the role of cartilage. Here we report the development of nanometer-scale hydrophilic layers with varying charge (nonionic, cationic, anionic, or zwitterionic) on cross-linked PE (CLPE) surfaces, which could fully mimic the hydrophilicity and lubricity of the natural joint surface. We present evidence to support two lubrication mechanisms: the primary mechanism is due to the high level of hydration in the grafted layer, where water molecules act as very efficient lubricants; and the secondary mechanism is repulsion of protein molecules and positively charged inorganic ions by the grafted polyelectrolyte layer. Thus, such nanometer-scaled hydrophilic polymers or polyelectrolyte layers on the CLPE surface of acetabular cup bearings could confer high durability to THA prosthetics., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

Objective: Aseptic loosening of artificial knee joints induced by wear particles from a tibial polyethylene (PE) insert is a serious problem limiting their longevity. This study investigated the effects of grafting with our original biocompatible phospholipid polymer 2-methacryloyloxyethyl phosphorylcholine (MPC) on the insert surface., Methods: The hydrophilicity of the PE surface was determined by the contact angle of a water droplet, and the friction torque was measured against a cobalt-chromium alloy component. The wear amount was compared among PE inserts with or without cross-linking and MPC grafting during 5x10(6) cycles of loading in a knee joint simulator. The surfaces of the insert and the wear particles in the lubricant were subjected to electron and laser microscopic analyses. The mechanical properties of the inserts were evaluated by the small punch test., Results: The MPC grafting increased hydrophilicity and decreased friction torque. In the simulator experiment, the wear of the tibial insert was significantly suppressed in the cross-linked PE (CLPE) insert, and even more dramatically decreased in the MPC-grafted CLPE insert, as compared to that in the non-cross-linked PE insert. Surface analyses confirmed the wear resistance by the cross-linking, and further by the MPC grafting. The particle size distribution was not affected by cross-linking or MPC grafting. The mechanical properties of the insert material remained unchanged during the loading regardless of the cross-linking or grafting., Conclusion: Surface grafting with MPC polymer furnished the PE insert with wear resistance in an artificial knee joint through increased hydrophilicity and decreased friction torque., (Copyright 2010 Osteoarthritis Research Society International. Published by Elsevier Ltd. All rights reserved.)

Poly(ether-ether-ketone) (PEEK)s are a group of polymeric biomaterials with excellent mechanical properties and chemical stability. In the present study, we demonstrate the fabrication of an antibiofouling and highly hydrophilic high-density nanometer-scaled layer on the surface of PEEK by photo-induced graft polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) without using any photo-initiators, i.e., "self-initiated surface graft polymerization." Our results indicated that the diphenylketone moiety in the polymer backbone acted as a photo-initiator similar to benzophenone. The density and thickness of the poly(MPC) (PMPC)-grafted layer were controlled by the photo-irradiation time and monomer concentration during polymerization, respectively. Since MPC is a highly hydrophilic compound, the water wettability (contact angle <10 degrees) and lubricity (coefficient of dynamic friction <0.01) of the PMPC-grafted PEEK surface were considerably lower than those of the untreated PEEK surface (90 degrees and 0.20, respectively) due to the formation of a PMPC nanometer-scale layer. In addition, the amount (0.05 microg/cm(2)) of BSA adsorbed on the PMPC-grafted PEEK surface was considerably lower, that is more than 90% reduction, compared to that (0.55 microg/cm(2)) for untreated PEEK. This photo-induced polymerization process occurs only on the surface of the PEEK substrate; therefore, the desirable mechanical properties of PEEK would be maintained irrespective of the treatment used., ((c) 2009 Elsevier Ltd. All rights reserved.)

Migration of the artificial femoral head to the inside of the pelvis due to the degeneration of acetabular cartilage has emerged as a serious issue in resurfacing or bipolar hemi-arthroplasty. Surface modification of cobalt-chromium-molybdenum alloy (Co-Cr-Mo) is one of the promising means of improving lubrication for preventing the migration of the artificial femoral head. In this study, we systematically investigated the surface properties, such as lubricity, biocompatibility, and stability of the various modification layers formed on the Co-Cr-Mo with the biocompatible 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer by dip coating or grafting. The cartilage/poly(MPC) (PMPC)-grafted Co-Cr-Mo interface, which mimicked a natural joint, showed an extremely low friction coefficient of <0.01, as low as that of a natural cartilage interface. Moreover, the long-term stability in water was confirmed for the PMPC-grafted layer; no hydrolysis of the siloxane bond was observed throughout soaking in phosphate-buffered saline for 12 weeks. The PMPC-grafted Co-Cr-Mo femoral head for hemi-arthroplasty is a promising option for preserving acetabular cartilage and extending the duration before total hip arthroplasty.

Aseptic loosening of the artificial hip joint with osteolysis due to the wear particles from polyethylene cup has remained as a serious issue. To reduce this wear and develop a novel artificial hip joint system, we produced a superlubricious metal-bearing material: for this, we grafted a 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer onto the surface of a cobalt-chromium-molybdenum (Co-Cr-Mo) alloy. For ensuring long-term benefit retention of poly(MPC) on the Co-Cr-Mo alloy for application as a novel artificial hip joint system, several issues must be considered: strong bonding between poly(MPC) and Co-Cr-Mo surface, high mobility of free end groups of the poly(MPC) layer, and high density of the introduced poly(MPC). Considering these issues, we introduced a 3-methacryloxypropyl trimethoxysilane (MPSi) intermediate layer and a photoinduced graft polymerization technique to create a strong covalent bond between the Co-Cr-Mo substrate and the poly(MPC) chain via the MPSi layer. The thickness and density of the poly(MPC) layer on the surface increased with the MPC concentration and photoirradiation time. The grafted poly(MPC) layer successfully provided super-lubricity to the Co-Cr-Mo surface. The poly(MPC)-grafted crosslinked polyethylene/poly(MPC)-grafted Co-Cr-Mo or cartilage/poly(MPC)-grafted Co-Cr-Mo bearing interface mimicking natural joints showed an extremely low friction coefficient of 0.01, which is as low as that of natural cartilage interface. A superlubricious metal-bearing surface would enable the development of a novel biocompatible artificial hip joint system-artificial femoral head for partial hemiarthroplasty and metal-on-polymer/metal type for total hip arthroplasty., (Copyright 2008 Wiley Periodicals, Inc.)

Surface modification is important for the improvement in medical device materials. 2-Methacryloyloxyethyl phosphorylcholine (MPC) polymers have attracted considerable attention as surface modifiable polymers for several medical devices. In this study, we hypothesize that the structure of the surface modification layers might affect the long-term stability, hydration kinetics, wear resistance, and so forth, of medical devices such as artificial joints, and the poly(MPC) (PMPC) grafted surface might assure the long-term performance of such devices. Therefore, we investigate the surface properties of various surface modifications by using dip coatings of MPC-co-n-butyl methacrylate (PMB30) and MPC-co-3-methacryloxypropyl trimethoxysilane (PMSi90) polymers, or photoinduced radical grafting of PMPC and also the effects of the surface properties on the durability of cross-linked polyethylene (CLPE) for artificial joints. The PMPC-grafted CLPE has an extremely low and stable coefficient of dynamic friction and volumetric wear as compared to the untreated CLPE, PMB30-coated CLPE, and PMSi90-coated CLPE. It is concluded that the photoinduced radical graft polymerization of MPC is the best method to retain the benefits of the MPC polymer used in artificial joints under variable and multidirectional loads for long periods with strong bonding between the MPC polymer and the CLPE surface, and also to retain the high mobility of the MPC polymer.

Aseptic loosening of artificial hip joints induced by wear particles from the polyethylene (PE) liner remains the ruinous problem limiting their longevity. We reported here that grafting with a polymer, poly(2-methacryloyloxyethyl phosphorylcholine (MPC)) (PMPC), on the PE liner surface dramatically decreased the wear production under a hip joint simulator condition. We examined that the effect of properties of both PE by cross-linking and femoral head by changing the materials on wearing properties of PE. The PMPC grafting on the liners increased hydrophilicity and decreased friction torque, regardless of the cross-linking of the PE liner or the difference in the femoral head materials. During the hip joint simulator experiments (5 x 10(6) cycles of loading), cross-linking caused a decrease of wear amount and a reduction of the particle size, while the femoral head materials did not affect it. The PMPC grafting abrogated the wear production, confirmed by almost no wear of the liner surface, independently of the liner cross-linking or the femoral head material. We concluded that the PMPC grafting on the PE liner surpasses the liner cross-linking or the change of femoral head materials for extending longevity of artificial hip joints.

Osteolysis caused by wear particles from polyethylene in the artificial hip joints is a serious issue. We have used photo-induced radical graft polymerization to graft 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer onto the surface of cross-linked polyethylene (CLPE-g-MPC) in order to reduce friction and wear at the bearing surface of the joint. The physical and mechanical properties of CLPE and CLPE-g-MPC were not significantly different, expect that the friction coefficient of untreated CLPE cups was 0.0075, compared with 0.0009 for CLPE-g-MPC cup, an 88% reduction. After 3.0 x 10(6) cycles in the hip joint simulator test, we could not observe any wear of CLPE-g-MPC cups. We concluded that the advantage of photo-induced radical graft polymerization technique was that the grafted MPC polymer gave a high lubricity only on the surface and has no effect on the bulk properties of the CLPE substrate.

Osteolysis caused by wear particles from polyethylene in artificial hip joints is of great concern. Various bearing couple combinations, bearing material improvements, and surface modifications have been attempted to reduce such wear particles. With the aim of reducing the wear and developing a novel artificial hip-joint system, we created a highly lubricious metal-bearing material: A 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer was grafted onto the surface of the cobalt-chromium-molybdenum (Co-Cr-Mo) alloy. For ensuring the long-term retention of poly(MPC) on the Co-Cr-Mo alloy, we used a 4-methacryloxyethyl trimellitate anhydride (4-META) intermediate layer and photo-induced graft polymerization technique to create a strong bonding between the Co-Cr-Mo substrate and the poly(MPC) chain via the 4-META layer. The Co-Cr-Mo alloy was pretreated with nitric acid and O(2) plasma to facilitate efficient interaction between the 4-META carboxyl group and the surface hydroxyl group on the Cr oxide passive layer of the Co-Cr-Mo alloy. After MPC grafting, the MPC unit peaks were clearly observed in the Fourier-transform infrared spectroscopy with attenuated total reflection (FT-IR/ATR) and X-ray photoelectron spectroscopy (XPS) spectra of the Co-Cr-Mo surface. Tribological studies with a pin-on-plate machine revealed that surface MPC grafting markedly lowered the friction coefficient. We concluded that the grafted poly(MPC) layer successfully provided high lubricity to the Co-Cr-Mo surface.

We developed a cross-linked polyethylene (CLPE) modified with a phospholipid polymer in order to address the serious problem of osteolysis caused by wear particles derived from the polyethylene components of artificial hip joints. Our goal of preventing aseptic loosening could be achieved by avoiding any formation of CLPE wear particles or suppressing the activation of cell systems by the wear particles. We investigated the surface and wear resistance properties of 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer grafted onto the surface of CLPE (CLPE-g-MPC). The relative density of MPC polymer chains was determined by the P-O group index. Generally, polymerization times correspond to the number of polymer chains in radical polymerization. After 3.0 x 10(6) cycles in a hip joint simulator test, the steady wear rates of the untreated CLPE and CLPE-g-MPC cups with a low P-O group index were as high as 4 mg/10(6) cycles; those of the CLPE-g-MPC cups with high P-O group indexes, that is, 0.46 and 0.48, markedly decreased to -1.12 and 0.16 mg/10(6) cycles, respectively. Therefore, the grafting of an MPC polymer with high density would be essential in order to maintain the long-term wear resistance of CLPE-g-MPC as an orthopedic bearing material., (Copyright 2007 Wiley Periodicals, Inc.)

Periprosthetic osteolysis-bone loss in the vicinity of a prosthesis-is the most serious problem limiting the longevity of artificial joints. It is caused by bone-resorptive responses to wear particles originating from the articulating surface. This study investigated the effects of graft polymerization of our original biocompatible phospholipid polymer 2-methacryloyloxyethyl phosphorylcholine (MPC) onto the polyethylene surface. Mechanical studies using a hip-joint simulator revealed that the MPC grafting markedly decreased the friction and the amount of wear. Osteoclastic bone resorption induced by subperiosteal injection of particles onto mouse calvariae was abolished by the MPC grafting on particles. MPC-grafted particles were shown to be biologically inert by culture systems with respect to phagocytosis and resorptive cytokine secretion by macrophages, subsequent expression of receptor activator of NF-kappaB ligand in osteoblasts, and osteoclastogenesis from bone marrow cells. From the mechanical and biological advantages, we believe that our approach will make a major improvement in artificial joints by preventing periprosthetic osteolysis.

We used biodegradable poly-L-lactide screws in rotational acetabular osteotomy in 41 hips of 41 patients, and studied the complications after an average follow-up of 4.9 years (range 1.0-7.7 years). There were 39 females and 2 males, their average age at the time of the operation was 32 years (range 12-55 years). A small subcutaneous abscess appeared around the non-absorbable sutures in 2 patients after surgery. There was 1 case of thrombophlebitis and 1 of local dermatitis. The small subcutaneous abscess resolved after the removal of the suture material in the 2 cases, and the thrombophlebitis resolved with aspirin. The local dermatitis persisted but was cured by local steroid therapy over 5.8 years. The incidence of local dermatitis after the use of biodegradable implants should be further investigated.