Time course of surface characteristics of alkali- and heat-treated titanium dental implants during vacuum storage.

Current efforts to shorten the healing times of life-long dental implants and prevent their fouling by organic impurities have focused on using surface-modification treatments and alternative packaging, respectively. In this study, we investigated the time course of the surface characteristics, including the wettability, a protein-adsorption and apatite-formation abilities, of alkali- and heat-treated (AH-treated) Ti samples during storage in vacuum over a period of 52 weeks. The AH treatment resulted in the formation of a nanometer-scale needle-like rougher surface of the Ti samples. Although the water contact angle of the AH-treated Ti sample increased slightly, it remained as low as approximately 10° even after storage in vacuum for 52 weeks. There was no significant difference in the protein-adsorption and apatite-formation abilities of the AH-treated Ti sample before and after storage. Further, the AH-treated Ti sample exhibited greater protein-adsorption and apatite-formation abilities compared with the untreated one; regardless of the samples stored in vacuum or not. Apatite formed only on the AH-treated Ti surface. Therefore, subjecting Ti dental implants to the AH treatment and storing them in vacuum should help prevent their surfaces from getting contaminated. Further, it is expected that AH-treated Ti dental implants controllably aged during a shelf storage will exhibit high stability and bone-bonding bioactivity. © 2016 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 105B: 1453-1460, 2017.

Effect of bacterial media on the evaluation of the antibacterial activity of a biomaterial containing inorganic antibacterial reagents or antibiotics.

Several studies have been performed to assess the effectivesness of the antibacterial coating of a biomaterial to reduce surgical site infection. However, evaluations of these materials are inconsistent, and therefore it is difficult to compare their antibacterial performance. In this study, we evaluated the influence of different media such as nutrient broth (NB), Mueller-Hinton broth (MHB) and fetal bovine serum (FBS) on the antibacterial activity of AgNO3- or gentamicin-added bone cement using a modified ISO 22196 standard to devise a method to evaluate the antibacterial activity of biomaterials in vitro. The antibacterial activity results against Staphylococcus aureus and Escherichia coil were different in each medium. The antibacterial activity of AgNO3 in FBS was lower than the other media, whereas the antibacterial activity of gentamicin in FBS was higher than in the other media. It was assumed that the fluctuating antibacterial activity was influenced by serum components. The results showed that the ISO 22196 antibacterial evaluation method is suitable to evaluate antibacterial biomaterials after modifying the medium to FBS.

Lubricity and stability of poly(2-methacryloyloxyethyl phosphorylcholine) polymer layer on Co-Cr-Mo surface for hemi-arthroplasty to prevent degeneration of articular cartilage.

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.

Development of novel thermal sprayed antibacterial coating and evaluation of release properties of silver ions.

Several studies have addressed the use of antibacterial coating to reduce implant-associated infections. In this study, novel silver (Ag)-containing calcium-phosphate (CP) coating technology based on the thermal spraying method was developed. The coating's physical and chemical properties, in vitro antibacterial activity, hydroxyapatite (HA)-forming ability, and release of Ag ions were evaluated. An amorphous structure of the coating was confirmed by X-ray diffraction, and Ag residue in the coating was determined by elementary analysis. The coating showed strong antibacterial activity to methicillin-resistant Staphylococcus aureus in fetal bovine serum (FBS) along with HA-forming ability in simulated body fluid. Therefore, it is expected that the coating would confer antibacterial and bone bonding abilities to the implant surface. Time course release testing of Ag ions from the coating on immersion in FBS showed pronounced Ag release for up to 24 h after immersion, with consistent strong antibacterial activity at the early postoperative stage. In repeated testing, the amount of released Ag ions was about 6500 parts per billion (ppb, microg/L) for the first release test, after which it gradually decreased. However, retention of significant release of Ag ions after a sixth repeat implies that Ag release from the coating is slow in FBS.

Effects of mobility/immobility of surface modification by 2-methacryloyloxyethyl phosphorylcholine polymer on the durability of polyethylene for artificial joints.

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.

Superlubricious surface mimicking articular cartilage by grafting poly(2-methacryloyloxyethyl phosphorylcholine) on orthopaedic metal bearings.

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.

Enhanced wear resistance of orthopaedic bearing due to the cross-linking of poly(MPC) graft chains induced by gamma-ray irradiation.

We assumed that the extra energy supplied by gamma-ray irradiation produced cross-links in 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer grafted cross-linked polyethylene (CLPE-g-MPC) and investigated its effects on the tribological properties of CLPE-g-MPC. In this study, we found that the gamma-ray irradiation produced cross-links in three kinds of regions of CLPE-g-MPC: poly(MPC) layer, CLPE-MPC interface, and CLPE substrate. The dynamic coefficient of friction of CLPE-g-MPC slightly increased with increasing irradiation doses. After the simulator test, both the nonsterilized and gamma-ray sterilized CLPE-g-MPC cups exhibited lower wear than the untreated CLPE ones. In particular, the gamma-ray sterilized CLPE-g-MPC cups showed extremely low and stable wear. As for the nonsterilized CLPE-g-MPC cups, the weight change varied with each cup. When the CLPE surface is modified by poly(MPC) grafting, the MPC graft polymer leads to a significant reduction in the sliding friction between the surfaces that are grafted because water thin films formed can behave as extremely efficient lubricants. Such a cross-link of poly(MPC) slightly increases the friction of CLPE by gamma-ray irradiation but provides a stable wear resistant layer on the friction surface. The cross-links formed by gamma-ray irradiation would give further longevity to the CLPE-g-MPC cups.

Effect of 2-methacryloyloxyethyl phosphorylcholine concentration on photo-induced graft polymerization of polyethylene in reducing the wear of orthopaedic bearing surface.

Photo-induced graft polymerization of 2-methacryloyloxyethyl phosphorylcholine (MPC) on cross-linked polyethylene (CLPE) has been developed as a novel technology for reducing wear of orthopaedic bearings. In this study, the effect of MPC concentration on graft polymerization and the resultant properties of the grafted poly (MPC) layer have been investigated. The grafted poly (MPC) layer thickness increased with the MPC concentration in feed. The hip simulator wear test confirmed that CLPE-g-MPC cups exhibited minimal wear compared with untreated CLPE cups. Since MPC is a highly hydrophilic methacrylate, the water-wettability of CLPE-g-MPC was greater than that of untreated CLPE due to the formation of a poly(MPC) nanometer-scale layer. The CLPE-g-MPC orthopaedic bearing surface exhibited high lubricity, because of the present of the poly(MPC) layer even at a thickness of 10 nm. This layer is considered responsible for the improved wear resistance. Nanometer-scale modification of CLPE with poly(MPC) is expected to significantly increase the durability of the orthopaedic bearings. Poly (MPC) layer thickness can be controlled by changing the MPC concentration in feed. In order to achieve nanometer-scale modification of poly(MPC) in this manner, it is necessary to use a long photo-irradiation time for the MPC graft polymerization system, which contains a high-concentration monomer without its gelation.

High lubricious surface of cobalt-chromium-molybdenum alloy prepared by grafting poly(2-methacryloyloxyethyl phosphorylcholine).

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.

Apatite formation on zirconium metal treated with aqueous NaOH.

Previous studies by the authors have shown that titanium metal, titanium alloys and tantalum metal which were subjected to aqueous NaOH solution and subsequent heat treatments form an apatite surface layer upon immersion in a simulated body fluid (SBF) with ion concentrations nearly equal to those in human blood plasma. These metals form the apatite surface layer even in living body, and bond to living bone through the apatite layer. In the present study, the apatite-forming ability of NaOH-treated zirconium metal in SBF has been investigated. A hydrated zirconia gel layer was formed on the surface of the zirconium metal on exposure to 1-15 M NaOH aqueous solutions at 95 degrees C for 24h. It was observed that the metals treated in NaOH aqueous solutions with concentrations above 5 M form an apatite layer on their surface in SBF. This indicates that the Zr-OH group of the zirconia gel induces apatite nucleation. The present study points to the possibility of obtaining bioactive zirconium after treatment by NaOH.