Search

This study investigated the efficacy of copper (Cu) as an antibacterial element incorporated on titanium (Ti) surface by electrochemical treatment. Cu was incorporated onto Ti surface by micro-arc oxidation (MAO). A small amount of Cu was incorporated into the oxide layer and was found to be in oxidized states. Cu-incorporated samples exhibited no-harmful effect on the proliferation of osteoblastlike cells. Moreover, the difference in antibacterial property between fresh and incubated samples was evaluated using gram-positive and gram-negative facultative anaerobic bacteria. The specific antibacterial property of Cu incorporated into the Ti surface were confirmed. The antibacterial property prolonged upon immersion in physiological saline for 28 days. In other words, MAO-treated Ti containing Cu in this study is expected to achieve long-term antibacterial property in practical usage.

Chemical transitions after atmospheric pressure plasma irradiation were investigated by evaluating intermolecular attractions and atomic and molecular reactions. Gold, titanium and stainless-steel alloy samples were ground with #800 grit SiC waterproof paper and nitrogen gas atmospheric plasma irradiation was conducted. The surface free energies of the treated alloys were calculated and compared statistically. X-ray photoelectron spectroscopy analysis was performed.The surface free energies of all metal surfaces treated by plasma irradiation were 1.5-times higher than those of the untreated metals. The energy of the hydrogen bonding component increased, and all alloy surfaces were coated with metal oxide after only a short period of plasma irradiation. The surfaces oxidized by plasma exhibited a high active energy, mainly due to an increase in the hydrogen bonding component. Reactions with oxygen in the air were promoted on the clean surfaces with exposed reactive elements.

To elucidate the mechanism of adhesion of soft and hard tissues to yttria-stabilized tetragonal zirconia polycrystalline (Y-TZP), Y-TZP and titanium disks were immersed in ultrapure water and in Hanks' solution, and the changes in the surface compositions and chemical states were characterized using X-ray photoelectron spectroscopy. After immersion in ultrapure water for 60 days, the concentration of hydroxyl groups on the Y-TZP surface increased. In addition, only phosphate ions were incorporated into the surface during immersion in Hanks' solution, while other ions did not react. On the other hand, the surface of Ti was also hydrated in ultrapure water; however, calcium phosphate formed on it during immersion in Hanks' solution. Therefore, the reactivity of Y-TZP with electrolytes was lower than that of Ti. We conclude that the formation of the phosphate on the Y-TZP surface in physiological conditions possibly enhances the adhesion of soft and hard tissues to Y-TZP.

Recently, the problem of infection on implanted devices caused by the formation of biofilms has been recognized. Surface treatment to prevent the initial stages of bacterial adhesion and subsequent bacterial growth is the only possible solution against such infection. In this study, simple electrochemical treatment was used for introducing silver, an antibiotic agent, on the titanium surface. A porous oxide layer containing small amounts of silver was formed on the metal of the substrate. This was done by microarc oxidation using the electrolyte with silver nitrate. The porous oxide layer was almost amorphous with a small fraction of anatase phase. The samples prepared using the electrolyte containing 0.04 mM or a higher concentration of silver nitrate showed an excellent antibacterial effect against both

A customized micro arc oxidation (MAO) treatment technique was developed to obtain desirable antibacterial properties on titanium surfaces. The two-step MAO treatment was applied to fabricate a specimen containing both Ag and Zn in its surface oxide layer. Surface analyses and metal-ion release tests were performed to evaluate the presence of Ag and Zn and the ion release behavior for simulating practical usage, respectively. Additionally, the antibacterial properties of the specimens were also evaluated using gram-negative facultative anaerobic bacteria. The MAO-treated specimens containing both Ag and Zn showed excellent antibacterial properties against Escherichia coli, and the properties were sustained even after 28 days of immersion in physiological saline to simulate the living environment.

Recent studies indicate that biodegradable magnesium alloys and composites are attracting a great deal of attention in orthopedic applications. In this study, magnesium&ndash, hydroxyapatite (Mg&ndash, HAP) composites with different compositions and grain size were fabricated by a spark plasma sintering (SPS) method. Their mechanical properties and corrosion behavior in a pseudo-physiological environment were investigated by pH measurements and inductivity coupled plasma (ICP) elemental analysis after an immersion test using Hanks&rsquo, solution. The results clearly showed that the addition of HAP improved both the mechanical properties and corrosion resistance. The results also indicated that the finer grain size improved most of the properties that are needed in a material for an orthopedic implant. Furthermore, the authors reveal that there is a strong correlation between the compressive strength and the porosity. In order to achieve the same compressive strength as human bone using these fabrication conditions, it is revealed that the porosity should be lower than 1.9%.

Recently, silver (Ag) and copper (Cu) have been incorporated into a titanium (Ti) surface to realize their antibacterial property. This study investigated both the durability of the antibacterial effect and the surface change of the Ag- and Cu-incorporated porous titanium dioxide (TiO2) layer. Ag- and Cu-incorporated TiO2 layers were formed by micro-arc oxidation (MAO) treatment using the electrolyte with Ag and Cu ions. Ag- and Cu-incorporated specimens were incubated in saline during a period of 0&ndash, 28 days. The changes in both the concentrations and chemical states of the Ag and Cu were characterized using X-ray photoelectron spectroscopy (XPS). The durability of the antibacterial effects against Escherichia coli (E. coli) were evaluated by the international organization for standardization (ISO) method. As a result, the Ag- and Cu-incorporated porous TiO2 layers were formed on a Ti surface by MAO. The chemical state of Ag changed from Ag2O to metallic Ag, whilst that of Cu did not change by incubation in saline for up to 28 days. Cu existed as a stable Cu2O compound in the TiO2 layer during the 28 days of incubation in saline. The concentrations of Ag and Cu were dramatically decreased by incubation for up to 7 days, and remained a slight amount until 28 days. The antibacterial effect of Ag-incorporated specimens diminished, and that of Cu was maintained even after incubation in saline. Our study suggests the importance of the time-transient effects of Ag and Cu on develop their antibacterial effects.

Osseointegrated implants have been recognized as being very reliable and having long-term predictability. However, host defense mechanisms against infection have been known to be impaired around a dental implant because of the lack of a periodontal ligament (PDL). The purpose of our experimental design was to produce cementum and PDL on the implant surface adopting cell sheet technology. To this aim we used PDL-derived cells, which contain multipotential stem cells, as the cell source and we cultured them on an implant material constituted of commercially pure titanium treated with acid etching, blasting, and a calcium phosphate (CaP) coating to improve cell attachment. Implants with adhered human PDL cell sheets were transplanted into bone defects in athymic rat femurs as a xenogeneic model. Implants with adhered canine PDL-derived cell sheets were transplanted into canine mandibular bone as an autologous model. We confirmed that PDL-derived cells cultured with osteoinductive medium had the ability to induce cementum formation. The attachment of PDL cells onto the titanium surface with three surface treatments was accelerated, compared with that onto the smooth titanium surface, at 40 min after starting incubation. Results in the rat model showed that cementum-like and PDL-like tissue was partly observed on the titanium surface with three surface treatments in combination with adherent PDL-derived cell sheets. On the other hand, osseointegration was observed on almost all areas of the smooth titanium surface that had PDL-derived cell sheets, but did not have the three surface treatments. In the canine model, histological observation indicated that formation of cementum-like and PDL-like tissue was induced on the titanium surface with surface treatments and that the PDL-like tissue was perpendicularly oriented between the titanium surface with cementum-like tissue and the bone. Results demonstrate that a periodontal-like structure was formed around a titanium implant, which is similar to the environment existing around a natural tooth. The clinical application of dental implants combined with a cell sheet technique may be feasible as an alternative implant therapy. Furthermore, application of this methodology may play an innovative role in the periodontal, prosthetic, and orthodontic fields in dentistry.

Superior mechanical and chemical properties of Zr70Ni16Cu6Al8 bulk metallic glass (BMG) demonstrate its promise as a novel biomaterial for fabrication of implants. The aim of the present study was to validate mechanical, chemical, and biological properties of Zr70Ni16Cu6Al8 BMG through comparison with titanium (Ti). Our data indicated higher tensile strength, lower Young’s modulus, and reduced metal ion release of Zr70Ni16Cu6Al8 BMG compared with Ti. Biosafety of bone marrow mesenchymal cells on Zr70Ni16Cu6Al8 BMG was comparable to that of Ti. Next, screw-type implant prototypes made of Zr70Ni16Cu6Al8 BMG were fabricated and inserted into rat long bones. Zr70Ni16Cu6Al8 BMG implants indicated a higher removal-torque value and lower Periotest value compared with Ti implants. In addition, higher amounts of new bone formation and osseointegration were observed around Zr70Ni16Cu6Al8 BMG implants compared with Ti implants. Moreover, gene expression analysis displayed higher expression of osteoblast- and osteoclast-associated genes in the Zr70Ni16Cu6Al8 BMG group compared with the Ti group. Importantly, loading to implants upregulated bone formation, as well as osteoblast- and osteoclast-associated gene expression in the peri-implant area. No significant difference in concentrations of Ni, Al, Cu, and Zr in various organs was shown between in the Zr70Ni16Cu6Al8 BMG and Ti groups. Collectively, these findings suggest that Zr70Ni16Cu6Al8 BMG is suitable for fabricating novel implants with superior mechanical properties, biocompatibility, stability, and biosafety compared with Ti. Statement of Significance Titanium is widely used to fabricate orthopedic and dental implants. However, Titanium has disadvantages for biomedical applications in regard to strength, elasticity, and biosafety. Recently, we developed a novel hypoeutectic Zr70Ni16Cu6Al8 BMG, which has superior mechanical and chemical properties. However, the validity of Zr70Ni16Cu6Al8 BMG for biomedical application has not been cleared. The aim of the present study was to validate the mechanical, chemical, and biological properties of Zr70Ni16Cu6Al8 BMG for biomedical applications through comparison with Titanium. The present study clarifies that Zr70Ni16Cu6Al8 BMG has good mechanical properties, corrosion resistance, and osteogenic activity, which are necessary features for biomedical applications. The present study provides for the first time the superiority of Zr70Ni16Cu6Al8 BMG implants to Titanium implants for biomedical applications.

Recently, biofilm formation caused by bacterial adhesion and colonization has been recognized as the major cause of failure in orthopedic and dental implant surgeries. In this study, a customized micro-arc oxidation (MAO) treatment technique was developed to obtain desirable antibacterial properties on Ti surfaces. The two-step MAO treatment was applied in the fabrication of specimens with Ag and with/without Zn in their surface oxide layer. In order to simulate practical usage, surface analyses and immersion tests were performed to evaluate the incorporation of Ag and Zn into the resulting oxide layer and ion release behavior, respectively. Additionally, the antibacterial properties of the specimens after long-term immersion in physiological saline were evaluated using Gram-negative facultative anaerobic bacteria. The MAO-treated specimens containing Ag and Zn exhibited excellent antibacterial properties against Escherichia coli, which were sustained even after 6 months of immersion in physiological saline to simulate practical usage. Moreover, the Ag ions released from the surface oxide indicate the antibacterial properties of the specimen in the early stage, while the release of the corrosion products of Zn demonstrates its antibacterial properties in the later stage.

To clarify the effects of micron/submicron hybrid topography on cell morphology and functionalization, we investigated the adhesion and differentiation of human mesenchymal stem cells (hMSCs) to titanium (Ti) surfaces with three different topographies: micron, submicron, and hybrid grooves created using a femtosecond laser. hMSCs cultured on Ti specimens showed high alignment on micron and hybrid surfaces after 6 h of incubation, whereas cells attached to submicron and hybrid surfaces were elongated. An examination of vinculin-positive adhesion plaques indicated that micron grooves affected cellular alignment by modifying the initial cell polarization, whereas submicron grooves affected cellular extension. A superposition effect of topography was evidenced by the highly aligned and elongated morphology of hMSCs grown on the hybrid surface, which promoted osteogenic and chondrogenic differentiation. These findings provide a basis for the design of novel biomaterial surfaces that can control specific cellular functions.

This study investigated the time transient effect of zinc (Zn) in the porous titanium dioxide formed by micro-arc oxidation (MAO) treatment routinely performed for Zn-containing electrolytes. The aim of our analysis was to understand the changes in both the chemical and biological properties of Zn in physiological saline. The morphology of the Zn-incorporated MAO surface did not change, and a small amount of Zn ions were released at early stages of incubation in saline. We observed a decrease in Zn concentration in the oxide layer because its release and chemical state (Zn2+ compound to ZnO) changed over time during incubation in saline. In addition, the antibacterial property of the Zn-incorporated MAO surface developed at late periods after the incubation process over a course of 28 days. Furthermore, osteogenic cells were able to proliferate and were calcified on the specimens with Zn. The changes related to Zn in saline had non-toxic effects on the osteogenic cells. In conclusion, the time transient effect of Zn in a porous titanium dioxide layer was beneficial to realize dual functions, namely the antibacterial property and osteogenic cell compatibility. Our study suggests the importance of the chemical state changes of Zn to control its chemical and biological properties.

Surface charge is one of the essential physicochemical properties of titanium surfaces for extracellular protein adsorption. Titanium surfaces are generally electronegatively charged at physiological pH. Typical cellular adhesive proteins and cell membranes are also negatively charged. Therefore, there are no direct electric interactions between proteins and titanium surfaces at physiological pH. The objective of this study was to determine how different electrical charges on titanium surfaces affect protein adsorption. Commercially pure grade-2 titanium disks, 19 mm in diameter and 1.5 mm in thickness, having acid-etched micro-roughed surfaces, were prepared. Electropositive charge was supplied by soaking in LiOH solution at concentrations of 0.05, 0.1, 0.25, 0.5, and 1.0 M. After LiOH treatment, X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) were performed. The zeta potential, isoelectric point, and wettability of titanium surfaces were measured. The adsorption levels of proteins, including albumin, laminin, and fibronectin, were evaluated. Osteoblastic cell attachment level was also determined. Incorporation of Li was detected in the oxide layer of titanium without surface morphological modification. The zeta potential was shifted up and the isoelectric point was increased from 3.94 to 5.63 by LiOH treatment. Long-term super-hydrophilicity was also obtained on Li-treated surfaces. The adsorption of albumin and laminin increased with increasing concentration of LiOH treatment solution, whereas fibronectin adsorption was highest upon treatment with 0.25 M. The osteoblastic cell attachment level was shown to be dependent on the amount of fibronectin adsorbed. In conclusion, LiOH treatment enhances biological adhesion on titanium with an increase in surface charge and hydrophilicity. This study suggests that modifying the surface charge provides a direct protein-to-materials interaction and the optimal application of Li should be investigated further.

Micro-arc oxidation (MAO) is one of the methods of surface modification of metal substrates and is a relatively simple procedure. The MAO surface is suitable for biomaterials because of its rough complex geometry and the ability to incorporate various ions. The conditions of MAO coatings can be optimized using some parameters, such as electrolytes and electrical factors. In this chapter, the principle of MAO is explained in the first section. The applications of MAO to biomedical fields are introduced in subsequent sections. The second section describes the efficacy on bioactivity of metallic biomaterials in vitro. The third section describes the methodology of in vivo evaluation of the osseointegration capability of titanium implants. Because direct integration of titanium implant to bone tissue is closely involved in bone formation around titanium surfaces without fibrous soft tissue, the evaluation of histological and three-dimensional morphology of bone tissue is absolutely imperative. Furthermore, the stability of titanium implants evaluated by mechanical test has an impact on the clinical situation.

The microstructures and magnetic properties of Zr–Ta binary alloys were examined in the study presented here. The Zr–Ta alloys (Zr-(0–50) mass% Ta) were prepared from 99.5 mass% zirconium a...

To clarify the mechanism of localized corrosion on zirconium in chloride environments, corrosion tests of zirconium and its alloys were performed using conventional and micron-scale measurement systems with surface areas of 0.35 cm2 and less than 0.04 cm2, respectively. The pitting potential significantly dropped by more than 1 V when zirconium was alloyed with over 10 mol% of tin. Zr4Sn and Zr5Sn3 intermetallics hindered the formation of passive films on the substrate. Additionally, tin was found on the surface of a commercially pure zirconium. From the micron-scale measurement results, the inclusion with the highest concentration of tin (at least 0.44 mol%) in the tested area was selected as the preferential initiation site for pitting corrosion. Thus, tin played an important role in determining the corrosion resistance of zirconium in chloride environments.

Made available in DSpace on 2018-12-11T16:52:26Z (GMT). No. of bitstreams: 0 Previous issue date: 2018-06-25 Japan Agency for Medical Research and Development Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq) Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) In this study, a micro-arc oxidation treatment was applied to Ti-15Zr-xMo (x = 0, 5, 10 and 15 wt%) alloys to produce porous oxide layers enriched with bioactive ions (calcium and phosphorus) for use as osseointegrative implants. Biocompatibility studies, namely metabolic activity, mineralization and differentiation studies were conducted with human osteoblastic cell line SAOS-2. A typical porous coating was obtained in all samples, with similar morphologies and thicknesses, which were found to be dependent on the maximum applied voltage. Calcium and phosphorus ions were incorporated into the films, as indicated by EDX analysis. Chemical analyses indicated that the films were composed preferentially of Ti and Zr oxides. XRD patterns revealed mostly substrate Ti phases. However, cross-sectional TEM imaging and automated phase and orientation mapping showed distinct amorphous and nanocrystalline regions within the films, with a higher fraction of Ca atoms incorporated in the outer layer. After immersion in Hanks’ Balanced Salt Solution (HBSS) for seven days, small amounts of calcium phosphate precipitates were observed at the surface of all samples which were confirmed by ICP-AES measurements, indicating that the MAO treatment possibly introduced a considerable bioactive response in the samples. Biological results indicate that Ti-15Zr-15Mo MAO-treated surfaces are biocompatible and induce a higher osteoblasts viability and mineralization. The combination of porous structure and bioactive composition of the oxide layers can be suitable for use as advanced biomedical implants with osseointegration ability. IBTN/BR – Brazilian Branch Institute of Biomaterials Tribocorrosion and Nanomedicine IFSP – Federal Institute of Education Science and Technology UNESP – Univ Estadual Paulista Laboratório de Anelasticidade e Biomateriais Postgraduate Program in Biotechnology National Institute of Metrology Quality and Technology UNIGRANRIO - University of Grande Rio Post-Graduate Program on Translational Biomedicine INMETRO - National Institute of Metrology Quality and Technology Metrology Materials Division CBPF – Centro Brasileiro de Pesquisas Físicas UFSCar – Federal University of São Carlos Department of Materials Engineering TMDU - Tokyo Medical and Dental University Graduate School of Medical and Dental Sciences TMDU - Tokyo Medical and Dental University Institute of Biomaterials and Bioengineering The University of Tokyo Graduate School of Engineering UNESP – Univ Estadual Paulista Laboratório de Anelasticidade e Biomateriais FAPESP: 00851-6/2015 CNPq: 207417/2015-6 CAPES: 99999.008666/2014-08

Single-walled carbon nanotubes (SWNTs) have unique near-infrared absorption and photoemission properties that are attractive for in vivo biological applications such as photothermal cancer treatment and bioimaging. Therefore, a smart functionalization strategy for SWNTs to create biocompatible surfaces and introduce various ligands to target active cancer cells without losing the unique optical properties of the SWNTs is strongly desired. This paper reports the design and synthesis of a SWNT/gel hybrid containing maleimide groups, which react with various thiol compounds through Michael addition reactions. In this hybrid, the method called carbon nanotube micelle polymerization was used to noncovalently modify the surface of SWNTs with a cross-linked polymer gel layer. This method can form an extremely stable gel layer on SWNTs; such stability is essential for in vivo biological applications. The monomer used to form the gel layer contained a maleimide group, which was protected with furan in endo-form. The resulting hybrid was treated in water to induce deprotection via a retro-Diels-Alder reaction and then functionalized with thiol compounds through Michael addition. The functionalization of the hybrid was explored using a thiol-containing fluorescent dye as a model thiol, and the formation of the SWNT-dye conjugate was confirmed by energy transfer from the dye to SWNTs. Our strategy offers a promising SWNT-based platform for biological functionalization for cancer targeting, imaging, and treatment.

In this study, osteogenic differentiation and calcification of preosteoblast (MC3T3-E1) cultured on sputter-deposited titanium (Ti), zirconium (Zr), and gold (Au) on cover glasses were evaluated to understand the differences in bone formation ability among these three metals; these metals show the same high corrosion resistance, but Ti and Zr are covered by surface passive oxide film while Au is not covered by the oxide film. Ti and Zr promoted cellular proliferation without osteogenic differentiation. Cells cultured on Ti and Zr expressed higher levels of Runx2, Col1α1, and Akp2 at an earlier stage, which indicated faster promotion of osteogenic differentiation, as compared to those cultured on Au. Moreover, after 21 days of culture, the Bglap1 and Ifitm5 expression peaks in cells cultured on Ti and Zr were higher than those in cells cultured on Au, which indicated faster promotion of calcification. Cells cultured on Ti showed an advantage in osteogenic differentiation at an early stage, while cells on Zr showed better calcification promotion with a long-term culture. The amount of extracellular calcified deposits was in good agreement with the gene expression results. On the other hand, the intracellular calcium content of cells on Au specimens was higher than that of cells on Ti and Zr specimens. The results indicate that preosteoblasts on Ti and Zr showed faster osteogenic differentiation and calcification than those on Au, whereas Au improved the intracellular calcium content. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 104A: 639-651, 2016.

2-Methacryloyloxyethyl phosphorylcholine (MPC) polymers for electrodeposition to titanium surfaces were synthesized. The polymers were block-type copolymers composed of a poly(MPC) segment and a poly(2-aminoethylmethacrylate (AEMA)) segment, which could electronically adsorb to a titanium oxide film on the titanium surface. The polymer was synthesized as expected by nuclear magnetic resonance and gel permeation chromatography. In a 0.26 mmol L−1 PMbA solution adjusted to pH 11, −3.0 V (vs. an Ag/AgCl electrode) was applied to a titanium substrate for 300 s. We evaluated the effects of the molecular structure of poly(MPC-block-AEMA) (PMbA) with a different polymerization degree of MPC unit, whereas the polymerization degree of the AEMA units was fixed. The 15-min electrodeposition of PMbA100 was the most efficient condition in this study. On the other hand, the results of the water contact angle and the amount of adsorbed protein did not change, even when altering the MPC unit number and electrodeposition time. This indicates that the immobilization by electrodeposition of PMbA is important for the inhibition of protein adsorption, while the polymerization degree of the MPC unit and the electrodeposition time do not influence them. This study will enhance the understanding of effective polymer structures for electrodeposition and electrodeposition conditions.

To develop metallic materials with thromboresistance, a block-type copolymer (PMbA) was immobilized onto a titanium surface with electrodeposition. The polymer was composed of a poly(2-(methacryloyloxy)ethyl phosphorylcholine (MPC)) segment and a poly(2-aminoethylmethacrylate) segment, which was designed to electronically adsorb to the surface oxide layer on the titanium surface. We confirmed that the polymer was synthesized as expected by nuclear magnetic resonance and gel permeation chromatography. In a 0.26 mmol L−1 PMbA solution adjusted to pH 11, −3.0 V (vs. an Ag/AgCl electrode) was applied to a titanium substrate for 300 s. The immobilization of PMbA on the titanium was confirmed with X-ray photoelectron spectroscopy and an atomic force microscope. The water contact angle and amount of adsorbed protein on the PMbA-modified surface were decreased. Thrombus formation was not observed all over the surface even when the surface was contacted with human blood without an anticoagulant. Therefore, PMbA covered the surface with even density and poly(MPC) segments in PMbA inhibited platelet adsorption. Electrodeposition with PMbA improves the blood compatibility of a titanium substrate in a simple process. © 2015 Wiley Periodicals, Inc. J Biomed Mater Res Part B: Appl Biomater, 2015.

A Velcro-like poly(ethylene glycol) (PEG) interface was prepared in order to control the friction dynamics of material surfaces. Graft- and loop-type PEGs were formed on mirror-polished Ti surfaces using an electrodeposition method with mono- and di-amine functionalized PEGs. The friction dynamics of various combinations of PEG surfaces (i.e., graft-on-graft, loop-on-loop, graft-on-loop, and loop-on-graft) were investigated by friction testing. Here, only the Velcro-like combinations (graft-on-loop and loop-on-graft) exhibited a reversible friction behavior (i.e., resetting the kinetic friction coefficient and the reappearance of the maximum static friction coefficient) during the friction tests. The same tendency was observed when the molecular weights of loop- and graft-type PEGs were tested at 1 k and 10 k, respectively. This indicates that a Velcro-like friction behavior could be induced by simply changing the conformation of PEGs, which suggests a novel concept of altering polymer surfaces for the effective control of friction dynamics.

Synthesis of a crosslinked polymer on single-walled carbon nanotubes (SWNTs) is a promising method for functionalization of the SWNTs due to their high coating stability together with their intactn...

Diamond-like carbon (DLC) material is used in blood contacting devices as the surface coating material because of the antithrombogenicity behavior which helps to inhibit platelet adhesion and activation. In this study, DLC films were doped with boron during pulsed plasma chemical vapor deposition (CVD) to improve the blood compatibility. The ratio of boron to carbon (B/C) was varied from 0 to 0.4 in the film by adjusting the flow rate of trimethylboron and acetylene. Tribological tests indicated that boron doping with a low B/C ratio of 0.03 is beneficial for reducing friction (μ = 0.1), lowering hardness and slightly increasing wear rate compared to undoped DLC films. The B/C ratio in the film of 0.03 and 0.4 exhibited highly hydrophilic surface owing to their high wettability and high surface energy. An in vitro platelet adhesion experiment was conducted to compare the blood compatibility of TiNb substrates before and after coating with undoped and boron doped DLC. Films with highly hydrophilic surface enhanced the blood compatibility of TiNb, and the best results were obtained for DLC with the B/C ratio of 0.03. Boron doped DLC films are promising surface coatings for blood contacting devices.

In this study, surface treatment of a Co–Ni–Cr–Mo alloy (MP35N) was attempted to attain biocompatibility using an anodic oxidation technique. To determine the optimal condition of the anodic oxidation treatment for stent applications, anodic polarization of the alloy was first conducted. After anodic oxidation, the surface topology and wettability were examined, and the composition and chemical states of the surface oxide were characterized. For biocompatibility, stent surfaces must have both cell adhesion and antithrombogenic properties. Therefore, the anodically oxidized surface was assessed with an endothelial cell attachment test and an in vitro platelet adhesion test. The results indicated that the topography, wettability, and composition of the surface oxide film on the alloy were changed by anodic oxidation at a voltage near the passive and transpassive region. The surface roughness and wettability increased after anodic oxidation. The major content of the oxide layer after anodic oxidation was Cr containing a small amount of Mo, and Ni and Co were almost eliminated from the layer. Platelet activation of the alloy decreased significantly after anodic oxidation at an optimal potential, whereas the cytocompatibility remained constant. Therefore, the anodic oxidation is an effective process for treating this alloy for stent applications.

Susceptibility artifacts generated in magnetic resonance (MR) images were quantitatively evaluated for various metals using a three-dimensional (3-D) artifact rendering to demonstrate the correlation between magnetic susceptibility and artifact volume. Ten metals (stainless steel, Co-Cr alloy, Nb, Ti, Zr, Mo, Al, Sn, Cu and Ag) were prepared, and their magnetic susceptibilities measured using a magnetic balance. Each metal was embedded in a Ni-doped agarose gel phantom and the MR images of the metal-containing phantoms were taken using 1.5 and 3.0 T MR scanners under both fast spin echo and gradient echo conditions. 3-D renderings of the artifacts were constructed from the images and the artifact volumes were calculated for each metal. The artifact volumes of metals decreased with decreasing magnetic susceptibility, with the exception of Ag. Although Sn possesses the lowest absolute magnetic susceptibility (1.8×10(-6)), the artifact volume from Cu (-7.8×10(-6)) was smaller than that of Sn. This is because the magnetic susceptibility of Cu was close to that of the agarose gel phantom (-7.3×10(-6)). Since the difference in magnetic susceptibility between the agarose and Sn is close to that between the agarose and Ag (-17.5×10(-6)), their artifact volumes were almost the same, although they formed artifacts that were reversed in all three dimensions.

To enhance hard-tissue compatibility of Ti, galvanic current between titanium (Ti) and gold (Au) may be available. Prior to the design of medical devices with the capability to generate a galvanic current, it is necessary to understand the control mechanism. In this study, we first measured galvanic current between Ti and Au with various surface areas in Hanks’ solution. The galvanic current increased immediately after connection of two electrodes, followed by an abrupt decrease and a steady state. The galvanic current varied with the combinations of Ti and Au areas. We, thereafter, evaluated the formation of calcium phosphate on Ti under a condition of applying simulated galvanic current. Surface characterization was revealed in which the calcium phosphate formation was enhanced accompanied by growth of Ti oxide layer under the galvanic current application. A similar result was observed on Ti with patterned Au coating without outer electric power. Therefore, galvanic current is useful to enhance hard-tissue compatibility, and this technique has potential for applications to metallic biomaterials. [doi:10.2320/matertrans.MC201204]

Micro-arc oxidation (MAO) was performed on a β-type Ti–29Nb–13Ta–4.6Zr alloy (TNTZ) in this study to improve its bioactivity in a body fluid and its hard-tissue compatibility. The surface oxide layer formed on TNTZ by MAO treatment in a mixture of calcium glycerophosphate and magnesium acetate was characterized using various surface analyses. The oxide layer was mainly composed of two types of TiO 2 (rutile and anatase), and it also contained Ca, P, and Mg, which were incorporated from the electrolyte during the treatment. The calcium phosphate formation on the surface of the specimens after immersion in Hanks’ solution was evaluated to determine the bioactivity of TNTZ with and without MAO treatment. As a result, thick calcium phosphate layers formed on the TNTZ specimen that underwent MAO treatment, whereas only a small amount of precipitate was observed on TNTZ without treatment. Thus, the MAO treatment is a promising method to improve the bioactivity and hard-tissue compatibility of TNTZ.

Strontium (Sr) ions were added to calcium- and phosphate-containing porous titanium oxide layers formed by micro-arc oxidation (MAO) of titanium (Ti) substrates to improve their osseointegration. An MC3T3-E1 preosteoblast was used to evaluate the effect of the incorporated Sr species on cell calcification. Similar surface microporous morphologies of the oxide layers were observed for all specimens produced by MAO, while the contents of the incorporated Sr ions increased with increasing Sr concentrations in MAO electrolytes. The calcium- and phosphate-containing porous layers promoted the cell alkaline phosphatase (ALP) activity, while cell calcification was promoted by the Sr addition. In particular, the ALP activity significantly increased after 10 days of culture, and larger areas of calcified deposits were observed for the specimens treated with MAO electrolytes containing 0.15 mol L(-1) of Sr species. The effect of Sr addition on the calcification of the MAO-treated Ti oxide layers was established in this study.

Electrochemical surface treatments of micro-arc oxidation (MAO) and following cathodic polarization were performed on zirconium (Zr) disks in this study to enhance the bioactivity of Zr. The surface oxide layers formed with electrochemical treatments on Zr disks were characterized using surface analyses; the calcium phosphate formation on the specimens after immersion in Hanks’ solution was evaluated. As a result, thick calcium phosphate layers formed on only Zr specimens that underwent both MAO treatment with a mixture of calcium glycerophosphate and magnesium acetate and subsequent cathodic polarization treatment with sodium sulfate solution, while no precipitate was observed without treatment. Thus, this technique was confirmed to be a promising method to improve the bioactivity of Zr.

The air-formed surface oxide films used for stents were characterized to determine their composition and chemical state on a Co–Ni–Cr–Mo alloy. The change of the films in Hanks’ solution was used to estimate the reconstruction of the film in the human body. Angle-resolved X-ray photoelectron spectroscopy was used to characterize the composition of the film and substrate, as well as the film's thickness. The surface oxide film on the Co–Ni–Cr–Mo alloy (when mechanically polished) consists of oxide species of cobalt, nickel, chromium, and molybdenum, contains a large amount of OH − , and has a thickness of approximately 2.5 nm. Cations exist in the oxide as Co 2+ , Ni 2+ , Cr 3+ , Mo 4+ , Mo 5+ , and Mo 6+ . Chromium is enriched and cobalt and nickel are depleted in the oxide; however, nickel is enriched and cobalt is depleted in the substrate alloy just under the surface oxide film. Concentration of chromium was low and that of nickel was high at small take-off angles. This indicates that distribution of chromium is greater in the inner layer, but nickel is distributed more in the outer layer of the surface oxide film. During immersion in Hanks’ solution, cobalt and nickel dissolved, and the film composition changed to mostly chromium oxide (Cr 3+ ), along with small amounts of cobalt, nickel, and molybdenum oxides, and calcium phosphate containing magnesium, potassium, and carbonate. After immersion in Hanks’ solution, the thickness of the surface layer containing calcium phosphate increased to more than 4 nm, while the amount of OH − increased. The amount of cobalt and nickel in the surface oxide film and in the substrate alloy just below the oxide decreased during immersion.

The use of micro-arc oxidation titania (MAO TiO2) coatings to modify titanium surfaces improves the biocompatibility of implant surfaces. To obtain hydrophilic MAO TiO2 coating surfaces electric polarization, which induces surface electric fields in the materials and produces surface charges, was performed in this study. Electric polarization of the MAO TiO2 coatings was confirmed by measuring the thermally stimulated depolarization current. After electric polarization treatment the MAO TiO2 coatings did not exhibit any obvious changes in surface roughness, morphology, or phase components. X-ray photoelectron spectroscopy results indicated that electric polarization resulted in oxidation of the cathodic-faced surfaces and reduction of the anodic-faced surfaces. This result suggests that the existence of a concentration gradient of oxide ions/oxygen vacancies produced the stored space charge in the coatings. Reduction of the deionized water contact angle on the polarized MAO TiO2 surfaces was maintained for longer periods compared with the non-polarized surface. Our study demonstrated that metastable electric fields across the MAO TiO2 coating produced by electric polarization made it durably wettable by reducing the interfacial surface tension between the material and water.

Recent studies have suggested that low levels of 25-hydroxyvitamin D (25OHD) are associated with cardiovascular risks in medical patients. However, these associations have not been well documented in high risk surgical patients. We hypothesized that serum 25OHD, 1,25-dihydroxyvitamin D (1,25OHD) would be associated with the cardiac operative risk stratification score. The study was conducted with a cross-sectional design at a single academic medical center in Japan. Two hundred five adult patients scheduled for major cardiovascular surgery were included consecutively. Cardiac operative risk was evaluated with the European System for Cardiac Operative Risk Evaluation (EuroSCORE) scoring system. Correlations between 25OHD and 1,25OHD, and EuroSCORE were assessed using simple and multiple linear regression models. Mean 25OHD and 1,25OHD were 20.1 ± 7.1 ng/mL and 51.2 ± 19.2 pg/mL, respectively. Half and 88% of the study population showed deficient (

The corrosion behavior of the Ti-33.5Nb-5.7Ta alloy (Ti-Nb-Ta) as a biocompatible Beta-type Ti alloy during long-term immersion in simulated body fluid was investigated. Like pure Ti, pitting corrosion did not occur on Ti-Nb-Ta during anodic polarization. Thus, alloying of Ti with Nb and Ta did not change the chloride-ion sensitivity. Metal ion release of Ti, Nb, and Ta was detected after 7-d immersion in the solution; however, the amounts of ions were much smaller than those from Type316L stainless steel. X-ray photoelectron spectroscopy revealed that the fractions of Nb and Ta in the passive layer increased during the immersion while that of Ti decreased. The corrosion rate of Ti-Nb-Ta determined by electrochemical impedance spectroscopy kept decreasing over a period of 15 d while the thickness of the passive layer did not change after 1 d. Thus, the reconstruction of the passive layer of the alloy was proven to be important for metal ion release during long-term implantation in a living body. Thus, Ti-Nb-Ta has sufficient corrosion resistance as a biocompatible Beta-type Ti alloy.

This article deals with preparation of nanocomposite which comprised of nanophase separated structure of polymer chains and metal oxide. By grafting poly(hydroxyethyl methacrylate), poly(HEMA) on the surface of titanium which is covered by passive titanium oxide by atom transfer radical polymerization (ATRP) and executing anodic polarization, hierarchy nanophase separated structure with controlled thickness can be obtained. The titanium ions would be cationically charged and completely filled up the unoccupied binding sites of the polymer chains via electrochemical reaction, eventually covering the polymer chains with titanium oxide. However, this structure can be obtained when the anodic polarization is executed at initial applied voltage exceeding 10 VSCE. The control of thickness is possible by controlling the initial applied voltage. These results prove that the conventional polymer can form composite structure with metal oxide without using fillers or special polymers designed for composite.

The cathodic polarization technique to form an alkaline environment on a zirconium (Zr) surface, discussed in the present study, is unique, and gives the ability to form calcium phosphate in a simulated body fluid to Zr; on the other hand, many previous studies have been conducted using immersion in alkaline solutions. In this study, two discrete techniques were investigated. Zr was cathodically polarized in an electrolyte without calcium and phosphate ions, and Zr was cathodically polarized in another electrolyte containing calcium and phosphate ions, Hanks’ solution, to directly form a calcium phosphate layer. The surface was characterized using X-ray photoelectron spectroscopy, and the performance of the material was evaluated by immersion in Hanks’ solution. As a result, the ability to form calcium phosphate in Hanks’ solution was given by cathodic polarization in the Na2SO4 solution containing H2O2. In addition, a cathodic potential under −1.5 VSCE is required to form hydroxyapatite directly in Hanks’ solution. This research clearly reveals useful surface modification techniques giving the ability to form calcium phosphate in a simulated body fluid by cathodic polarization.

Protein-resistant coatings have been studied for inhibiting biofilm formation on implant devices. In this study, titanium (Ti) surfaces were biofunctionalized with poly(ethylene glycol) (PEG) by electrodeposition and were evaluated as biofilm substrates under an oral simulated environment. Streptococcus gordonii, an early colonizer of oral biofilms, was inoculated on Ti and PEG-electrodeposited Ti (PEG-Ti) surfaces and was analyzed quantitatively and topographically. Streptococcus mutans supplemented with sucrose, a late colonizer mainly found in dental plaque, was also used to form biofilms on the surfaces of Ti and PEG-Ti for 20 h followed by sonication as a means of detaching the biofilms. The results indicated that the attachment of S. gordonii on PEG-Ti surfaces was inhibited compared with Ti, and the S. mutans biofilm was easier to be detached from the surface of PEG-Ti than that of Ti. Moreover, the presence of PEG electrodeposited on Ti surface inhibited salivary protein adsorption. The degree of detachment of biofilms from PEG-Ti was associated with the inhibition of the salivary protein adsorption, suggesting weak basal attachment of the biofilms to the electrodeposited surfaces. Therefore, controlling protein adsorption at the initial stage of biofilm formation may be an effective strategy to protect metal surfaces from bacterial contamination not only in dental manipulations but also in orthopedic applications.

Porous Ti (pTi)/hydroxylapatite (HA) composites were fabricated by an infiltration method in a vacuum and sintering. The Young’s modulus of the composites was evaluated before and after the immersion in Hanks’ solution. The strength of the composites was also evaluated by four-point bending test. The Young’s modulus of the compacts was governed by the porosity and was comparable to the human bone in the porosity range from 24 to 34%. The Young’s modulus of sintered pTi/HA composites was larger than that of pTi. The Young’s modulus of the sintered pTi/HA composites decreased after immersion in Hanks’ solution. The proof and bending strengths of the sintered pTi/HA composites were larger than those of pTi. Solid solution hardening of Ti by oxygen contributed the increase of the proof strength. [doi:10.2320/matertrans.M2010092]

Titanium and zirconium were immersed in Hanks’ solution with and without calcium and phosphate ions, and the surfaces were characterized with X-ray photoelectron spectroscopy (XPS) to determine the mechanism of calcium phosphate formation on titanium in simulated body fluids and in a living body. In addition, they were cathodically polarized in the above solutions. As a result, neither calcium nor phosphate stably exists alone on titanium, and calcium phosphate is naturally formed on it; calcium phosphate formed on titanium is stable and protective. On the other hand, calcium is never incorporated on zirconium, while zirconium phosphate, which is easily formed on zirconium, is highly stable and protective.

Both terminals of a poly(ethylene glycol) (PEG) molecule were terminated with amines. The PEG was electrodeposited onto titanium (Ti) to give it the biofunctions such as blood compatibility. The effects of the amine of PEG terminals and the pH at PEG solution on the adsorption amount of PEG molecules and the thickness of PEG layer immobilized on the Ti surface were evaluated using quartz crystal microbalance technique and X-ray photoelectron spectroscopy. The interfacial reactivity between PEG terminals and the Ti surface was the largest at pH 11, according to the interaction between the charge of terminal amines of PEG and the point of zero charge of Ti oxide. The orientations of PEG molecules immobilized on the Ti surface with immersion or electrodeposition at pH 11 were determined by Fourier transform infrared reflection absorption spectroscopy. Consequently, the terminal amines of PEG were oriented perpendicularly to the surface in electrodeposition rather than in immersion. The charged PEG randomly immobilized on the Ti surface with immersion led to platelet aggregation, whereas U-shaped PEG molecule immobilized with electrodeposition inhibited platelet adhesion and aggregation. The immobilization manners of PEG on the Ti surface were strongly associated with a biofunction such as platelet adhesion.