Chikara Ohtsuki

Mechanism of apatite formation on CaOSiO2P2O5 glasses in a simulated body fluid

It has been shown for various types of glasses and glass-ceramics that the essential condition for them to bond to living bone is the formation of an apatite layer on their surfaces in the body. CaO,SiO 2 -based glasses formed the surface apatite layer in a simulated body fluid, whereas CaO,P 2 O 5 -based glasses did not form it. This means that the rate of the apatite nucleation on the surfaces of the former glasses is much higher than that of the latter glasses. The increase in the degree of the supersaturation of the surrounding fluid with respect to the apatite due to dissolution of the calcium ion from the CaO,SiO 2 -based glasses was almost equal to that due to dissolution of the phosphate ion from the CaO,P 2 O 5 -based glasses. The high rate of the apatite nucleation on the surface of the former glasses is therefore attributed to the lower interface energy between the apatite and the glass surfaces. The CaO,SiO 2 -based glasses form a silica hydrogel on their surfaces prior to formation of the apatite layer. This means that the hydrated silica provides specific favorable sites for the apatite nucleation.

Bioactivity of titanium treated with hydrogen peroxide solutions containing metal chlorides

Commercially available pure metallic titanium was chemically treated at 60 degrees C for 24 h with H2O2 solutions containing various metal chlorides to provide titanium with bioactivity, that is, to give it the ability to form a biologically active bone-like apatite layer on the surface. After the chemical treatment the titanium specimens were soaked in a simulated body fluid (the Kokubo solution). Apatite was found to deposit on the specimens treated with the H2O2/TaCl5 and H2O2/SnCl2 solutions. X-ray photoelectron spectroscopic (XPS) study of the specimens treated with those H2O2 solutions indicated that basic Ti-OH groups in titania hydrogel layers on their surfaces were responsible for apatite nucleation and growth.

Chemical reaction of bioactive glass and glass-ceramics with a simulated body fluid

Glass-ceramic A-W containing crystalline apatite and wollastonite in an MgO-CaO-SiO2 glassy matrix bonds to living bone through an apatite layer which is formed on its surface in the body. The parent glass G of glass-ceramic A-W and glass-ceramic A, which has the same composition as glass-ceramic A-W but contains only the apatite, also bond to living bone through the surface apatite layer, whereas glass-ceramic A-W(Al), which contains the apatite and wollastonite in an MgO-CaO-SiO2-Al2O3 glassy matrix, neither forms the surface apatite layer nor bonds to living bone. In the present study, in order to reveal the mechanism of formation of the surface apatite layer, changes in ion concentrations of a simulated body fluid with immersion of these four kinds of glass and glass-ceramics were investigated. Bioactive glass G and glass-ceramics A and A-W all showed appreciable increases in Ca and Si concentrations, accompanied by an appreciable decrease in P concentration, whereas non-bioactive glass-ceramic A-W(Al) hardly showed any element concentration change. It was speculated from these results that dissolution of the Ca(II) and Si(IV) ions from bioactive glass and glass-ceramics plays an important role in forming the apatite layer on their surfaces in the body.

Review Paper: Behavior of Ceramic Biomaterials Derived from Tricalcium Phosphate in Physiological Condition

Various calcium phosphates are used for bone repair. Although hydroxyapatite (HA) sintered ceramics are widely used due to their osteoconductivity, its bioresorbability is so low that HA remains in the body for a long time after implantation. In contrast, tricalcium phosphate (TCP) ceramics show resorbable characters during bone regeneration, and can be completely substituted for the bone tissue after stimulation of bone formation. Therefore, much attention is paid to TCP ceramics for scaffold materials for supporting bone regeneration. This paper reviews bioresorbable properties of calcium phosphate ceramics derived from β-TCP and α-TCP.

Process of formation of bone-like apatite layer on silica gel

It has been proposed that a hydrated silica plays an important role in forming a biologically active apatite layer on the surfaces of bioactive glasses and glass-ceramics in the body. Recent experiments have shown that a silica hydrogel actually induces apatite formation on its surface in a simulated body fluid (SBF). In the present study the process of apatite formation on silica gel was investigated by means of thin-film X-ray diffraction, Fourier-transformed infrared reflection spectroscopy and scanning electron microscopic observation of the surface of the silica gel, as well as the measurement of changes in the ion concentration of the fluid. It was found that the induction period for the apatite nucleation on the surface of the silica gel was about 6 days. Once the apatite nuclei were formed they grew, taking a spherulitic form by consuming the calcium and phosphate ions from the surrounding fluid. Each spherulite consisted of a lot of flake that clustered into a petal-like morphology. The flake was carbonate-containing hydroxyapatite of small-crystallites and/or defective structure. The Ca/P ratio of the apatite was estimated as 1.5–1.6. Thus, the apatite formed was able to induce secondary nucleation of the apatite.

Mechanism of bonelike apatite formation on bioactive tantalum metal in a simulated body fluid

Development of tantalum metal with bone-bonding ability is paid much attention because of its attractive features such as high fracture toughness, high workability and its achievement on clinical usage. Formation of bonelike apatite is an essential prerequisite for artificial materials to make direct bond to living bone. The apatite formation can be assessed in vitro using a simulated body fluid (SBF) that has almost equal compositions of inorganic ions to human blood plasma. The present authors previously showed that the apatite formation on tantalum metal in SBF was remarkably accelerated by treatment with NaOH aqueous solution and subsequent firing at 300 degrees C, while untreated tantalum metal spontaneously forms the apatite after a long soaking period. The purpose of the present study is to clarify the reason why the NaOH and heat treatments accelerate the apatite formation on tantalum metal. X-ray photoelectron spectroscopy was used to analyze changes in surface structure of the tantalum metal at an initial stage after immersion in SBF. Untreated tantalum metal had tantalum oxide passive layer on its surface, while amorphous sodium tantalate was formed on the surface of the tantalum metal by the NaOH and heat treatments. After soaking in SBF, the untreated tantalum metal sluggishly formed small amount of Ta-OH groups by a hydration of the tantalum oxide passive layer on its surface. In contrast, the treated tantalum metal rapidly formed Ta-OH groups by exchange of Na+ ion in the amorphous sodium tantalate on its surface with H3O+ ion in SBF. Both the formed Ta-OH groups combined with Ca2+ ion to form a kind of calcium tantalate, and then with phosphate ion, followed by combination with large amount of Ca2+ ions and phosphate ions to build up apatite layer. The formation rate of Ta-OH groups on the treated tantalum metal predominates the following process including adsorption of Ca2+ ion and phosphate ion on the surface. It is concluded that the acceleration of the apatite nucleation on the tantalum metal in SBF by the NaOH and heat treatments was attributed to the fast formation of Ta-OH group, followed by combination of the Ta-OH groups with Ca2+ and phosphate ions.

Apatite deposition on polyamide films containing carboxyl group in a biomimetic solution

The development of organic–inorganic hybrids composed of hydroxyapatite and organic polymers is attractive because of their novelty in being materials that show a bone-bonding ability, i.e. bioactivity, and because they have mechanical properties similar to those of natural bone. The biomimetic process has received much attention for fabricating such a hybrid, where bone-like apatite is deposited under ambient conditions on polymer substrates in a simulated body fluid (SBF) having ion concentrations nearly equal to those of human extracellular fluid or related solutions. It has been shown that the carboxyl group is effective for inducing heterogeneous nucleation of apatite in the body. In the present study, apatite deposition on polyamide films containing various numbers of carboxyl groups was investigated in 1.5 SBF, which had ion concentrations 1.5 times those of a normal SBF. The effect of incorporation of calcium chloride on the formation of apatite was examined. Polyamide films containing ≤33 mol % CaCl2 did not form apatite, even after soaking in 1.5 SBF for 7 days, and even when the polymer film contained 50 mol % carboxyl group. On the other hand, those modified with ≥40 mass % CaCl2 formed apatite on their surfaces in 1.5 SBF. The ability of the modified film to form an apatite layer increased, and the adhesion of the apatite layer bonded to the film improved, with increasing carboxyl group content. It is concluded that novel apatite–polyamide hybrids can be prepared by a biomimetic process.

Bioactive ceramic-based materials with designed reactivity for bone tissue regeneration

Bioactive ceramics have been used clinically to repair bone defects owing to their biological affinity to living bone; i.e. the capability of direct bonding to living bone, their so-called bioactivity. However, currently available bioactive ceramics do not satisfy every clinical application. Therefore, the development of novel design of bioactive materials is necessary. Bioactive ceramics show osteoconduction by formation of biologically active bone-like apatite through chemical reaction of the ceramic surface with surrounding body fluid. Hence, the control of their chemical reactivity in body fluid is essential to developing novel bioactive materials as well as biodegradable materials. This paper reviews novel bioactive materials designed based on chemical reactivity in body fluid.

A unified in vitro evaluation for apatite-forming ability of bioactive glasses and their variants

The aim of this study was to propose and validate a new unified method for testing dissolution rates of bioactive glasses and their variants, and the formation of calcium phosphate layer formation on their surface, which is an indicator of bioactivity. At present, comparison in the literature is difficult as many groups use different testing protocols. An ISO standard covers the use of simulated body fluid on standard shape materials but it does not take into account that bioactive glasses can have very different specific surface areas, as for glass powders. Validation of the proposed modified test was through round robin testing and comparison to the ISO standard where appropriate. The proposed test uses fixed mass per solution volume ratio and agitated solution. The round robin study showed differences in hydroxyapatite nucleation on glasses of different composition and between glasses of the same composition but different particle size. The results were reproducible between research facilities. Researchers should use this method when testing new glasses, or their variants, to enable comparison between the literature in the future.

Heterogeneous nucleation of hydroxyapatite on protein: structural effect of silk sericin

Acidic proteins play an important role during mineral formation in biological systems, but the mechanism of mineral formation is far from understood. In this paper, we report on the relationship between the structure of a protein and hydroxyapatite deposition under biomimetic conditions. Sericin, a type of silk protein, was adopted as a suitable protein for studying structural effect on hydroxyapatite deposition, since it forms a hydroxyapatite layer on its surface in a metastable calcium phosphate solution, and its structure has been reported. Sericin effectively induced hydroxyapatite nucleation when it has high molecular weight and a β sheet structure. This indicates that the specific structure of a protein can effectively induce heterogeneous nucleation of hydroxyapatite in a biomimetic solution, i.e. a metastable calcium phosphate solution. This finding is useful in understanding biomineralization, as well as for the design of organic polymers that can effectively induce hydroxyapatite nucleation.