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Abstract: Some ceramics show bone-bonding ability, i.e. bioactivity. Apatite formation on ceramics is an essential condition to bring about direct bonding to living bone when implanted into bony defects. A controlled surface reaction of the ceramic is an important factor governing the bioactivity and biodegradation of the implanted ceramic. Among bioactive ceramics, glass–ceramic A–W containing apatite and wollastonite shows high bioactivity, as well as high mechanical strength. In this study, glass–ceramics containing zinc oxide were prepared by modification of the composition of the glass–ceramic A–W. Zinc oxide was selected to control the reactivity of the glass–ceramics since zinc is a trace element that shows stimulatory effects on bone formation. Glass–ceramics were prepared by heat treatment of glasses with the general composition: xZnO·(57.0− x)CaO·35.4SiO2 ·7.2P2O5 ·0.4CaF2 (where x =0–14.2mol.%). Addition of ZnO increased the chemical durability of the glass–ceramics, resulting in a decrease in the rate of apatite formation in a simulated body fluid. On the other hand, the release of zinc from the glass–ceramics increased with increasing ZnO content. Addition of ZnO may provide bioactive CaO–SiO2–P2O5–CaF2 glass–ceramics with the capacity for appropriate biodegradation, as well as enhancement of bone formation. [Copyright &y& Elsevier]

Polydimethylsiloxane (PDMS)–CaO–SiO2 hybrids with starting compositions containing PDMS/(Si(OC2H5)4+PDMS) weight ratio=0.30, H2O/Si(OC2H5)4 molar ratio=2, and Ca(NO3)2/Si(OC2H5)4 molar ratios=0–0.2, were prepared by the sol–gel method. The apatite-forming ability of the hybrids increased with increasing calcium content in the Ca(NO3)2/Si(OC2H5)4 molar ratio range 0–0.1. The hybrids with a Ca(NO3)2/Si(OC2H5)4 molar ratio range 0.1–0.2 formed apatite on their surfaces in a simulated body fluid (SBF) within 12 h. The hybrid with a Ca(NO3)2/Si(OC2H5)4 molar ratio of 0.10 showed an excellent apatite-forming ability in SBF with a low release of silicon into SBF. It also showed mechanical properties analogous to those of human cancellous bones. This hybrid is expected to be useful as a new type of bioactive material. [ABSTRACT FROM AUTHOR]

Selenium, a crucial trace element for many organisms, including prokaryotes and humans, is toxic at high concentrations, necessitating its removal from wastewater. This study investigates the use of jarosite, a naturally occurring iron sulfate mineral with excellent heavy metal attenuation properties, for selenate (Se(VI)) removal for the first time. Biogenic jarosite was synthesized through Fe(II) oxidation by Acidithiobacillus ferrooxidans at an initial pH ranging from 1.5 to 4.0 (J-1.5 to J-4.0). This resulted in the formation of morphologically diverse particles of biogenic jarosite owing to varying Fe(II) oxidation and precipitation rates. For comparative analysis, non-biogenic jarosite (J-90C) and biogenic schwertmannite (S-2.5) were also synthesized. At 0.2 mM initial Se(VI) concentration, J-2.5 demonstrated superior Se(VI) removal compared to J-3.5 and J-90C. At 2.0 mM Se(VI), J-2.5 still outperformed J-3.5 and J-90C although its overall removal efficiency decreased. Notably, at 0.2 mM concentration, Se(VI) removal by J-2.5 was 63 %, which is comparable to 77 % removal by S-2.5. Furthermore, sulfate release from J-2.5 was significantly lower than that from S-2.5 in both Se-free and Se-containing solutions. This study provides critical insights into the synthesis and application of biogenic jarosite as a replacement for metastable schwertmannite, emphasizing its potential as an excellent Se sink for wastewater treatment., Competing Interests: Declaration of Competing Interest The authors declare that they have no competing financial intrests or personal relationships that may have influenced the work reported in this study., (Copyright © 2024 The Authors. Published by Elsevier B.V. All rights reserved.)

Novel calcium phosphate cements (CPCs) that can be resorbed into the human body need to be developed. One approach for improving bioresorbability is reducing the content of calcium phosphate in CPCs; however, this may induces difficulties in setting the cement and increases the risk of decay. Adding bioresorbable polymers to a liquid solution can shorten the setting time and inhibit decay during setting. A novel bioresorbable polymer, phosphorylated pullulan (PPL), was recently reported. The effect of adding PPL to α-tricalcium phosphate (α-TCP)-based CPCs was examined and compared to that of adding bioresorbable polymers such as collagen, chitosan, and alginate. Collagen did not significantly inhibit the conversion of α-TCP to hydroxyapatite (HA), and its combination with calcium phosphate decreased the setting time and suppressed decay; chitosan decreased the setting time when combined with calcium phosphate; and alginate inhibited the conversion of α-TCP to HA and contributed to suppressing the decay. In contrast, PPL slightly inhibited the conversion of α-TCP to HA; however, its combination with calcium phosphate decreased the setting time. Thus, selecting bioresorbable polymers can help effectively control the properties of CPCs., Competing Interests: Declaration of conflicting interestsThe author(s) declared no potential conflicts of interest with respect to the research, authorship, and/or publication of this article.

Among the CaCO 3 polymorphs, aragonite demonstrates a better performance as a filler material in the paper and plastic industries. Despite being ideal from the environmental protection perspective, the production of aragonite particles via CO 2 mineralization of rocks is hindered by the difficulty in achieving high production efficiencies and purities, which, however, can be mitigated by exploiting the potential ability of chelating agents on metal ions extraction and carbonation controlling. Herein, chelating agent N,N-dicarboxymethyl glutamic acid (GLDA) was used to enhance the extraction of Ca from calcium silicate and facilitate the production of aragonite particles during the subsequent Ca carbonation. CO 2 mineralization was promoted in the presence of 0.01-0.1 M GLDA at ≤ 80 °C, with the maximal CaCO 3 production efficiency reached 308 g/kg of calcium silicate in 60 min using 0.03 M GLDA, which is 15.5 times higher than that without GLDA. In addition, GLDA showed excellent effects on promoting aragonite precipitation, e.g., the content of aragonite was only 5.1% in the absence of GLDA at 50 °C, whereas highly pure (> 90%, increased by a factor of 18) and morphologically uniform aragonite was obtained using ≥ 0.05 M GLDA under identical conditions. Aragonite particle morphologies could also be controlled by varying the GLDA concentration and carbonation temperature. This study proposed a carbon-negative aragonite production method, demonstrated the possibility of enhanced and controlled aragonite particle production during the CO 2 mineralization of calcium silicates in the presence of chelating agents.

Octacalcium phosphate (OCP; Ca 8 (HPO 4 ) 2 (PO 4 ) 4  ∙ 5H 2 O) is a precursor of hydroxyapatite found in human bones and teeth, and is among the inorganic substances critical for hard tissue formation and regeneration in the human body. OCP has a layered structure and can incorporate carboxylate ions into its interlayers. However, studies involving the incorporation of tetracarboxylic and multivalent (pentavalent and above) carboxylic acids into OCP have not yet been reported. In this study, we investigate the incorporation of pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid), a type of tetracarboxylic acid, into OCP. We established that pyromellitate ions could be incorporated into OCP by a wet chemical method using an acetate buffer solution containing pyromellitic acid. The derived OCP showed a brilliant blue emission under UV light owing to the incorporated pyromellitate ions. Incorporation of a carboxylic acid into OCP imparted new functions, which could enable the development of novel functional materials for biomedical applications., (© 2021. The Author(s).)

The adhesion behavior of microorganisms on different materials was examined to obtain basic knowledge for designing support materials for microorganisms. The microorganisms were isolated from soil, and their adhesion behavior on hydroxyapatite (HA), carbon-coated HA (Carbon), poly (vinyl chloride) (PVC), and polyurethane (PU) pellets was investigated. The total metabolic activity on and adherence of microorganisms to the tested materials were in the following order: HA > Carbon > PVC > PU. This order was consistent with the extent of hydrophilicity of the materials. Morphological examination and polymerase chain reaction denaturing gradient gel electrophoresis (PCR-DGGE) analysis of microorganisms adhered to the materials revealed that the activities and states of microorganisms were affected by the composition of the pellets. PCR-DGGE analysis revealed various species of microorganisms adhered to the HA pellet. HA ceramics are expected to be one of the most suitable materials for supporting microorganisms.

Unlabelled: Foreign body giant cells (FBGCs) and osteoclasts are multinucleated giant cells (MNGCs), both of which are formed by the fusion of macrophage-derived mononuclear cells. Osteoclasts are distinct from FBGCs due to their bone resorption ability; however, not only morphological, but also functional similarities may exist between these cells. The characterization and diversity of FBGCs that appear in an in vivo foreign body reaction currently remain incomplete. In the present study, we investigated an in vivo foreign body reaction using an extraskeletal implantation model of hydroxyapatite (HA) with different microstructures. The implantation of HA granules in rat subcutaneous tissue induced a foreign body reaction that was accompanied by various MNGCs. HA granules composed of rod-shaped particles predominantly induced cathepsin K (CTSK)-positive FBGCs, whereas HA granules composed of globular-shaped particles predominantly induced CTSK-negative FBGCs. Plasma, which was used as the binder of ceramic granules, stimulated the induction of CTSK-positive FBGCs more strongly than purified fibrin. Furthermore, the implantation of HA composed of rod-shaped particles with plasma induced tartrate-resistant acid phosphatase (TRAP)-positive MNGCs in contrast to HA composed of globular-shaped particles with purified fibrin, which predominantly induced CTSK-negative and TRAP-negative typical FBGCs. These results suggest that CTSK-positive, TRAP-positive, and CTSK- and TRAP-negative MNGCs are induced in this subcutaneous implantation model in a manner that is dependent on the microstructure of HA and presence or absence of plasma., Statement of Significance: We attempted to elucidate the mechanisms responsible for the foreign body reaction induced by the implantation of hydroxyapatite granules with different microstructures in rat subcutaneous tissue with or without plasma components as the binder of ceramic granules. By analyzing the expression of two reliable osteoclast markers, we detected tartrate-resistant acid phosphatase-positive multinucleated giant cells, cathepsin K-positive multinucleated giant cells, and tartrate-resistant acid phosphatase- and cathepsin K-negative multinucleated giant cells. The induction of tartrate-resistant acid phosphatase-positive multinucleated giant cells was plasma component-dependent while the induction of cathepsin K-positive multinucleated giant cells was influenced by the microstructure of hydroxyapatite. This is the first study to show the conditions dividing the three kinds of multinucleated giant cells in the foreign body reaction., (Copyright © 2016 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

The implantation of biomaterials induces a granulomatous reaction accompanied by foreign body giant cells (FBGCs). The characterization of multinucleated giant cells (MNGCs) around bone substitutes implanted in bone defects is more complicated because of healing with bone admixed with residual bone substitutes and their hybrid, and the appearance of two kinds of MNGCs, osteoclasts and FBGCs. Furthermore, the clinical significance of osteoclasts and FBGCs in the healing of implanted regions remains unclear. The aim of the present study was to characterize MNGCs around bone substitutes using an extraskeletal implantation model and evaluate the clinical significance of osteoclasts and FBGCs. Beta-tricalcium phosphate (β-TCP) granules were implanted into rat subcutaneous tissue with or without bone marrow mesenchymal cells (BMMCs), which include osteogenic progenitor cells. We also compared the biological significance of plasma and purified fibrin, which were used as binders for implants. Twelve weeks after implantation, osteogenesis was only detected in specimens implanted with BMMCs. The expression of two typical osteoclast markers, tartrate-resistant acid phosphatase (TRAP) and cathepsin-K (CTSK), was analyzed, and TRAP-positive and CTSK-positive osteoclasts were only detected beside bone. In contrast, most of the MNGCs in specimens without the implantation of BMMCs were FBGCs that were negative for TRAP, whereas the degradation of β-TCP was detected. In the region implanted with β-TCP granules with plasma, FBGCs tested positive for CTSK, and when β-TCP granules were implanted with purified fibrin, FBGCs tested negative for CTSK. These results showed that osteogenesis was essential to osteoclastogenesis, two kinds of FBGCs, CTSK-positive and CTSK-negative, were induced, and the expression of CTSK was plasma-dependent. In addition, the implantation of BMMCs was suggested to contribute to osteogenesis and the replacement of implanted β-TCP granules to bone.

Spherical porous granules of hydroxyapatite (HA) containing magnetic nanoparticles would be suitable for the hyperthermia treatment of bone tumor, because porous HA granules act as a scaffold for bone regeneration, and magnetic nanoparticles generate sufficient heat to kill tumor cells under an alternating magnetic field. Although magnetic nanoparticles are promising heat generators, their small size makes them difficult to support in porous HA ceramics. We prepared micrometer-sized composites of magnetic and HA nanoparticles, and then supported them in porous HA granules composed of rod-like particles. The spherical porous HA granules containing the composites of magnetic and HA nanoparticle were successfully prepared using a hydrothermal process without changing the crystalline phase and heat generation properties of the magnetic nanoparticles. The obtained granules generated sufficient heat for killing tumor cells under an alternating magnetic field (300 Oe at 100 kHz). The obtained granules are expected to be useful for the hyperthermia treatment of bone tumors.

In addition to calcium phosphate-based ceramics, glass-based materials have been utilized as bone substitutes, and silicate in these materials has been suggested to contribute to their ability to stimulate bone repair. In this study, a silicate-containing α-tricalcium phosphate (α-TCP) ceramic was prepared using a wet chemical process. Porous granules composed of silicate-containing α-TCP, for which the starting composition had a molar ratio of 0.05 for Si/(P + Si), and silicate-free α-TCP were prepared and evaluated in vivo. When implanted into bone defects that were created in rat femurs, α-TCP ceramics either with or without silicate were biodegraded, generating a hybrid tissue composed of residual ceramic granules and newly formed bone, which had a tissue architecture similar to physiological trabecular structures, and aided regeneration of the bone defects. Supplementation with silicate significantly promoted osteogenesis and delayed biodegradation of α-TCP. These results suggest that silicate-containing α-TCP is advantageous for initial skeletal fixation and wound regeneration in bone repair.

Optimum design of support materials for microorganisms is required for the construction of bioreactors. However, the effects of support materials on microorganisms are still unclear. In this study, we investigated the adhesion behavior of Escherichia coli (E. coli) on hydroxyapatite (HA), polyurethane (PU), poly(vinyl chloride) (PVC), and carbon (Carbon) to obtain basic knowledge for the design of support materials. The total metabolic activity and number of E. coli adhering on the samples followed the order of HA ≈ Carbon>PVC>PU. On the other hand, the water contact angle of the pellet surfaces followed the order of HA

Octacalcium phosphate (OCP) is composed of apatitic and hydrated layers, and can incorporate dicarboxylate ions in its hydrated layers by substitution of HPO4(2-). The (100) interplanar spacing of OCP is increased by incorporation of dicarboxylate ions. Herein, we report continuous expansion of the interplanar spacing of OCP by incorporation of dicarboxylate ions with a side chain. We synthesized OCP with incorporated succinic acid (Suc) and mercaptosuccinic acid (Msuc) by a wet chemical process. The (100) interplanar spacing of OCP synthesized with Suc increased non-continuously as the amount of Suc used in the synthesis increased. In contrast, the (100) interplanar spacing of OCP synthesized with Msuc increased continuously with the amount of Msuc used during synthesis, and thus in the OCP. The values of the (100) interplanar spacing of OCP synthesized with Msuc first increased and then became constant as the amount of Msuc increased. OCP with incorporated Msuc formed a continuous solid solution. The expansion of the (100) interplanar spacing of OCP with incorporated Suc and Msuc depended on the chemical structure of the incorporated dicarboxylate ions. The only structural difference between Suc and Msuc is a mercapto (R-SH) side chain. Therefore, continuous solid solution formation was most likely induced by the R-SH side chain of Msuc. These results suggest that incorporation of dicarboxylic acids with a side chain is one approach to obtain OCP with arbitrary interlayer distance.

Octacalcium phosphate (OCP) is regarded as an in vivo precursor of hydroxyapatite (HA). It is important to understand the mechanism of transformation of OCP to HA in order to reveal the mechanism of mineralization and help in the development of artificial bone-repairing materials. Herein, we have examined the behavior of OCP in a simulated body fluid (SBF) and pure water. The OCP particles immersed in the SBF at 37 °C did not transform to HA even after 720 h of immersion, though the particles showed crystal growth. In distilled water at 60 °C, the OCP particles transformed to HA but the unreactive period was observed. Although the immersed solution became supersaturated with HA within 12h of immersion, the OCP was not transformed in the first 36 h of immersion. These results indicate that the nucleation of HA is the rate-determining step in the transformation of OCP to HA., (Copyright © 2014 Elsevier B.V. All rights reserved.)

We compared the healing of bone defects in ovariectomized rats implanted with beta-tricalcium phosphate (b-TCP)composed of rod-shaped particles, which were prepared using the applied hydrothermal method (HTCP), and that of bone defects implanted with conventional b-TCP composed of globular-shaped particles (CTCP), which were prepared by normal sintering. Eight week-old female Wistar rats were ovariectomized, and 2 weeks after the operation, 0.5- to 0.6-mm diameter spherical granules of each ceramic were implanted in a bone defect created in the distal end of the femur. Four, 8, and 12 weeks after implantation, the amount of newly formed bone implanted with HTCP was significantly larger than that implanted with CTCP and was equivalent to that in non-ovariectomized sham-operated rats. Without implantation, spontaneous repair of the trabecular bone was barely observed. The physiological structure of the trabecular network was maintained in the region implanted with HTCP, but that in the region implanted with CTCP was severely destroyed. Gene expression microarray analysis revealed that the expression of genes involved in interferon signaling pathways was upregulated in osteoclasts cultured on HTCP compared with that cultured on CTCP. Our results suggest that the microstructure of b-TCP affected the biological behavior of osteoclasts and regulated local bone metabolism., (© 2013 Orthopaedic Research Society. Published by Wiley Periodicals, Inc.)

In designing the biomaterials, it is important to control their surface morphologies, because they affect the interactions between the materials and cells. We previously reported that porous calcium-deficient hydroxyapatite (HA) ceramics composed of rod-like particles had advantages over sintered porous HA ceramics; however, the effects of the surface morphology of calcium-deficient HA ceramics on cell behavior have remained unclear. Using a hydrothermal process, we successfully prepared porous calcium-deficient HA ceramics with different surface morphologies, composed of plate-like particles of 200-300, 500-800 nm, or 2-3 μm in width and rod-like particles of 1 or 3-5 μm in width, respectively. The effects of these surface morphologies on the behavior of osteoblast-like cells were examined. Although the numbers of cells adhered to the ceramic specimens did not differ significantly among the specimens, the proliferation rates of cells on the ceramics decreased with decreasing particle size. Our results reveal that controlling the surface morphology that is governed by particle shape and size is important for designing porous calcium-deficient HA ceramics.

The biological activity of osteoblasts and osteoclasts is regulated not only by hormones but also by local growth factors, which are expressed in neighbouring cells or included in bone matrix. Previously, we developed hydroxyapatite (HA) composed of rod-shaped particles using applied hydrothermal methods (HHA), and it revealed mild biodegradability and potent osteoclast homing activity. Here, we compared serum proteins adsorbed to HHA with those adsorbed to conventional HA composed of globular-shaped particles (CHA). The two ceramics adsorbed serum albumin and γ-globulin to similar extents, but affinity for γ-globulin was much greater than that to serum albumin. The chemotactic activity for macrophages of serum proteins adsorbed to HHA was significantly higher than that of serum proteins adsorbed to CHA. Quantitative proteomic analysis of adsorbed serum proteins revealed preferential binding of vitamin D-binding protein (DBP) and complements C3 and C4B with HHA. When implanted with the femur of 8-week-old rats, HHA contained significantly larger amount of DBP than CHA. The biological activity of DBP was analysed and it was found that the chemotactic activity for macrophages was weak. However, DBP-macrophage activating factor, which is generated by the digestion of sugar chains of DBP, stimulated osteoclastogenesis. These results confirm that the microstructure of hydroxyapatite largely affects the affinity for serum proteins, and suggest that DBP preferentially adsorbed to HA composed of rod-shaped particles influences its potent osteoclast homing activity and local bone metabolism., (© 2013 The Authors. Journal of Cellular and Molecular Medicine published by John Wiley & Sons Ltd and Foundation for Cellular and Molecular Medicine.)

Spherical Ca-deficient hydroxyapatite (HA) granules are expected to be useful drug carriers in bony sites because of their bone regeneration and adsorption ability. In order to control drug loading and release ability of the granules, a controlled surface microstructure was constructed. Spherical Ca-deficient granules composed of micron-sized rod-shaped particles were prepared by hydrothermal treatment of α-tricalcium phosphate (α-TCP) granules, and then, submicron HA particles were precipitated on the obtained granules by immersion in a supersaturated calcium phosphate (CP) solution. When bovine serum albumin was used as a drug model, precipitation of submicron particles causes the loading capability to increase and the release rate to decrease. The spherical Ca-deficient HA granules with the controlled surface microstructure are expected to be useful drug carriers that can act as scaffolds for bone repair., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The aim of this study was to evaluate the influence of mechanical unloading on the repair of bone defects with implantation of biodegradable bone substitutes. Spherical granules of biodegradable hydroxyapatite composed of rod-shaped particles (RHA) or beta-tricalcium phosphate composed of rod-shaped particles (RTCP) were implanted into a bone defect created in the distal end of the right femur of 8-week-old Wistar rats. Two, 6, 10, and 22 weeks after implantation, part of the sciatic nerve in the thigh was resected and exposed to mechanical unloading for 2 weeks. Then, 4, 8, 12 and 24 weeks after implantation, repair of the bone defect was analyzed. As a control, the bone defect without implantation of ceramic granules was also analyzed. Both RHA and RTCP tended to be reduced, but the reduction was not obvious during the experimental period. At 12 and 24 weeks after implantation, the amount of newly formed bone in the animal implanted with RHA was significantly greater than that at 4 weeks after implantation, but that in the animal implanted with RTCP or without implantation was not significantly different. The number of osteoclasts in the region implanted with RHA was significantly larger than that of the region implanted with RTCP or without implantation at 12 and 24 weeks. The activities of alkaline phosphatase in osteoblasts and tartrate-resistant acid phosphatase in osteoclasts were remarkably increased in the bone defects with implantation compared with those in the bone defects without implantation. These results suggested that RHA stimulated osteogenesis and osteoclastogenesis even after 2 weeks of mechanical unloading, and that RHA could be expected to improve the repair of bone defects in patients under the condition of skeletal unloading.

Nanosized porous hydroxyapatite (HA) granules are expected to be useful as DNA and drug carriers for cells. We attempted to synthesize nanosized HA granules in an agarose gel by electrophoresis of calcium and phosphate ions. Wells were prepared on an agarose gel, and a CaCl(2) solution was placed in the wells on the positive side and a Na(2)HPO(4) solution was placed in the wells on the negative side. After a potential was applied, white precipitates appeared in the gel. The precipitates were calcium-deficient HA granules of approximately 300-600 nm in diameter. These granules were composed of fiber-like particles and had a porous structure. The diameters of the granules were decreased by an increase in the gel concentration. Hence, we successfully synthesized nanosized porous HA granules to be used as DNA and drug carriers., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Octacalcium phosphates (OCPs) co-incorporated with various molar ratios of succinate and suberate ions were synthesized by wet processing. The interplanar spacings of the (100) planes (d(100)) of OCPs formed in the presence of succinic acid (Suc) or suberic acid (Sub) were larger than those of OCPs formed without addition of a dicarboxylic acid to the reaction solvent. The increases in the interplanar spacings of the (100) planes were caused by substitution of HPO(4)(2-) by dicarboxylate ions. The OCPs with co-incorporated succinate and suberate ions, i.e. solid solutions of OCP with incorporated Suc and Sub, were formed by reactions in the presence of Suc and Sub. When the Suc/(Suc + Sub) values in the starting compositions were in the range 0.45-1.0, Suc was preferentially incorporated into the OCP. In contrast, when the Sub/(Suc + Sub) values in the starting compositions were in the range 0.60-1.0, Sub was preferentially incorporated into the OCP crystals.

Preparation of colloidal hydroxyapatite (HAp) particles under body fluid conditions was investigated with focusing on the effect of preparative conditions on crystallinity of the resulting particles. Tris(hydroxymethyl)aminomethane was added to 1.5SBF (a solution having 1.5 times higher ion concentrations than those of a simulated body fluid, SBF) to increase the solution pH, which resulted in induction of homogeneous nucleation of HAp in the solution. Colloidal HAp particles having diameters about 300 nm were obtained. When the reaction was proceeded at 70°C and the sample was dried by heating, it was effective to obtain HAp particles having high crystallinity. Experimental results support that remaining water in the sample contributed to increase HAp crystallinity., (Copyright © 2011 Elsevier B.V. All rights reserved.)

A polymeric percutaneous device with good biocompatibility and resistance to bacterial infection is required clinically. In this study, a fibroblast growth factor-2 (FGF-2)-hydroxyapatite (HAp) composite layer (FHAp layer) was formed on the surfaces of ethylene-vinyl alcohol copolymer (EVOH) specimens using a coating process in a supersaturated calcium phosphate solution supplemented with FGF-2. FGF-2 in the FHAp layer retained its biological activity to promote proliferation of fibroblasts. The EVOH specimens coated with HAp and FHAp layers were percutaneously implanted in the scalp of rats. Not only the HAp layer but also the FHAp layer showed good biocompatibility, and FGF-2 showed no harmful effects on the skin tissue responses to the implanted specimen as long as 14 d. No significantly higher infection resistance was verified for the FHAp layer over the HAp layer, although an FHAp layer coated on a metallic percutaneous device for bone fixation demonstrated higher resistance to bacterial infection over an HAp layer in the previous study. The efficacy of FHAp layers coated on percutaneous implants in resistance to bacterial infection depends on physical factors including fixation condition, stiffness and movement of implants.

Alpha-tricalcium phosphate (alpha-TCP) ceramic is a bioresorbable material that degrades in bone tissue after implantation, since it exhibits higher solubility than beta-tricalcium phosphate (beta-TCP) ceramics. The high solubility of alpha-TCP in an aqueous solution causes its transformation into hydroxyapatite (HAp) through hydrolysis. While one expects the formation of hydroxyapatite after exposure to an aqueous solution mimicking a body environment, we occasionally find variation in HAp formation in the simulated body fluid (SBF). In the present study, HAp formation resulting from exposure to SBF was investigated for some types of alpha-TCP ceramics with different porosities and specific surface area. Reduced porosity and large surface area of porous specimens may increase the local density of Ca2+ in the surrounding SBF to increase the degree of supersaturation with respect to HAp. Thus, the porosity and specific surface area are significant parameters for determining not only bioabsorbability but also the ability to form HAp.

The osteoconduction potential of artificial materials is usually evaluated in vitro by apatite formation in a simulated body fluid (SBF) proposed by Kokubo and his colleagues. This paper reports the compositional dependence of apatite formation on organic-inorganic hybrids in the CaO-SiO(2)-PO(5/2)-poly(tetramethylene oxide) system, initiated from tetraethoxysilane (TEOS), triethyl phosphate (OP(OEt)(3)), calcium chloride (CaCl(2)) and poly(tetramethylene oxide)(PTMO) modified with alkoxysilane. Formation of an apatite layer was observed on the surface of the organic-inorganic hybrids with molar ratios of TEOS/OP(OEt)(3) ranging from 100/0 to 20/80. The rate of apatite formation remarkably decreased when the hybrids were synthesized with TEOS/OP(OEt)(3) ratios of 40/60 or less. Hybrids without TEOS showed no apatite formation in SBF for up to 14 days. Addition of small amounts of OP(OEt)(3) to TEOS in the hybrids led to the high dissolution of calcium and silicate, while addition of large amounts of OP(OEt)(3) decreased the dissolution of calcium and silicate ions and resulted in reduced apatite formation regardless of the dissolution of phosphate ions from the hybrids.

Biomimetic mineralization of supramolecular scaffolds consisting of biomolecules or their analogues has received much attention recently from the viewpoint of creation of novel biomaterials. This study investigated biomimetic deposition of hydroxyapatite (HAp) on cerasomes, morphologically stable organic-inorganic hybrid vesicles. Scanning electron microscopy, energy-dispersive X-ray spectroscopy, and X-ray diffraction studies revealed that the pristine cerasomes induced heterogeneous nucleation of HAp when they were immersed in 1.5SBF, a solution having 1.5 times higher ion concentration than that of a simulated body fluid (SBF). The HAp deposition was further accelerated when dicarboxylic and monocarboxylic acid groups were displayed on cerasome surfaces. These carboxylic acid groups are expected to enhance calcium ion binding to the cerasome surface, causing an increase of HAp nucleation sites. At lower surface concentrations on the cerasome surface, the dicarboxylic acid group is apparently more effective for HAp deposition than the monocarboxylic acid group. The resultant HAp-cerasome hybrids are useful as biocompatible materials having unique properties deriving from the lipid bilayer structure of the cerasomes.

A simulated body fluid (SBF) with ion concentrations similar to body fluid, proposed by Kokubo et al., is widely used to evaluate bone-bonding potential through the formation of an apatite layer. To be confident of the evaluation of the potential for the apatite formation in SBF, standard substrates are required. Although Na(2)O-CaO-SiO(2) glasses have been focused upon as candidate standard substrates, it has not been clarified whether the preparation conditions of the glasses affect their apatite formation potential in SBF. In this study, Na(2)O-CaO-SiO(2) glasses were prepared by a conventional melting-quenching method with different melting periods and annealing processes to examine their properties, including apatite formation in SBF. The Na(2)O-CaO-SiO(2) glasses show reproducible apatite-forming ability when prepared using moderate melting and annealing processes, and can be useful substrates to test the reproducibility of SBF.

Calcium-deficient hydroxyapatite (HA) granules with a unique spherical shape were prepared using an applied hydrothermal method. Spherical stoichiometric HA granules were also prepared by normal sintering and both granules were used for implantation into rat tibiae to compare the biological responses to each implant. Twelve and 24 weeks after implantation, the volume of calcium-deficient HA granules was significantly less than that of stoichiometric HA granules, and the biodegradability of calcium-deficient HA granules was confirmed. The larger number of osteoclasts, larger osteoblast surface and larger bone volume in the implanted area of calcium-deficient HA than those of stoichiometric HA suggested that osteoclastic resorption of calcium-deficient HA affected osteogenesis in that area. To analyze the direct contribution of osteoclasts to osteogenesis, C2C12 multipotent myoblastic cells, which have the potential to differentiate into osteoblasts in the presence of bone morphogenetic protein 2, were cultured with supernatants of osteoclasts cultured on calcium-deficient HA, stoichiometric HA, beta-tricalcium phosphate disks or plastic dishes, or bone marrow macrophages cultured on plastic dishes. Supernatants of osteoclasts but not bone marrow macrophages stimulated the expression of Runx2 and osteocalcin in C2C12 cells in concert with bone morphogenetic protein 2. The expression of alkaline phosphatase was stimulated with supernatants of osteoclasts cultured on ceramic disks. These results suggested that osteoclasts produced certain soluble factors which stimulated osteoblastic differentiation and they were thought to be associated with the induction of a larger osteoblast surface and bone volume in the animals implanted with calcium-deficient HA granules.

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.

We investigated synthetic conditions for the fabrication of bioactive hybrid gels from monomers of 2-hydroxyethylmethacrylate (HEMA) and 3-methacryloxypropyltrimethoxysilane (MPS) in combination with CaCl(2), at a starting molar ratio of HEMA: MPS : CaCl(2) of 9 : 1 : 1. Hydroxyapatite formation, essential to show bone bonding, was observed on the HEMA- MPS-CaCl( 2) hybrid gels with the added catalysts NH(3) or HCl with a molar ratio to MPS of 0.1, but not on the hybrid gel with HCl at a molar ratio to MPS of 1. The mechanical properties of the gels were dependent on the catalysts, which may affect the microstructures that develop during sol-gel processing.

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 beta-TCP and alpha-TCP.

A newly developed calcium-deficient hydroxyapatite composed of rod-shaped particles synthesized by the hydrothermal method (HHA) and stoichiometric hydroxyapatite (SHA) synthesized by the sintering method was used for in vivo implantation and in vitro culture systems to compare these biological responses. In the rabbit femur, implanted HHA was slowly resorbed and about 80% of the implant remained 24 weeks after implantation; however, up to 72 weeks after implantation, most of the implanted HHA was resorbed. The implanted SHA was unresorbed throughout the experimental period, but degradation by the invasion of newly formed bone was seen at 72 weeks after implantation. Bone histomorphometry showed that the volume of newly formed bone and the number of osteoclasts in the implanted region were significantly higher in HHA than in SHA 24 weeks after implantation. In vitro culture of C2C12 cells with the induction of osteoblastic phenotypes using recombinant bone morphogenetic protein-2 showed similar cell density and the induction of alkaline phosphatase activity between the cells on HHA and SHA discs. In vitro osteoclastogenesis of HHA and SHA discs using bone marrow macrophages and recombinant receptor activator of nuclear factor-kappaB ligand showed higher TRAP activity of osteoclasts cultured on HHA discs. These results showed that slow biodegradability did not always correlate to final replaceability in bone tissue, and suggested that the activity of osteoclasts correlated to the bone-forming activity of osteoblasts.

Collagens are widely used in medical applications, but animal-derived collagens have several drawbacks, such as low thermal stability, nonspecific cell attachment, and susceptibility to contamination by infectious pathogens, such as prions, which may transfect humans. We have previously reported the chemical synthesis of polypeptides consisting of a Pro-Hyp-Gly sequence and the high thermostability of their triple-helical structure. To clarify the biomaterial characteristics of the poly(Pro-Hyp-Gly) polypeptide, we assessed its biodegradability and its capability for skin regeneration. Eight weeks after implantation, a poly(Pro-Hyp-Gly) freeze-dried sponge embedded subcutaneously into a rat dorsal area degraded at the same rate as Terudermis, which is made from bovine type I atelocollagen and is used as an artificial dermis. Surprisingly, compared with Terudermis, the poly(Pro-Hyp-Gly) sponge significantly promoted epithelialization of a full-thickness wound on a rabbit's ear pad. This chemically synthesized polypeptide may be useful as a scaffold for tissue engineering and tissue regeneration., (Copyright 2007 Wiley Periodicals, Inc.)

Deposition of a hydroxyapatite layer with similar structure to bone mineral is an attractive approach to the fabrication of bioactive coating layers to achieve direct bonding to living bone. To get successful coating of a hydroxyapatite layer on an organic polymer using a biomimetic solution, it is essential to find organic substrates that can effectively induce heterogeneous nucleation of hydroxyapatite after exposure to the body environment. Our previous study showed that sericin, a type of silk protein, has the ability to induce hydroxyapatite nucleation in a biomimetic solution when the sericin has a beta sheet structure. To confirm the effectiveness of the beta sheet structure in hydroxyapatite nucleation, we focused on investigating hydroxyapatite deposition on a synthetic polypeptide with a beta sheet structure in a biomimetic solution. The beta sheet forming polypeptides with and without carboxyl groups, poly(FE)(3)FG, poly(FQ)(3)FG, poly(LE)(3)LG and poly(LQ)(3)LG, were synthesized in this study. All the polypeptides had mainly beta sheet structure. After soaking the polypeptide films in 1.5SBF, which has 1.5 times the inorganic ion concentrations of human blood plasma, hydroxyapatite formed on the surfaces of the polypeptides with carboxyl groups, poly(FE)(3)FG and poly(LE)(3)LG, within 2 days, but not on those without carboxyl groups, poly(FQ)(3)FG and poly(LQ)(3)LG. We confirmed that the beta sheet structure was effective for hydroxyapatite nucleation even in the synthetic polypeptide. This finding is useful for the future design of organic polymers that can effectively induce nucleation of hydroxyapatite.

Materials with bioactivity, i.e. bone-bonding ability, form a bone-like apatite layer on their surfaces in the body and bond to living bone through this bone-like apatite layer. Bone-like apatite is carbonated hydroxyapatite with small crystallites and low crystallinity. The coating of the bone-like apatite layer on the substrates is expected to be a useful technique to induce bioactivity on the substrates. The bone-like apatite layer can be formed on the surface of substrates in a solution mimicking body fluid when some functional groups are introduced to the substrates. This process is called a biomimetic process. Coating of bone-like apatite layers through this biomimetic process has received much attention in the fabrication of novel composites with bioactivity. An overview of the coating of bone-like apatite is described.

An optical oxygen-sensing activity of anchored porphyrin derivatives on ordered porous aluminium oxide plates was studied in relevance to development of new oxygen-sensing systems. Porphyrin derivatives, 5,10,15,20-tetrakis(4-carboxylundecane-1-oxy)porphyrin, 5-[4-(11-carboxylundecane-1-oxy)-10,15,20-triphenyl]porphyrin, 5-(4-carboxylphenyl)-10,15,20-triphenylporphyrin, and their platinum complexes, 5,10,15,20-tetrakis(4-carboxylundecane-1-oxy)porphyrinatoplatinum(II), 5-[4-(11-carboxylundecane-1-oxy)-10,15,20-triphenyl]porphyrinatoplatinum(II), 5-(4-carboxylphenyl)-10,15,20-triphenylporphyrinatoplatinum(II), were synthesized and anchored by an equilibrium adsorption method on aluminium oxide plates, which were prepared by an anodic oxidation. The excitation spectra of the porphyrin-anchored layers showed a broadened and blue-shifted Soret band compared with the corresponding porphyrins in DMSO. The luminescence intensity decreased with increasing oxygen concentrations. The oxygen-sensing ability estimated from I(0)/I(100) (I(0) and I(100) denote the luminescence intensity in 0 and 100% oxygen) was 9.08, 6.78, 8.71, 81.9, 35.5, and 39.1, which are greater than those of corresponding porphyrin derivatives in DMSO under the measured conditions, and indicates the remarkable enhancement effect of platinum(II). Non-linear Stern-Volmer plots were well fitted by the two component system to give the oxygen-sensitive constant (K(SV1)/%(-1)), the oxygen-insensitive constant (K(SV2)/%(-1)), and the former contribution (f(1)): 0.232, 3.32 x 10(-2), and 0.642; 0.141, 2.05 x 10(-2), and 0.687; 0.143, 1.05 x 10(-2), and 0.882; 17.3, 7.04 x 10(-3), and 0.980; 10.2, 1.43 x 10(-2), and 0.935; 16.3, 8.35 x 10(-3), and 0.954. The response time for the change of the atmospheric gas from argon to oxygen was 9.4 s, 12.5 s, 9.6 s, 5.0 s, 8.9 s, and 4.6 s, indicating the shortening effect of platinum. The reverse effect of platinum was observed in the change from oxygen to argon: 15.5 s, 17.0 s, 20.8 s, 667.4 s, 590.1 s, and 580.4 s, indicating the specific interaction of oxygen to the platinum(II) center.

Modification of organic polymer with silanol groups in combination with calcium salts enables the polymer to show bioactivity, that is, the polymer forms apatite on its surface after exposure to body environment. However, how modification with silanol groups influences ability of apatite formation on the polymer substrate and adhesive strength between polymer and apatite is not yet known. In the present study, polyamide containing carboxyl groups was modified with different amounts of silanol groups, and its apatite-forming ability in 1.5SBF, which contained ion concentrations 1.5 times those of simulated body fluid (SBF), was examined. The rate of apatite formation increased with increasing content of silanol groups in the polyamide films. This may be attributed to enhancement of dipole interactions. A tendency for the adhesive strength of the apatite layer on the polyamide film to be decreased with increasing content of silanol groups was observed. This may be attributed to swelling in 1.5SBF and having a high degree of shrinkage after drying. These findings clearly show that modification of organic polymers with the functional groups induces apatite deposition, and also determines the adhesive strength of the apatite layer to the organic substrates.

Poly(tetramethylene oxide) (PTMO)-CaO-Ta2O5 hybrids were prepared by hydrolysis and polycondensation of triethoxysilane-functionalized PTMO (Si-PTMO), tantalum ethoxide (Ta(OEt)5) and CaCl2. In the system CaO-free PTMO-Ta2O5, Si-PTMO/Ta(OEt)5 weight ratios were 30/70, 40/60 and 50/50 (hybrids PT30Ca0, PT40Ca0 and PT50Ca0, respectively). In the system PTMO-CaO-Ta2O5, the Si-PTMO/Ta(OEt)5 weight ratio was 40/60 and CaCl2/Ta(OEt)5 mole ratios were 0.05, 0.10 and 0.15 (hybrids PT40Ca5, PT40Ca10 and PT40Ca15, respectively). Crack-free transparent monolithic hybrids were obtained for all the examined compositions except for PT30Ca0. Even CaO-free hybrids PT40Ca0 and PT50Ca0 formed apatite on their surfaces in a simulated body fluid (SBF) within 14 days. Hybrid PT40Ca0 showed higher mechanical strength, which was increased by soaking in SBF, and larger strain to failure than human cancellous bone. The CaO-containing hybrids showed higher apatite-forming ability than the CaO-free hybrids, and its apatite-forming ability increased with increasing CaO content. Hybrids PT40Ca10 and PT40Ca15 formed apatite within 3 days. The mechanical strength of PT40Ca15 was, however, lower than PT40Ca0 and was decreased by soaking in SBF. Thus obtained flexible bioactive CaO-free PTMO-Ta2O5 hybrids are expected to be useful as bone substitutes.

Bone-like apatite is a carbonated hydroxyapatite with a small crystallite and low crystallinity. The formation of a layer consisting of bone-like apatite is an essential condition for bioactive materials to achieve direct bonding with living bone. A bone-like apatite layer can be formed on the surface of organic substrates in a solution mimicking a body fluid when some functional groups are introduced to organic substrates. This process is a biomimetic process because a simulated body fluid and related solutions are used to deposit bone-like apatite crystals and promote crystal growth. Coating of bone-like apatite layers through biomimetic processes has received much attention in the fabrication of novel composites with bone-bonding properties, i.e. bioactivity, and mechanical properties analogous to those of living bone tissues. This paper reviews recent developments in coating with bone-like apatite layers using biomimetic processes., (2007 John Wiley & Sons, Ltd)

Some harmful volatile organic compounds (VOCs), such as formaldehyde, are regulated atmospheric pollutants. Therefore, development of a material to remove these VOCs is required. We focused on hydroxyapatite, which had been biomimetically coated on a polyamide film, as an adsorbent and found that formaldehyde was successfully removed by this adsorbent. The amount of formaldehyde adsorbed increased with the area of the polyamide film occupied by hydroxyapatite. The amount of adsorbed formaldehyde and its rate of adsorption were larger for hydroxyapatite deposited on polyamide film than for the commercially available calcined hydroxyapatite powder. This high adsorption ability is achieved by the use of nanosized particles of hydroxyapatite with low crystallinity and containing a large number of active surface sites. Therefore, hydroxyapatite biomimetically coated on organic substrates can become a candidate material for removing harmful VOCs such as formaldehyde.