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記述言語：英語   出版者・発行元：Elsevier Inc.  

Objectives: Although the functional monomer glycero-phosphate dimethacrylate (GPDM) has since long been used in several dental adhesives and more recently in self-adhesive composite cements and restoratives, its mechanism of chemical adhesion to hydroxyapatite (HAp) is still unknown. We therefore investigated the chemical interaction of GPDM with HAp using diverse chemical analyzers and ultra-structurally characterized the interface of a GPDM-based primer formulation with dentin. Methods: HAp particles were added to a GPDM solution for various periods, upon which they were thoroughly washed with ethanol and water prior to being air-dried. As control, 10-methacryloyloxydecyl dihydrogen phosphate (MDP) was used. The molecular interaction of GPDM with HAp was analyzed using X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (NMR) spectroscopy. Crystal formation upon application of GPDM onto dentin was analyzed using thin-film XRD (TF-XRD). Its hydrophobicity was measured using contact-angle measurement. The interaction of GPDM with dentin was characterized using transmission electron microscopy (TEM). Results: XRD revealed the deposition of dicalcium phosphate dihydrate (DCPD: CaHPO4·2H2O) on HAp after 24 h. NMR confirmed the adsorption of GPDM onto HAp. However, GPDM was easily removed after washing with water, unlike MDP that remained adhered to HAp. Dentin treated with GPDM appeared more hydrophilic compared to dentin treated with MDP. TEM disclosed exposed collagen in the hybrid layer produced by the GPDM-based primer formulation. Significance: Although GPDM adsorbed to HAp, it did not form a stable calcium salt. The bond between GPDM and HAp was weak, unlike the strong bond formed by MDP to HAp. Due to its high hydrophilicity, GPDM might be an adequate monomer for an etch-and-rinse adhesive, but appears less appropriate for a ‘mild’ self-etch adhesive that besides micro-retention ionically interacts with HAp, or for a self-adhesive restorative material.

DOI： 10.1016/j.dental.2018.04.003

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© 2017 Elsevier B.V. Chitosan microspheres can address challenges associated with poor bioavailability or unsustained drug release when used as drug delivery systems thanks to their mucoadhesiveness, which allows the drug dosage to be retained in the gastrointestinal track for extended periods. Chitosan-3-glycidoxypropyltrimethoxysilane-β-glycerophosphate (chitosan-GPTMS-β-GP) hybrid microspheres were synthetized through sol-gel processing using a microfluidic approach. Microspheres with uniform spherical shapes and sizes of approximately 650 μm were obtained. The microstructures of the microspheres consisted of four different siloxane structures. The degradation behaviors of the hybrid microspheres were examined under acidic pH conditions mimicking those found in the gastrointestinal track. Microspheres with different GPTMS molar ratios were incubated under several pH conditions for 2 weeks. The microspheres incubated at pH 7.4 extended the lowest weight loss (27%–32%), whereas those incubated at pH 1.7 and pH 5.4 showed greater weight losses of 43–59% and 69–77%, respectively. The inhibition of the degradation at low pH was dependent on the siloxane network in the chitosan matrix. Phosphate was mostly released in early stages, and the released amount of silicon was dependent on the composition. GPTMS was released with a chitosan chain via the hydrolysis of a chitosan molecule. The pelargonidin was incorporated in the microspheres and the slow releasing was observed at acidic condition. The resistance of these hybrid microspheres to low-pH conditions for longer than a full digestion cycle is promising for gastrointestinal drug delivery applications.

DOI： 10.1016/j.msec.2017.08.035

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Autograft has been carried out for anterior cruciate ligament (ACL) reconstruction surgery. However, it has negative aspect because patients lose their healthy ligaments from other part. We focus on a chitosan-hydroxyapatite (HAp) composite fiber as a scaffold of ligament regeneration. Chitosan- HAp composite fiber was made by using coagulation method. Chitosan-NaH2PO4 solution was coagulated with coagulation bath including calcium ion to get the mono-fiber and then treated with sodium hydroxide solution to form HAp in fiber matrix. The mechanical property of the fiber was improved by the stretching of the wet one because of the orientation of chitosan molecule and the interaction between chitosan and HAp. Maximum stress was improved with increasing of sodium dihydrogen phosphate until 0.03 M. The swelling ratio of the fiber was inhibited by composited with HAp. Additionally, bone-bonding ability was confirmed by SBF soaking tests. (C) 2017 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.carbpol.2017.07.072

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

We demonstrate that NMR/DNP (Dynamic Nuclear Polarization) allows an unprecedented description of carbonate substituted hydroxyapatite (CHAp). Key structural questions related to order/disorder and clustering of carbonates are tackled using distance sensitive DNP experiments using C-13-C-13 recoupling. Such experiments are easily implemented due to unprecedented DNP gain (orders of magnitude). DNP is efficiently mediated by quasi one-dimensional spin diffusion through the hydroxyl columns present in the CHAp structure (thought of as "highways" for spin diffusion). For spherical nanoparticles and phi < 100 nm, it is numerically shown that spin diffusion allows their study as a whole. Most importantly, we demonstrate also that the DNP study at 100 K leads to data which are comparable to data obtained at room temperature (in terms of spin dynamics and line shape resolution). Finally, all 2D DNP experiments can be interpreted in terms of domains exhibiting well identified types of substitution: local order and carbonate clustering are clearly favored.

DOI： 10.1021/acs.analchem.7b01332

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記述言語：英語   出版者・発行元：NATURE PUBLISHING GROUP  

Currently, the functional monomer 10-methacryloyloxy-decyl-dihydrogen-phosphate (10-MDP) was documented to chemically bond to zirconia ceramics. However, little research has been conducted to unravel the underlying mechanisms. This study aimed to assess the chemical interaction and to demonstrate the mechanisms of coordination between 10-MDP and zirconium oxide using H-1 and P-31 magic angle spinning (MAS) nuclear magnetic resonance (NMR) and two dimensional (2D) H-1 -> P-31 heteronuclear correlation (HETCOR) NMR. In addition, shear bond-strength (SBS) tests were conducted to determine the effect of 10-MDP concentration on the bonding effectiveness to zirconia. These SBS tests revealed a 10-MDP concentration-dependent SBS with a minimum of 1-ppb 10-MDP needed. P-31-NMR revealed that one P-OH non-deprotonated of the PO3H2 group from 10-MDP chemically bonded strongly to zirconia. H-1-P-31 HETCOR NMR indicated that the 10-MDP monomer can be adsorbed onto the zirconia particles by hydrogen bonding between the P=O and Zr-OH groups or via ionic interactions between partially positive Zr and deprotonated 10-MDP (P-O-). The combination of H-1 NMR and 2D H-1-P-31 HETCOR NMR enabled to describe the different chemical states of the 10-MDP bonds with zirconia; they not only revealed ionic but also hydrogen bonding between 10-MDP and zirconia.

DOI： 10.1038/srep45563

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

One prominent cause of implant failure is infection; therefore, research is focusing on developing surface coatings that render the surface resistant to colonization by micro-organisms. Permanently attached coatings of antimicrobial molecules are of particular interest because of the reduced cytoxicity and lower risk of developing resistance compared to controlled release coatings. In this study, we focus on the chemical grafting of bioactive molecules on titanium. To concentrate the molecules at the metallic implant surface, we propose electrophoretic deposition (EPD) applying alternating current (AC) signals with an asymmetrical wave shape. We show that for the model molecule bovine serum albumin (BSA), as well as for the clinically relevant antifungal lipopeptide caspofungin (CASP), the deposition yield is drastically improved by superimposing a DC offset in the direction of the high-amplitude peak of the AC signal. Additionally, in order to produce immobilized CASP coatings, this experimental AC/DC-EPD method is combined with an established surface activation protocol. Principle component analysis (PCA) of time of-flight secondary ion mass spectrometry (ToF-SIMS) data confirm the immobilization of CASP with higher yield as compared to a diffusion-controlled process, and higher purity than the clinical CASP starting suspensions. Scratch testing data indicate good coating adhesion. Importantly, the coatings remain active against the fungal pathogen C. albicans as shown by in vitro biofilm experiments. In summary, this paper delivers a proof-of-concept for the application of AC-EPD as a fast grafting tool for antimicrobial molecules without compromising their activities.

DOI： 10.1021/acsami.6b16433

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Objective. The functional monomer 10-MDP has been considered as one of the best performing functional monomers for dental adhesives. Different adhesives containing 10-MDP are commercially available, among which many so-called 'universal' adhesives. We hypothesize that the quality of the functional monomer 10-MDP in terms of purity may affect bonding performance.
Methods. We therefore characterized three different 10-MDP versions (10-MDP_KN provided by Kuraray Noritake; 10-MDP_PCM provided by PCM; 10-MDP_DMI provided by DMI) using NMR, and analyzed their ability to form 10-MDP_Ca salts on dentin using XRD. The 'immediate' and 'aged' micro-tensile bond strength (mu TBS) to dentin of three experimental 10-MDP primers was measured. The resultant interfacial adhesive-dentin ultra-structure was characterized using TEM.
Results. NMR disclosed impurities and the presence of 10-MDP dimer in 10-MDP_PCM and 10-MDP_DMI. 10-MDP_PCM and 10-MDP_DMI appeared also sensitive to hydrolysis. 10-MDP_KN, on the contrary, contained less impurities and dimer, and did not undergo hydrolysis. XRD revealed more intense 10-MDP_Ca salt deposition on dentin induced by 10-MDP_KN. The adhesive based on the experimental 10-MDP_KN primer resulted in a significantly higher 'immediate' bond strength that remained stable upon aging; the mu TBS of the experimental 10-MDP_PCM and 10-MDP_DMI adhesives significantly dropped upon aging. TEM revealed thicker hybridization and more intense nano-layering for 10-MDP_KN.
Significance. It was concluded that primer impurities and the presence of 10-MDP dimer affected not only hybridization, but also reduced the formation of 10-MDP_Ca salts and nano-layering. 10-MDP in a high purity grade is essential to achieve durable bonding. (C) 2015 Published by Elsevier Ltd on behalf of Academy of Dental Materials. All rights reserved.

DOI： 10.1016/j.dental.2015.09.019

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

A potential standard method for measuring the relative dissolution rate to estimate the resorbability of calcium-phosphate-based ceramics is proposed. Tricalcium phosphate (TCP), magnesium-substituted TCP (MgTCP) and zinc-substituted TCP (ZnTCP) were dissolved in a buffer solution free of calcium and phosphate ions at pH 4.0, 5.5 or 7.3 at nine research centers. Relative values of the initial dissolution rate (relative dissolution rates) were in good agreement among the centers. The relative dissolution rate coincided with the relative volume of resorption pits of ZnTCP in vitro. The relative dissolution rate coincided with the relative resorbed volume in vivo in the case of comparison between microporous MgTCPs with different Mg contents and similar porosity. However, the relative dissolution rate was in poor agreement with the relative resorbed volume in vivo in the case of comparison between microporous TCP and MgTCP due to the superimposition of the Mg-mediated decrease in TCP solubility on the Mg-mediated increase in the amount of resorption. An unambiguous conclusion could not be made as to whether the relative dissolution rate is predictive of the relative resorbed volume in vivo in the case of comparison between TCPs with different porosity. The relative dissolution rate may be useful for predicting the relative amount of resorption for calcium-phosphate-based ceramics having different solubility under the condition that the differences in the materials compared have little impact on the resorption process such as the number and activity of resorbing cells.
Statement of significance
The evaluation and subsequent optimization of the resorbability of calcium phosphate are crucial in the use of resorbable calcium phosphates. Although the resorbability of calcium phosphates has usually been evaluated in vivo, establishment of a standard in vitro method that can predict in vivo resorption is beneficial for accelerating development and commercialization of new resorbable calcium phosphate materials as well as reducing use of animals. However, there are only a few studies to propose such an in vitro method within which direct comparison was carried out between in vitro and in vivo resorption. We propose here an in vitro method based on measuring dissolution rate. The efficacy and limitations of the method were evaluated by international round-robin tests as well as comparison with in vivo resorption studies for future standardization. This study was carried out as one of Versailles Projects on Advanced Materials and Standards (VAMAS). (C) 2015 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2015.07.040

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記述言語：英語   出版者・発行元：SPRINGER  

Dry titania layers on air-oxidized titanium substrates have been found to be active enough to cause apatite to be deposited in Kokubo's simulated body fluid (SBF) in narrow confined spaces, such as those in narrow grooves and thin gaps. Such in vitro apatite deposition is the basis of the GRAPE (R) technique. The aim of the present study is to determine why GRAPE conditions favor apatite deposition when laminar SBF flow (at 0.01-0.3 ml/min) passes through a shallow channel (0.5 mm) between a pair of titanium substrates each with a dry layer of titania. Assessing the factors that control the heterogeneous nucleation process led to the proposal of the working hypothesis that there are nucleation pre-embryos, ion assemblies that can be stabilized to form embryos, on the titania layer but that they are removed by the SBF flow. Specimens were subjected to different combinations of processes. One combination was that titania layers were exposed to still or flowing SBF, and the other was that half of a specimen, the inlet or outlet side, was exposed to still or flowing SBF with the other half being covered. The surface morphologies of the specimens were then compared in detail. The conclusion was that exposure to still SBF for 2 days before exposure to flowing SBF was required for apatite to be deposited. Some complicated apatite deposition modes were observed, e.g., apatite was deposited even on areas unexposed to still SBF. All of the results were successfully interpreted using the working hypothesis. The conclusion was that the GRAPE (R) technique depends on the confined space holding pre-embryo and embryo assemblies.

DOI： 10.1007/s10856-015-5552-x

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記述言語：英語   出版者・発行元：SPRINGER  

Pure titanium substrates were chemically oxidized with H2O2 and subsequent thermally oxidized at 400 degrees C in air to form anatase-type titania layer on their surface. The chemically and thermally oxidized titanium substrate (CHT) was aligned parallel to the counter specimen such as commercially pure titanium (cpTi), titanium alloy (Ti6Al4V) popularly used as implant materials or Al substrate with 0.3-mm gap. Then, they were soaked in Kokubo's simulated body fluid (SBF, pH 7.4, 36.5 degrees C) for 7 days. XRD and SEM analysis showed that the in vitro apatite-forming ability of the contact surface of the CHT specimen decreased in the order: cpTi > Ti6Al4V > Al. EDX and XPS surface analysis showed that aluminum species were present on the contact surface of the CHT specimen aligned parallel to the counter specimen such as Ti6Al4V and Al. This result indicated that Ti6Al4V or Al specimens released the aluminum species into the SBF under the spatial gap. The released aluminum species might be positively or negatively charged in the SBF and thus can interact with calcium or phosphate species as well as titania layer, causing the suppression of the primary heterogeneous nucleation and growth of apatite on the contact surface of the CHT specimen under the spatial gap. The diffusion and adsorption of aluminum species derived from the half-sized counter specimen under the spatial gap resulted in two dimensionally area-selective deposition of apatite particles on the contact surfaces of the CHT specimen.

DOI： 10.1007/s10856-015-5522-3

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記述言語：英語   出版者・発行元：Elsevier Ltd  

This chapter discusses in vitro degradation behaviors of calcium phosphate particles, such as nano-crystalline hydroxyapatite (HAp) and ion-substituted HAp synthesized by the wet-chemical processing method, and how their microstructure affects their initial dissolution profiles and kinetics. The chapter reviews several in vitro evaluation techniques for biodegradability of calcium phosphate ceramics and several models representing dissolution profiles and kinetics. The chapter then discusses the relationship between the heterogeneous structure of nano-crystalline HAp and the initial dissolution behaviors in acidic buffer solution.

DOI： 10.1016/B978178242033000004-3

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記述言語：英語   出版者・発行元：MANEY PUBLISHING  

Objectives: Post-operative scarring process on lumbar surgery is object of several studies mainly because of the epidural fibrosis formation. Hybrid chitosan have shown promising effect on fibrosis prevention. The aim of this study was to determine the influence of chitosan-silane membrane on the lumbar surgery scarring process. These membranes have improved mechanical strength which makes them suitable to maintain a predefined shape.
Methods: A two level lumbar laminectomy was performed in 14 New Zealand male rabbits. Laminectomy sites were randomly selected for biomaterial or control. Chitosan membranes were prepared and care was taken in order to make it adapted to the bone defect dimensions covering the totality of the defect including the bone margins. Histological analysis was performed by haematoxylin/eosin and by Masson's trichrome staining four weeks after laminectomy.
Results: Microscope observations revealed the presence of a well-organized regenerating tissue, integrated in the surrounding vertebral bone tissue with a regular and all-site interface on the chitosan sites, in clear contrast with the presence of a disorganized regenerating tissue with aspects consistent with the persistence of a chronic inflammatory condition, on control sites.
Discussion: The results of this study clearly demonstrated that hybrid chitosan had an organizing effect on post-operative scarring process. The presence of the hybrid chitosan membrane resulted on a well-organized tissue integrated in the surrounding vertebral bone tissue with signs of regenerative bone tissue in continuity with native bone. This can be a major feature on the dynamics of epidural fibrosis formation.

DOI： 10.1179/1743132814Y.0000000414

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記述言語：英語   出版者・発行元：WILEY-BLACKWELL  

Injectable systems can be used in minimally invasive surgical applications. Although chitosan-glycerophosphate hydrogel systems are biodegradable and biocompatible, the long periods of time required for their effective gelation have severely limited their clinical application. The challenges currently facing researchers in this field are therefore focused on shortening the gelation time and biocompatibility of these materials to develop hydrogels suitable for clinical application. Chitosan and -glycidoxypropyltrimethoxysilane (GPTMS) hybrids have recently demonstrated good cytocompatibility with respect to human osteoblastic cells (MG63) and human bone marrow cells. Although these precursor sols could form gels under physiological conditions, they required neutralization with a sodium hydroxide solution. In this study, the chitosan-GPTMS hybrid systems were neutralized with glycerophosphate to prepare injectable hydrogels. The results revealed that the gelation time of the hydrogels could be controlled by the amount of GPTMS in the precursor sols. The in vitro cytocompatibility of the hydrogels were evaluated in terms of the proliferation of MG63 cells cultured either directly onto the hydrogels or indirectly onto the cell culture plate under a hydrogel insert. In the former case, the cells showed good attachment and proliferated for up to 7 days. Similar results were observed in the in direct culture. These results suggest that this new chitosan-GPTMS hydrogel could potentially be used as an injectable biomaterial in clinical applications. (c) 2014 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 103A: 289-299, 2015.

DOI： 10.1002/jbm.a.35171

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記述言語：英語   出版者・発行元：Trans Tech Publications Ltd  

Nano-meter scale Ca-deficient hydroxyapatite (nano-apatite) is a potential candidate as artificial bone substitute materials owing to its similarity to the bone with respect to composition, morphology and osteoclastic degradation or adsorbent materials for blood purification therapy to remove pathogenic substances. The initial biodegradation behaviors, the initial cell-material interaction and the protein adsorption properties of nano-apatite must depend on the microstructure. The purpose of this study is the preparation of nano-apatite particles and their structural characterization by using X-ray diffraction (XRD) and solid-state NMR spectroscopy. The nano-apatite particles were prepared by precipitation processing method, and the effects of magnesium ions on the precipitation of calcium phosphate were examined, because Mg ions are well-known to play a role of inhibition of crystal growth. The addition of Mg ions led to the precipitation of nano-meter scale Ca-deficient apatite crystals having 1.33-1.63 of the molar ratio (Mg+Ca)/P. NMR analyses showed that the microstructure of Mg•HAp particles can be explained by a crystalline HAp core covered with a thin amorphous hydrated calcium phosphate layer.

DOI： 10.4028/www.scientific.net.KEM.631.57

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DOI： 10.1007/s10856-015-5522-3.

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

Calcium phosphates (CPs) were fabricated with using a continuous flow-type tube reactor under pH 6.4 and 9, within the temperature range from 0 to 100°C. The sample fabricated at the temperature range from 0 to 60°C involved not only dicalcium hydrogenphosphate dihydrate (DCPD) as the primary phase but also octacalcium phosphate (OCP). As the relative X-ray diffraction intensity of OCP increased with increase in the synthesis temperature, particles of a sheet-like shape appeared. The samples fabricated at 80 and 100°C have a crystalline phase of hydroxyapatite (HAp) and morphology of rod-like shape. Under pH 9, in contrast, the reactor fabricated HAp crystalline, irrespective of the synthesis temperature. In particular, at 80 and 100°C, only oval or spindle-shaped HAp was yielded. It was therefore confirmed that the present tube reactor system was versatile to control the size, shape, and crystalline phase of CPs. The morphology, particle size, and specific surface area dependent on the pH and temperature of synthesis were discussed the relative stability of the relevant calcium phosphate phases and equilibrium relations among the orthophosphate ions.

DOI： 10.2109/jcersj2.123.101

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記述言語：英語  

We have previously developed biodegradable β-tricalcium phosphate (β-TCP) cement based on the chelate-setting mechanism of inositol phosphate (IP6). The β-TCP cement powder for the cement fabrication was prepared via a novel powder preparation process, in which the starting β-TCP powders were prepared by simultaneous ball-milling and surface-modification in the IP6 solution. In the present study, the novel powder preparation process was applied to an α-TCP powder, and effect of milling time and beads size for ball-milling on the material properties of the a-TCP powders was investigated. The α-TCP powder ball-milled in 1000 ppm IP6 solution for 4 h with 2 mm-diameter beads was composed of single phase α-TCP with the smallest particle size of 2.2 um. Dissolution of 4 h-milled α-TCP powder was approximately twice higher than that of starting α-TCP powder before ball-milling. The α-TCP powder with high dissolution property prepared via the novel powder preparation process is potential candidate for fabrication of the chelate-setting cement.

DOI： 10.4028/www.scientific.net.KEM.631.113

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記述言語：英語   出版者・発行元：HINDAWI PUBLISHING CORPORATION  

This paper describes the apatite deposition of chitosan-silicate porous hybrids derived from chitosan and gamma-glycidoxypropyltrimethoxysilane (GPTMS) in alkaline phosphate solution. The preparation of porous hybrids with needle-like apatite on their surfaces is described. Following apatite deposition the porous hybrids maintained high porosity. The enzymatic degradation rate was low even after 6 months and the porous hybrids were very flexible and cut easily using surgical scissors.

DOI： 10.1155/2015/392940

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE SA  

Rough nanostructured anatase TiO2 surfaces containing many pores were prepared by the hydrothermal-based method. Surface modification with self-assembled monolayers (SAMs) of octadecylphosphonic acid (ODP) resulted in the superhydrophobic surface with an extremely high static water contact angle (CA) of 173.6 degrees +/- 1.7 degrees. This superhydrophobic surface could be converted into a superhydrophilic surface with a water CA of nearly 0 degrees by irradiating it with ultraviolet (UV) light, which induced photocatalytic decomposition of the ODP SAM. A superhydrophobic-superhydrophilic pattern with an extremely high wettability contrast (a water CA difference of over 170 degrees) could be fabricated on the ODP-modified TiO2 surface by area-selective UV irradiation through a photomask. This is the report of the TiO2-based superhydrophobic-superhydrophilic pattern with a water CA difference of over 170 degrees, and it may be possible to use such patterns for various applications. (C) 2014 Elsevier B. V. All rights reserved.

DOI： 10.1016/j.tsf.2014.02.060

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記述言語：英語  

High-purity (SupT) and reagent-grade (ST), stoichiometric and silicate-containing α-tricalcium phosphate (α-TCP: ST0/SupT0 and Si-TCP x = 0.10: ST10/SupT10) were prepared by solid-state reaction based on the substitution mechanism Ca 3 (PO 4 ) (2-x) (SiO 4 ) x . Samples were determined to be phase pure by X-ray diffraction (XRD), and Rietveld analysis performed on the XRD data confirmed inclusion of Si in the α-TCP structure as determined by increases in unit cell parameters; particularly marked increases in the b-axis and β-angle were observed. X-ray fluorescence (XRF) confirmed the presence of expected levels of Si in Si-TCP compositions as well as significant levels of impurities (Mg, Al and Fe) present in all ST samples; SupT samples showed both expected levels of Si and a high degree of purity. Phosphorus ( 31 P) magic-angle-spinning solid-state nuclear magnetic resonance (MAS NMR) measurements revealed that the high-purity reagents used in the synthesis of SupT0 can resolve the 12 expected peaks in the 31 P spectrum of α-TCP compared to the low-purity ST0 that showed significant spectral line broadening; line broadening was also observed with the inclusion of Si which is indicative of induced structural disorder. Silicon ( 29 Si) MAS NMR was also performed on both Si-TCP samples which revealed Q 0 species of Si with additional Si Q 1 /Q 2 species that may indicate a potential charge-balancing mechanism involving the inclusion of disilicate groups; additional Q 4 Si species were also observed, but only for ST10. Heating and cooling rates were briefly investigated by 31 P MAS NMR which showed no significant line broadening other than that associated with the emergence of β-TCP which was only realised with the reagent-grade sample ST0. This study provides an insight into the structural effects of Si-substitution in α-TCP and could provide a basis for understanding how substitution affects the physicochemical properties of the material. © 2013 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2013.11.014

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記述言語：英語  

DOI： 10.1016/j.actbio.2013.11.014

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記述言語：英語   出版者・発行元：SAGE PUBLICATIONS INC  

Among several functional monomers, 10-methacryloxydecyl dihydrogen phosphate (10-MDP) bonded most effectively to hydroxyapatite (HAp). However, more hydrolysis-resistant functional monomers are needed to improve bond durability. Here, we investigated the adhesive potential of the novel fluoro-carbon functional monomer 6-methacryloxy-2,2,3,3,4,4,5,5-octafluorohexyl dihydrogen phosphate (MF8P; Kuraray Noritake Dental Inc., Tokyo, Japan) by studying its molecular interaction with powder HAp using solid-state nuclear magnetic resonance (H-1 MAS NMR) and with dentin using x-ray diffraction (XRD) and by characterizing its interface ultrastructure at dentin using transmission electron microscopy (TEM). We further determined the dissolution rate of the MF8P_Ca salt, the hydrophobicity of MF8P, and the bond strength of an experimental MF8P-based adhesive to dentin. NMR confirmed chemical adsorption of MF8P onto HAp. XRD and TEM revealed MF8P_Ca salt formation and nano-layering at dentin. The MF8P_Ca salt was as stable as that of 10-MDP; MF8P was as hydrophobic as 10-MDP; a significantly higher bond strength was recorded for MF8P than for 10-MDP. In conclusion, MF8P chemically bonded to HAp. Despite its shorter size, MF8P possesses characteristics similar to those of 10-MDP, most likely to be associated with the strong chemical bond between fluorine and carbon. Since favorable bond strength to dentin was recorded, MF8P can be considered a good candidate functional monomer for bonding.

DOI： 10.1177/0022034513514447

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記述言語：英語   出版者・発行元：SPRINGER  

A recently developed "GRAPE(A (R)) technology" provides titanium or titanium alloy implants with spontaneous apatite-forming ability in vitro, which requires properly designed gaps and optimum heat treatment in air. In this study, titanium alloy and commercially pure (cp) titanium substrates were thermally oxidized in air before aligning pairs of specimens in the GRAPE(A (R)) set-up, i.e., titanium alloy and cp titanium substrates were aligned parallel to each other with optimum gap width (spatial design). A liquid phase deposition (LPD) technique was employed for titania coatings on titanium alloy substrate. Then, they were soaked in Kokubo's simulated body fluid (SBF, pH 7.4, 36.5 A degrees C) for 7 days to confirm the in vitro apatite formation on the substrates under the specific spatial design. Anatase-type titania coatings fabricated by using LPD technique led to the deposition of apatite particles within 7 days and showed apatite X-ray diffraction. On the other hand, thermally oxidized titanium alloy substrate in air and non-treated specimens did not show any apatite X-ray diffraction. These results indicated that the heterogeneous nucleation of apatite induced on anatase-type titania coating prepared by LPD technique when it was aligned parallel to thermally oxidized cp titanium substrate with optimum gap width.

DOI： 10.1007/s10856-013-5078-z

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記述言語：英語   出版者・発行元：Springer New York  

This chapter introduces nanocomposites of silica, titania, calcium phosphates, biologically active glasses, and their polymer-modified derivatives with meso- and macro-porous, nanotubular, or hollow nanoparticle-type structures that have been prepared via the sol-gel routes. Their applications for delivering drugs and DNAs, tissue-materials interactions, and tissue regeneration are briefly described.

DOI： 10.1007/978-1-4939-1209-4_7

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When solution of a polymer with some inorganic ions is electrospun, the polymer fibrils will be elongated within the spinning direction and those ions are held in the inter-fibril spaces. When those electrospun fibers are calcined, ceramic fibers will be obtained. The present study has attempted to employ such spaces formed in polyvinyl alcohol) (PVA) as nano- or micro-reactor spaces for precipitation of nano-crystalline particles. Exposing the spun PVA mats to ammonia vapor fixed metal ions in the form of hydroxide and, induced apatitic calcium phosphate crystallites when the precursor solution involved calcium and hydrogen orthophosphate ions.

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記述言語：英語  

There has been a resurgence of interest in alpha-tricalcium phosphate (α-TCP), with use in cements, polymer composites and in bi- and tri-phasic calcium phosphate bone grafts. The simplest and most established method for preparing α-TCP is the solid state reaction of monetite (CaHPO 4 ) and calcium carbonate at high temperatures, followed by quenching. In this study, the effect of the chemical composition of reagents used in the synthesis of α-TCP on the local structure of the final product is reported and findings previously reported pertaining to the phase composition and stability are also corroborated. Chemical impurities in the monetite reagents were identified and could be correlated to the calcium phosphate products formed; magnesium impurities favoured the formation of β-TCP, whereas single phase α-TCP was favoured when magnesium levels were low. Monetite synthesised in-house exhibited a high level of chemical purity; when this source was used to produce an α-TCP sample, the α-polymorph could be obtained by both quenching and by cooling to room temperature in the furnace at rates between 1 and 10 C/min, thereby simplifying the synthesis process. It was only when impurities were minimised that the 12 phosphorus environments in the α-TCP structure could be resolved by 31 P nuclear magnetic resonance; samples containing chemical impurity showed differing degrees of line-broadening. Reagent purity should therefore be considered a priority when synthesising/characterising the α-polymorph of TCP. © 2013 Elsevier B.V.

DOI： 10.1016/j.msec.2013.08.038

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記述言語：英語   掲載種別：書評論文，書評，文献紹介等   出版者・発行元：HINDAWI PUBLISHING CORPORATION  

The treatment of peripheral nerve injuries remains one of the greatest challenges of neurosurgery, as functional recover is rarely satisfactory in these patients. Recently, biodegradable nerve guides have shown great potential for enhancing nerve regeneration. A major advantage of these nerve guides is that no foreign material remains after the device has fulfilled its task, which spares a second surgical intervention. Recently, we studied peripheral nerve regeneration using chitosan-gamma-glycidoxypropyltrimethoxysilane (chitosan-GPTMS) porous hybrid membranes. In our studies, these porous membranes significantly improved nerve fiber regeneration and functional recovery in rat models of axonotmetic and neurotmetic sciatic nerve injuries. In particular, the number of regenerated myelinated nerve fibers and myelin thickness were significantly higher in rat treated with chitosan porous hybrid membranes, whether or not they were used in combination with mesenchymal stem cells isolated from the Wharton's jelly of the umbilical cord. In this review, we describe our findings on the use of chitosan-GPTMS hybrids for nerve regeneration.

DOI： 10.1155/2014/153808

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記述言語：英語   出版者・発行元：PHARMACEUTICAL SOC JAPAN  

Organic-inorganic hybrids of poly(dimethyl siloxane), gelatin, and chitosan with such silanes as tetraethoxysilane and 3-glycidoxytriethoxysilane are derived via the sol-gel routes. Their biomedical applications are discussed from biomimetic deposition of bone-like apatite, cell culture, and in vivo behavior.

DOI： 10.1248/bpb.b13-00526

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Silica nanotube sponges and solid silica fiber mats were fabricated using a collagen and electrospun poly(vinylalcohol) as the templates via the sol-gel route. In vitro reassembled collagen fibrils were treated in the Stöber sol-gel precursor mixture of tetraethoxysilane (TEOS), ethanol, water, and ammonia to produce the silica-coated collagen fibrils. The electrospun PVA fiber mats were soaked in the Stöber type as well as acid-catalyzed silica oligomer sol from TEOS. Those were calcined to yield apparently silica nano- or micro-fibers, but transmission and scanning electron microscope observations showed that the Stöber sol treatment resulted in silica nano- or micro-fibers with hollow structure, or nanotubes (silica NTs), while the acid-catalyzed sol yielded solid fibrous mats.

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Preparation of injectable hydroxyapatite/collagen bone-like nanocomposite (HAp/Col) paste utilizing sodium alginate (Na-Alg) and influence of additives on the paste properties were investigated. The HAp/Col at the HAp and collagen mass ratio of 80:20 synthesized by a simultaneous titration method was pelletized to 100-212 mu m. The HAp/Col powder and that treated with 100mM CaCl2 (Ca-HAp/Col) were used as starting powders. A paste was prepared by mixing of the starting powder and Na-Alg solution at one of several powder/liquid ratios. The paste was directly injected into 100mM CaCl2 solution to confirm setting capability, and examined a viscosity, hardening behavior, compressive strength and decay property. In addition, the paste supplemented with an organic acid or a calcium compound as an additive was also prepared to examine influences of the additive on paste properties. The organic acid was chosen from citric, succinic, malic, lactic and glycolic acids, and the calcium compound was chosen from Ca(OH)(2), Ca(CO)(3), CaSO4 center dot 0.5H(2)O and calcium citrate.
The prepared paste was set by direct injection to 100mM CaCl2 solution. The suitable mixing conditions of the paste were a P/L ratio of 0.6 at the 90:10 mass ratio of Ca-HAp/Col and solution of low viscous Na-Alg. All additives increased the paste viscosity; however, the mechanisms were different between organic acids and calcium compounds. Organic acids rapidly decreased pH to form Alg gel by deposition of Alg. Contrarily, calcium compounds supplied Ca2+ ions to form egg-box structure for gelation of Alg, and the reaction depended on solubility of compound. Additives also increased decaying time but could not realize anti-decay in the present conditions. The results suggested that the HAp/Col injectable paste can be utilized in rapid prototyping materials and might be good candidate for injectable artificial bone with further improvement in anti-decay property. (C)2013 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.121.775

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記述言語：英語  

© 2013 The American Ceramic Society. All rights reserved. Silica nanotube sponges and solid silica fiber mats were fabricated using a collagen and electrospun poly(vinylalcohol) as the templates via the sol-gel route. In vitro reassembled collagen fibrils were treated in the Stöber sol-gel precursor mixture of tetraethoxysilane (TEOS), ethanol, water, and ammonia to produce the silica-coated collagen fibrils. The electrospun PVA fiber mats were soaked in the Stöber type as well as acid-catalyzed silica oligomer sol from TEOS. Those were calcined to yield apparently silica nano- or micro-fibers, but transmission and scanning electron microscope observations showed that the Stöber sol treatment resulted in silica nano- or micro-fibers with hollow structure, or nanotubes (silica NTs), while the acid-catalyzed sol yielded solid fibrous mats.

DOI： 10.1002/9781118751015.ch7

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Objectives. The functional monomer 10-methacryloxydecyl dihydrogen phosphate (10-MDP), recently used in more self-etch adhesives, chemically bonds to hydroxyapatite (HAp) and thus tooth tissue. Although the interfacial interaction of the phosphoric-acid functional group of 10-MDP with HAp-based substrates has well been documented, the effect of the long carbon-chain spacer of 10-MDP on the bonding effectiveness is far from understood.
Methods. We investigated three phosphoric-acid monomers, 2-methacryloyloxyethyl dihydrogen phosphate (2-MEP), 6-methacryloyloxyhexyl dihydrogen phosphate (6-MHP) and 10-MDP, that only differed for the length of the carbon chain, on their chemical interaction potential with HAp and dentin, this correlatively using X-ray diffraction (XRD) and transmission electron microscopy (TEM). Commercial 6-MHP and 10-MDP containing adhesives were investigated as well.
Results. XRD revealed that on HAp only 10-MDP produced monomer-calcium salts in the form of 'nano-layering', while on dentin all monomers produced 'nano-layering', but with a varying intensity in the order of 10-MDP > 6-MHP > 2-MEP. TEM confirmed that 10-MDP formed the thickest hybrid and adhesive layer. XRD and TEM revealed 'nano-layering' for all commercial adhesives on dentin, though less intensively for the 6-MHP containing adhesive than for the 10-MDP ones.
Significance. It is concluded that not only the phosphoric-acid group but also the spacer group, and its length, affect the chemical interaction potential with HAp and dentin. In addition, the relatively strong 'etching'' effect of 10-MDP forms more stable monomer-Ca salts, or 'nano-layering', than the two shorter carbon-chain monomers tested, thereby explaining, at least in part, the better bond durability documented with 10-MDP containing adhesives. (c) 2013 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.dental.2013.05.006

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記述言語：英語   出版者・発行元：SPRINGER  

Glass polyalkenoate cements (GPCs) have exhibited potential as bone cements. This study investigates the effect of substituting TiO2 for SiO2 in the glass phase and the subsequent effect on cement rheology, mechanical properties, ion release and antibacterial properties. Glass characterization revealed a reduction in glass transition temperature (T (g) ) from 685 to 669 A degrees C with the addition of 6 mol % TiO2 (AT-2). Magic angle spinning nuclear magnetic resonance (MAS-NMR) revealed a shift from -81 ppm to -76pmm when comparing a Control glass to AT-2, indicating de-polymerization of the Si network. The incorporation of TiO2 also increased the working time (T (w) ) from 19 to 61 s and setting time (T (s) ) from 70 to 427 s. The maximum compressive strength (sigma (c) ) increased from 64 to 85 MPa. Ion release studies determined that the addition of Ti to the glass reduced the release of zinc, calcium and strontium ions, with low concentrations of titanium being released. Antibacterial testing in E. coli resulted in greater bactericidal effects when tested in aqueous broth for both titanium containing cements.

DOI： 10.1007/s10856-013-4880-y

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Anatase layer was derived on pure titanium substrates by the H 2O2 treatment and calcination, on which UV was irradiated in air (UVa) and in ultra pure water (UVw). The effects of the UV irradiation on in vitro apatite formation in Kokubo's simulated body fluid were interpreted in terms of the modified chemistry of the anatase layer. The UVa treatment reduced apatite formation while the contrary effects were observed for the UVw treatment. From Ols X-ray photoelectron spectroscopic (XPS) analysis, those results were correlated to the change in the relative amount of Ti-OH (basic TiOH) and Ti-O(H)-Ti (acidic Ti-OH). Combining the XPS analysis and the apatite growth characteristics, i.e., the number and size of the semi-spherical particles and their surface-coverage, derived a plausible model: proper assembly of those sites (Ti-OH and Ti-O(H)-Ti) that collect both calcium and phosphate ions together should only give rise to induction of apatite nucleation.

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Hydroxyapatite (HAp) particles were synthesized by two processing methods such as solid-state reaction and wet chemical reaction, and were characterized in terms of their chemical composition, disordered structure and in vitro biodegradability. XRD revealed that the prepared HAp particles were composed of single phase HAp, while 1D and 2D solid-state NMR analysis showed that the prepared HAp particles consisted of not only crystalline HAp but also disordered phase. The in vitro biodegradability was discussed by using a structure model for nano-crystalline HAp, in which the nano-crystals consist of a crystalline HAp core covered with a disordered surface layer (core-shell model).

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記述言語：英語   出版者・発行元：WILEY-BLACKWELL  

Implant surfaces must sometimes be modified to form strong bonds to host tissues. The method of depositing an anatase layer on chemically pure titanium by chemical oxidation with H2O2 and subsequent calcination (CHT) is known to deposit apatite under physiological conditions; it thus exhibits bone-bonding ability. UV irradiation should affect the bonding ability because the CHT anatase layer would experience certain chemical modifications, such as a decrease or an increase in the number of TiOH and TiO(H)Ti sites; these sites are considered active sites for apatite nucleation. When in vitro apatite deposition was examined, using Kokubo's simulated body fluid, UV irradiation in air reduced the apatite-forming ability of the CHT anatase layer, and UV irradiation on the samples in water enhanced the ability. These results were correlated to changes in the Ti?OH and TiO(H)Ti sites, as determined by O 1s X-ray photoelectron spectroscopy. Analysis of the number and size of the semi-spherical apatite particles and their surface coverage led to a model: proper assembly of the Ti?OH and TiO(H)Ti sites should only give rise to the induction of apatite nucleation, analogous to topotaxy effects.(C) 2012 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 101A: 712-719, 2013.

DOI： 10.1002/jbm.a.34370

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記述言語：英語   出版者・発行元：SPRINGER  

The silica gels, derived from water glass solution with pH adjusted at 3.0 and 9.9, were revisited to investigate their constitution, although water glass has been studied for last tens of decades on gelation. Solid-state nuclear magnetic resonance spectroscopy was applied to the nuclei H-1 and Si-29, by the use of magic angle spinning (MAS), H-1 -> Si-29 CP-MAS (CP: cross-polarization), and modern techniques such as 2D HETCOR (two dimensional heteronuclear correlation), and variable-contact time CP techniques. Gelation time (t(gel)) showed U-letter shape dependence on pH. All gels consisted of Q(n) groups (n: 2, 3, and 4), where Q(n) stands for a silicate unite [(O-1/2)(n)Si (-O-)(4-n)] (n: 0-4). The analysis of the H-1 -> Si-29 CP kinetics and H-1-Si-29 HETCOR spectra elucidated the presence of four kinds of H-1 nuclei, i.e., those giving a peak at 6.9 ppm in chemical shift delta: H-1-OSi hydrogen bonded to H2O molecules; one at 4.3 ppm: H-1 of adsorbed water molecules, hydrogen-bonded to the silanol groups; one at 1.7 ppm: H-1-OSi confined in the gel lattice, including that forming aggregations like Si-O-H/O-Na-Si; and one at 4.2 ppm: H-1 of water molecules on the outermost hydration layer.

DOI： 10.1007/s10971-012-2917-1

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The treatment of peripheral nerve injuries is still one of the most challenging tasks in neurosurgery, as functional recovery is rarely satisfactory in these patients. The concept behind the use of biodegradable nerve guides is that no foreign material should be left in place after the device has fulfilled its task, so as to spare a second surgical intervention. In a previous study, flexible and biodegradable chitosan-3-glycidoxypropyltrimethoxysilane (GPTMS) hybrid membranes exhibited better cytocompatibility in terms of osteoblastic cells than chitosan membrane. Porous chitosan hybrid membranes, derived by freeze-drying the hybrid gels, showed that the cells were attached and proliferated both on the surface and into pores. In this study, the porous chitosan-silicate hybrid membranes with non-differentiated human mesenchymal stem cells isolated from Wharton's jelly of umbilical cord were used to reconstruct the crushed peripheral nerve. Axonotmesis lesion of 3 mm was enwrapped with the hybrid membranes with or without a monolayer of non-differentiated human mesenchymal stem cells. Motor and sensory functional recovery was evaluated throughout a healing period of 12 weeks. The combination of hybrid membranes and human MSCs infiltration showed a slightly better recovery than the untreated control (the just crushed nerve). On the other hand, the hybrid membrane alone promoted the crushed peripheral nerve reconstruction. It is expected that the porous chitosan hybrid membranes is candidate for the clinical tool in peripheral nerve reconstructive surgery.

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Microsphere-based therapy is used to allow drug release to treat the critical site through the choice and formulation of variations drug-polymer combinations. They are also used to control the release of insoluble drug by the biodegradability of polymer. Chitosan is one of the candidates for the polymer matrix because their biodegradability and biocompatibility. Recently, we prepared and characterized the inorganic-organic hybrid derived from chitosan and siloxane units. This hybrid showed the excellent biocompatibility for the osteoblastic cells, fibroblastic cells, and nerve cells, etc. In this study, the microspheres were prepared from this hybrid using the microfluidic systems. The biodegradability, drug releasing behavior and cytocompatibility were investigated. © 2013 IEEE.

DOI： 10.1109/MHS.2013.6710442

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Nanocrystalline hydroxyapatite (HAp) and silicon-containing hydroxyapatite (SiHAp) particles were synthesized by a wet-chemical procedure and their heterogeneous structures involving a disordered phase were analyzed in detail by X-ray diffractometry (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FTIR) spectroscopy and solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The effects of heterogeneous structure on in vitro biodegradability and the biologically active Ca(II)- and Si(IV)-releasing property of SiHAp particles were discussed. The Si-29 NMR analysis revealed that the Si(IV) was incorporated in the HAp lattice in the form of Q(0) (SiO44- or HSiO43-) species, accompanied by the formation of condensed silicate units outside the HAp lattice structure, where the fraction and amount of Q(0) species in the HAp lattice depends on the Si content. The P-31 and H-1 NMR results agreed well with the XRD, TEM and FTIR results. NMR quantitative analysis results were explained by using a core-shell model assuming a simplified hexagonal shape of HAp covered with a disordered layer, where Si(IV) in Q(0) was incorporated in the HAp lattice and a disordered phase consisted of hydrated calcium phosphates involving polymeric silicate species and carbonate anions. With the increase in the Si content in the HAp lattice, the in vitro degradation rate of the SiHAps increased, while their crystallite size stayed nearly unchanged. The biologically active Ca(II)- and Si(IV)-releasing ability of the SiHAps was remarkably enhanced at the initial stage of reactions by an increase in the amount of Si(IV) incorporated in the HAP lattice but also by an increase of the amount of polymeric silicate species incorporated in the disordered phase. (C) 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2012.08.024

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記述言語：英語  

The treatment of peripheral nerve injuries is still one of the most challenging tasks in neurosurgery, as functional recovery is rarely satisfactory in these patients. The concept behind the use of biodegradable nerve guides is that no foreign material should be left in place after the device has fulfilled its task, so as to spare a second surgical intervention. In a previous study, flexible and biodegradable chitosan-γ-glycidoxypropyltrimethoxysilane (GPTMS) hybrid membranes exhibited better cytocompatibility in terms of osteoblastic cells than chitosan membrane. Porous chitosan hybrid membranes, derived by freeze-drying the hybrid gels, showed that the cells were attached and proliferated both on the surface and into pores. The aim of the present study was to evaluate the influence of these chitosan hybrid membranes in terms of their inflammatory response and remodeling of connective tissue during wound-healing processes before use as a periphery nerve graft. The porous chitosan hybrid membranes showed good biocompatibility and improved posttraumatic axonal regrowth and functional recovery. © (2013) Trans Tech Publications, Switzerland.

DOI： 10.4028/www.scientific.net/KEM.529-530.361

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記述言語：英語  

Hydroxyapatite (HAp) particles were synthesized by solid-state reaction and wet chemical reaction, and were characterized in terms of their chemical composition, disordered structure and in vitro biodegradability. An X-ray diffraction study revealed that the prepared HAp particles were composed of single phase HAp, while 1D and 2D solid-state NMR analysis showed that they consisted of not only crystalline HAp but also a disordered phase. An in vitro biodegradability test showed that wet chemically derived HAp particles were degraded quicker than commercially available HAP-100. The in vitro biodegradability was discussed by using a structure model for nano-crystalline HAp, in which the nano-crystals consist of a crystalline HAp core covered with a disordered surface layer (core-shell model). Although the specific surface area was the predominant factor on the rate of Ca ion dissolution, the disordered surface layer enhanced the release of Ca ions in the initial stage within 1 min, while the crystalline core of HAp also gave different release rate of Ca ions, depending on the chemical distribution in the P (V) environment. © (2013) Trans Tech Publications, Switzerland.

DOI： 10.4028/www.scientific.net/KEM.529-530.70

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記述言語：英語   出版者・発行元：TRANS TECH PUBLICATIONS LTD  

Silica gel macrospheres of 2 similar to 4 mm in size, and wrapped with Ca-alginate chelate film were prepared as the substrate for hydroxyapatite coating layer, using water glass as the silica source. Those Ca-SiO2 macrospheres were soaked in a 1:1 (volume) mixture of ethanol and 0.1 M Na2HPO4 to deposit hydroxyapatite layer (HAp-SiO2 macrospheres). Adsorption of bovine serum albumin and egg lysozyme on those Ca-SiO2 and HAp-SiO2 macrospheres under physiological pH (7.2) was well correlated to the Langmuir-type adsorption equation. The electrostatic interactions between the protein molecules and those macrospheres well interpret the adsorption isotherms, while the mesopores in the Ca-SiO2 contributed to some extent. A multi-layer adsorption model was proposed.

DOI： 10.4028/www.scientific.net/KEM.529-530.637

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Silica fiber mats were fabricated by soaking electro-spun poly(vinyl alcohol) fibril mat in NH4OH-catalyzed (Stober type) colloidal silica sol and silica oligomer solution from HCl-catalysis of the system tetraethoxysilane, ethanol, and water, followed by appropriate heat treatments. The silica fibrils from the Stober silica sol were hollow nano-tubes (NT) consisting of nano-sized silica particles, while the silica nanofibers (NF) from the acid-catalyzed sol were solid with minimal porosity. A model was proposed for the NF and NT formation processes. (C)2012 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.120.520

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記述言語：英語   出版者・発行元：SAGE PUBLICATIONS INC  

Previous research showed that the functional monomer 10-methacryloxydecyl dihydrogen phosphate (MDP) ionically bonds to hydroxyapatite (HAp) and forms a nano-layered structure at the interface with HAp-based substrates. Such hydrophobic nano-layering is considered to contribute to the long-term durability of the bond to tooth tissue. However, dental adhesives are complex mixtures usually containing different monomers. This study investigated the effect of the monomer 2-hydroxyethylmethacrylate (HEMA) on the chemical interaction of MDP with HAp by x-ray diffraction (XRD), nuclear magnetic resonance (NMR), and quartz crystal microbalance (QCM). We examined the chemical interaction of 5 experimental MDP solutions with increasing concentrations of HEMA. XRD revealed that addition of HEMA inhibits nano-layering at the interface, while NMR confirmed that MDP remained adsorbed onto the HAp surface. QCM confirmed this adsorption of MDP to HAp, as well as revealed that the demineralization rate of HAp by MDP was reduced by HEMA. It was concluded that even though the adsorption of MDP to HAp was not hindered, addition of HEMA inhibited interfacial nano-layering. Potential consequences with regard to bond durability necessitate further research.

DOI： 10.1177/0022034512460396

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記述言語：英語   出版者・発行元：SHENYANG EDITORIAL DEPT NEURAL REGENERATION RES  

Many studies have been dedicated to the development of scaffolds for improving post-traumatic nerve regeneration. The goal of this study was to assess the effect on nerve regeneration, associating a hybrid chitosan membrane with non-differentiated human mesenchymal stem cells isolated from Wharton's jelly of umbilical cord, in peripheral nerve reconstruction after crush injury. Chromosome analysis on human mesenchymal stem cell line from Wharton's jelly was carried out and no structural alterations were found in metaphase. Chitosan membranes were previously tested in vitro, to assess their ability in supporting human mesenchymal stem cell survival, expansion, and differentiation. For the in vivo testing, Sasco Sprague adult rats were divided in 4 groups of 6 or 7 animals each: Group 1, sciatic axonotmesis injury without any other intervention (Group 1-Crush); Group 2, the axonotmesis lesion of 3 mm was infiltrated with a suspension of 1 250-1 500 human mesenchymal stem cells (total volume of 50 mu L) (Group 2-CrushCell); Group 3, axonotmesis lesion of 3 mm was enwrapped with a chitosan type III membrane covered with a monolayer of non-differentiated human mesenchymal stem cells (Group 3-CrushChitIIICell) and Group 4, axonotmesis lesion of 3 mm was enwrapped with a chitosan type III membrane (Group 4-CrushChitIII). Motor and sensory functional recovery was evaluated throughout a healing period of 12 weeks using sciatic functional index, static sciatic index, extensor postural thrust, and withdrawal reflex latency. Stereological analysis was carried out on regenerated nerve fibers. Results showed that infiltration of human mesenchymal stem cells, or the combination of chitosan membrane enwrapment and human mesenchymal stem cell enrichment after nerve crush injury provide a slight advantage to post-traumatic nerve regeneration. Results obtained with chitosan type III membrane alone confirmed that they significantly improve post-traumatic axonal regrowth and may represent a very promising clinical tool in peripheral nerve reconstructive surgery. Yet, umbilical cord human mesenchymal stem cells, that can be expanded in culture and induced to form several different types of cells, may prove, in future experiments, to be a new source of cells for cell therapy, including targets such as peripheral nerve and muscle.

DOI： 10.3969/j.issn.1673-5374.2012.29.002

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Silica gel macrospheres were prepared from water glass as the silica source. The water glass solution was mixed with sodium alginate solution and added dropwisely to 1 M CaCl2 solution to form macrospheres with similar to 4 and 2.6 mm in diameter. Those SiO2 macrospheres were soaked in 1:1 (volume) mixture of ethanol and 0.1 M Na2HPO4 to deposit hydroxyapatite layer (HAp-SiO2 macrospheres). Bovine serum albumin (BSA) and egg lysozyme (LYZ) were adsorbed those SiO2 and HAp-SiO2 macrospheres. The amount of proteins adsorbed was well correlated to the Langmuir-type adsorption equation. The electrostatic interaction was predominant between the macrosphere surface and the protein molecules. Protein molecular entrapment in the mesopores (525 nm) was also probable for the SiO2 macrospheres but not applicable to the HAp-SiO2 ones without the mesopores. From consideration that protein molecule has a few groups with negative or positive partial charges, a multi-layer adsorption model was proposed. (c) 2012 The Ceramic Society of Japan. All rights reserved.

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE BV  

New class of hybrid composite was synthesized via sol-gel process with the combination of poly(vinyl alcohol) (PVA), TEOS, 3-glycidyloxypropyltrimethoxysilane (GPTMS) reacted with the cross-linking agent glutaraldehyde. The composites demonstrated a maximum high proton conductivity of 1.7 x 10(-2) S cm(-1) at 140 degrees C and a relative humidity of 50% RH. The swelling ratio was calculated in dry and wet conditions, and the composites were found capable of swelling. The structural formation of the composites was studied by techniques such as FTIR, TGA and impedance spectroscopy, and it was concluded that these PVA-SiO2/GPTMS/GA composite membranes exhibited excellent thermal, mechanical and conductivity properties. (C) 2012 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.matlet.2012.04.023

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記述言語：英語   出版者・発行元：John Wiley and Sons  

DOI： 10.1002/9781118346457.ch10

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記述言語：英語   出版者・発行元：SAGE PUBLICATIONS INC  

According to the 'Adhesion-Decalcification' concept, specific functional monomers within dental adhesives can ionically interact with hydroxyapatite (HAp). Such ionic bonding has been demonstrated for 10-methacryloyloxydecyl dihydrogen phosphate (MDP) to manifest in the form of self-assembled 'nano-layering'. However, it remained to be explored if such nano-layering also occurs on tooth tissue when commercial MDP-containing adhesives (Clearfil SE Bond, Kuraray; Scotchbond Universal, 3M ESPE) were applied following common clinical application protocols. We therefore characterized adhesive-dentin interfaces chemically, using x-ray diffraction (XRD) and energy-dispersive x-ray spectroscopy (EDS), and ultrastructurally, using (scanning) transmission electron microscopy (TEM/STEM). Both adhesives revealed nano-layering at the adhesive interface, not only within the hybrid layer but also, particularly for Clearfil SE Bond (Kuraray), extending into the adhesive layer. Since such self-assembled nano-layering of two 10-MDP molecules, joined by stable MDP-Ca salt formation, must make the adhesive interface more resistant to biodegradation, it may well explain the documented favorable clinical longevity of bonds produced by 10-MDP-based adhesives.

DOI： 10.1177/0022034512437375

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Chitosan-GPTMS (γ-Glycidoxypropyltrimethoxysilane) hybrid hydrogels were synthesized with β-glycerophosphate (β-GP) as the additive agent. Chitosan-GPTMS sols were fluid at room temperature and transformed to hydrogel at 36.5°C in several min. The gelation time of the hydrogels was shortened by the addition of GPTMS. From NMR experiments, this gelation behavior depended on some factors, namely, electrostatic interaction between the phosphate groups of β-GP and the amino groups of chitosan chains, crosslinking between the epoxy groups of GPTMS and the amino groups of chitosan, and polycondensation of the methoxy groups of GPTMS. The Si(IV) released from the hydrogels promoted the cell adhesion and ALP activity of osteoblastic cells MG63. © (2012) Trans Tech Publications.

DOI： 10.4028/www.scientific.net/KEM.493-494.698

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記述言語：英語  

Injectable hydroxyapatite/collagen nanocomposite (HAp/Col) artificial bone was prepared utilizing gelation of sodium alginate (Na-Alg). Mass ratio of the HAp/Col powder, with or without Ca adsorption treatment and Na-Alg (80-120, 300-400, 500-600 cP in viscosity at 10 g/dm 3) was fixed at 90/10. Injectable HAp/Col was prepared by mixing the HAp/Col powder with Na-Alg solution at several powder (HAp/Col)/liquid (Na-Alg solution) ratios (P/L ratio, g/cm 3). The result of consistency measurement suggested that the operability of injectable HAp/Col paste could be controlled by both the P/L ratio and the viscosity of Na-Alg solution. According to the consistency measurement and practical feelings during mixing, P/L=1/1.67 (80-120 cP) and 1/1.89 (300-400, 500-600 cP) were considered to be the highest P/L ratio allowed to mix the HAp/Col paste with a spatula. At the P/L=1/2.33 (80-120 cP), the paste prepared with the non-treated HAp/Col powder, placed in an incubator (37 °C,relative humidity 100%) for 24h, demonstrated gellike property, while the paste prepared with Ca-treated HAp/Col powder did putty-like property. The difference in their property might be caused by the initial bonding behavior between Alg and Ca 2+ after mixing. The setting time measurement with Gillmore needle was impossible because they were toosoft for this method. Even though, their operability and coalescence/settingproperty could be used as the injectable bone filler. © (2012) Trans Tech Publications.

DOI： 10.4028/www.scientific.net/KEM.493-494.689

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記述言語：英語  

A recently developed "GRAPE® technology" provides titanium or titanium alloy implants with spontaneous apatite-forming ability in vitro, which requires properly designed gaps and optimum heat treatment in air. In this study, pure titanium pieces were thermally oxidized in air and pre-irradiated by UV-light under different environmental conditions such as in air or in ultra-pure water before aligning pairs of specimens in the GRAPE® set-up, i.e., two pieces of titanium substrates were aligned parallel to each other with optimum gap width (spatial design). Then, they were soaked in Kokubo's simulated body fluid (SBF, pH7.4, 36.5°C) for 1-2 days to clarify how the UV-light pre-irradiation affects the in vitro apatite nucleation on the substrates under the specific spatial design. UV-light pre-irradiation in water led to the deposition of a large number of apatite particles within 1 day, and showed apatite X-ray diffraction, although UV-light pre-irradiation in air and non-pretreated specimens gave the deposition of a few apatite particles and did not show any apatite X-ray diffraction. These results indicated that the rate of primary heterogeneous nucleation of apatite increased by UV-light pre-irradiation in ultra-pure water. TFXRD patterns of the surface of the substrates thermally oxidized in air at 500°C showed the peak at 2θ= 27° assignable to the 110 diffraction of rutile phase of titanium dioxide (ICDD-JCPDS data #21-1276). Previous studies reported that the primary heterogeneous nucleation must be induced by Ti-OH groups on titanium oxide layer. Probably, the UV-light pre-irradiation in ultra-pure water can increase the number of Ti-OH groups on the surface, resulting in accelerated primary heterogeneous nucleation of apatite. © (2012) Trans Tech Publications.

DOI： 10.4028/www.scientific.net/KEM.493-494.936

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Silica gel macrospheres of a few millimeters in diameter were fabricated via the sol-gel route using water glass, calcium chloride, and sodium alginate as the precursor components. TiO2 coating on the silica gel macrosphere surface was conducted by soaking them in titania sol derived from hydrolysis of tetraethylorthotitanate (TEOT) under varied pH (HNO3), and temperature (50-80°C). X-ray diffraction analysis indicated deposition of anatases, and particular deposition (<1μm) on the surface was confirmed by scanning electron microscopy. Protein adsorption behavior was examined as a function of pH of the hydrolysis of TEOT, using bovine serum albumin (BSA) and lysozyme (LSZ) as the model proteins. BSA adsorption was little affected by the pH, while some effects were found for LSZ adsorption. BSA adsorption saturated at 20-25 min contact, while LSZ adsorption took longer time for the saturation. Moreover, BSA was adsorbed almost twice as much as LSZ, when saturation adsorption was compared. An effect of residual calcium ions with better affinity to BSA was proposed for partial interpretation since surface charge could not account for those adsorption behaviors.

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記述言語：英語   出版者・発行元：NATL INST MATERIALS SCIENCE  

Silica nanotube fibrous meshes were fabricated as multiple functional matrices for both delivering bone morphological protein-2 (BMP-2) and supporting osteoblast attachment and proliferation. The meshes were fabricated via a collagen-templated sol-gel route and consisted of tubular silica with open ends. BMP-2 was loaded to the meshes by soaking in BMP-2 solution. The meshes effectively enabled the attachment and proliferation of osteoblast MC3T3-E1 cells and delivered bioactive BMP-2 to stimulate cell differentiation. These results demonstrate the potential use of the meshes in bone generation applications.

DOI： 10.1088/1468-6996/12/6/065003

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Following the "adhesion-decalcification" concept, specific functional monomers possess the capacity to primary chemically interact with hydroxyapatite (HAp). Such ionic bonding with synthetic HAp has been demonstrated for 10-methacryloyloxydecyl dihydrogen phosphate (10-MDP), manifest as self-assembled "nanolayering". In continuation of that basic research this study aimed to explore whether nanolayering also occurs on enamel and dentin when a 10-MDP primer is applied following a common clinical application protocol. Therefore, the interaction of an experimental 10-MDP primer and a control, commercially available, 10-MDP-based primer (Clearfil SE Bond primer (C-SE), Kuraray) with enamel and dentin was characterized by X-ray diffraction (XRD), complemented with transmission electron microscopy interfacial ultrastructural data upon their reaction with enamel and dentin. In addition, XRD was used to study the effect of the concentration of 10-MDP on nanolayering on dentin. Finally, the stability of the nanolayers was determined by measuring the bond strength to enamel and dentin when a photoinitiator was added to the experimental primer or when interfacial polymerization depended solely on the photoinitiator supplied with the subsequently applied adhesive resin. XRD confirmed nanolayering on enamel and dentin, which was significantly greater on dentin than on enamel, and also when the surface was actively rubbed with the primer. Nanolayering was also proportional to the concentration of 10-MDP in the primer. Finally, the experimental primer needed the photoinitiator to obtain a tensile bond strength to dentin comparable with that of the control C-SE primer (which also contains a photoinitiator), but not when bonded to enamel. It is concluded that self-assembled nanolayering occurs on enamel and dentin, even when following a clinically used application protocol. The lower bonding effectiveness of mild self-etch adhesives to enamel should be ascribed in part to a lower chemical reactivity (nanolayering) with enamel HAP. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2011.04.026

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記述言語：英語   出版者・発行元：WILEY-BLACKWELL  

This study proposes a new guideline for designing biodegradable apatite ceramics. Boron-containing hydroxyapatite (BHAp) particles were prepared by a high-temperature solid-state reaction processing method and were characterized in terms of their chemical composition, apatite lattice defects and in vitro biodegradability. Solid-state nuclear magnetic resonance analysis showed that boron-incorporation into hydroxyapatite (HAp) derived by thermo-chemical reactions between borate and calcium phosphate phases led to disordered phases (BCaP) of a CaO-P2O5-B2O3-OH system covering the crystalline HAp core. X-ray diffraction analysis indicated that the BCaP phase must consist mainly of a crystalline oxyboroapatite (OBAp) phase. An in vitro biodegradability test showed that BHAp degraded quicker than HAp or beta-tricalcium phosphate. The biodegradability of BHAp particles can be controlled by boron incorporation into a HAp lattice leading to the formation of a disordered OBAp phase.

DOI： 10.1111/j.1551-2916.2011.04400.x

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記述言語：英語   出版者・発行元：SAGE PUBLICATIONS INC  

Previous research, in which the bonding effectiveness of the 3 self-etch monomers HAEPA, EAEPA, and MAEPA was determined, showed that MAEPA was most effective. In this study, the molecular interactions of these monomers with hydroxyapatite and dentin were investigated by combining x-ray diffraction, infrared spectroscopy, and scanning electron microscopy. We tested the null hypothesis that the bonding performance of these monomers does not correlate to the formation of monomer-calcium salts and to hydrolytic stability of these monomer-calcium complexes. Monomer/ethanol/water solutions were prepared and applied to synthetic hydroxyapatite and dentin. While HAEPA and EAEPA dissolved dentin considerably and deposited unstable calcium-phosphate salts (DCPD), MAEPA formed hydrolysis-resistant monomer-calcium salts that remained attached to the dentin surface even after being washed. The chemical stability of the monomer-Ca salts was thought to contribute in particular to the bond durability, but this study shows that the formation of stable monomer-calcium salts also enhances the 'immediate' bonding performance of self-etch adhesives.

DOI： 10.1177/0022034510397197

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Novel strategies for regenerating or reconstructing damaged bone tissues are of urgent necessity, because of limitations in conventional therapies for trauma, congenital defects, cancer, and other bone diseases. The tissue engineering approach to repair and regeneration is founded upon the use of biodegradable polymer scaffolds, which may manipulate bone cell functions, encourage the migration of bone cells from border areas to the defect site, and provide a source of inductive factors to support bone cell differentiation. During the past decades, scaffolds from natural biodegradable polymers such as collagen, gelatin, fibrin, and alginates, or synthetic biodegradable polymers such as polyglycolide, polylactides, and copolymers of glycolide with lactides have been extensively explored. On the other hand, it has been confirmed that the bonelike apatite layer, deposited spontaneously on the biomaterial surfaces, can enhance osteoconductivity. The presence of such bone-like apatite layers is also believed to be a prerequisite to conduction of osteogenic cells into various porous scaffolds or onto the surface of bioactive glasses. The formation of such bone-like apatite is favored by the cooperative behavior of a hydrated silica or titania gel surface with many Si-OH or Ti- OH groups, and calcium ions to be released into the body fluid when implanted. Thus, hybrid materials derived from the integration of biodegradable polymers with bioactive inorganic species may construct a new group of scaffolds appropriate for tissue engineering. Moreover, tissue engineering approach depends on the use of porous scaffolds that serve to support and reinforce the regenerating tissue. Controlled porous structures of these scaffolds allow cell attachment and migration, tissue generation, or vascularization. We have been studying the synthesis of novel chitosan-silicate hybrids derived from the integration of chitosan and γ-glycidoxypropyltrimethoxysilane (GPTMS). We introduce some of the results on this hybrid for biomedical application. © 2012 by Nova Science Publishers, Inc. All rights reserved.

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

A flow-micro-reactor system was employed to fabricate hydroxyapatite (HAp) in order to mimic the interface between calcium and phosphate solutions on a wet chemical procedure. The mixing ratio of calcium nitrate tetrahydrate and diammonium hydrogenphosphate solution was set to the stoichiometric atomic ratio HAp, 1.67, while pH value of the product suspension was varied from 6.4 to 10.0. The product morphology was changed from nano-sheet type to nano-particle type via nano-rod one, while their size was decreased from 100-500 nm to 50 nm. All as-prepared samples, irrespective of pH value of the resultant suspension, consisted of HAp, predominant phase, octacalcium phosphate (OCP), and dicalcium phosphate dihydrate (DCPD) or dicalcium phosphate anhydrate (DCPA). A batch system using the same solutions yielded very similar results, which confirmed that the reactions in this micro-reactor well reproduced a large-scale mixing system. Calcining sample obtained from pH 6.4 suspension for 2 h at lower temperatures (<400 degrees C) lead to decomposition of DCPD, DCPA, and OCP. Trace tricalcium phosphate (TCP) appeared on calcination above 400 degrees C. HAp remained the predominant phase throughout the process. After calcination at 600 degrees C, no other phases than HAp and TCP were present in the product. The analyzed ratio Ca/P (1.38) implied that those crystalline phases were highly Ca-deficient, and that amorphous calcium phosphates were involved in both as-prepared and calcined sample pH 6.4. (C)2011 The Ceramic Society of Japan. All rights reserved

DOI： 10.2109/jcersj2.119.116

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Fabrication of an assembly of nm-sized rods or wires of hydroxyapatite (HAp) would mimic the structure of dentin or enamel when they are tailored to align each other along a specific crystallographic axis. This study proposed new strategy for self-assembling one-dimensional HAp nano-rods with an organized superstructure. We prepared a nm-scale rod array of HAp having preferred orientation to the c-axis simply by soaking calcium-containing silicate glass substrates in aqueous Na2HPO4 solutions at 80°C for various periods, as inspired by the glass-apatite conversion procedure. Those HAp rods grew up perpendicularly to the glass surface, and the crystallites covered the glass entire surface uniformly, resulting in "dental enamel-like" rod array structure.

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Among several techniques proposed for fixing titanium bone implant in bone tissues by inducing apatite deposition on the implant surface, "GRAPE® Technology" is the simplest one, where optimum size of macro-grooving and heating in air are provided for pure titanium because samples with such grooves deposit apatite when soaked in an aqueous solution mimicking human blood plasma. The technique is needed to be confirmed by in vivo tests if it is effective for bone tissues, or if it is applicable to newly developed titanium alloy systems. In this study, the validity of GRAPE® Technology for a Ti-15Zr-4Ta-4Nb alloy was assessed with both in vitro and in vivo experiments. Here, alloy pieces with macro-grooves 500 μm in depth and 500 μm in width were heated at 500°C to induce thin titania layers on the surface. In vivo tests confirmed bone-ingrowth within 3 weeks in the samples with the macro-grooves but very less for those without the grooves. Those results indicated that GRAPE® Technology is effective for providing the Ti-15Zr-4Ta-4Nb-based implants with osteoconductivity.

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Chitosan-gamma-glycidoxypropyltrimethoxysilane (GPTMS)-tetraethoxysilane (TEOS) hybrid membranes were prepared by the sol-gel method. The effects of Si(IV) released from them on cell proliferation and differentiation were examined in terms of cell metabolic activity and the alkaline phosphatase (ALP) activity of MG63 osteoblastic cells. The amount of Si(IV) released from the hybrid membranes increased with the TEOS content. The released Si(IV) inhibited cell proliferation but promoted cell differentiation. Thus, the osteocompatibility of the chitosan hybrid membranes in the chitosan-GPTMS-TEOS system can be controlled by the amount of Si(IV) released from them when they are applied to cell culture. (C) 2010 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.118.989

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE BV  

Titanium and its alloys are employed as artificial joints, bone plates, wires, screws and bone prostheses in orthopedic and dental fields, because of their high corrosion resistance, good mechanical properties, and biocompatibility. Since they cannot directly bond to living bone-tissue through stable chemical interactions, a few surface modification techniques have been proposed for giving materials apatite-forming ability that secures bone-tissue bonding, such as chemical treatment with H2O2 or NaOH, electrochemical oxidation, electrophoretic apatite particle deposition, and UV-irradiation of surface titanium oxide layer. This study examined how the combination of H2O2 chemical treatment and UV-irradiation affected in vitro apatite-formation on TiO2 (anatase phase) layers as UV was irradiated under a few different conditions. TiO2 layer was prepared by the chemical treatment with H2O2 solution and subsequent heat-treatment (CHT). CHT samples were irradiated with UV-light for 1 h in air or in ultra-pure water. They were then soaked in Kokubo's simulated body fluid (SBF; pH 7.4) at 36.5 degrees C for 1 day. Their surface structure and morphology were examined by using a thin film X-ray diffractometer (TF-XRD), and a scanning electron microscope (SEM). The UV-irradiation of CHT in air reduced the number of active sites for apatite nucleation. On the contrary, however, the UV-irradiation in water increased them. These opposite results indicate that environmental factors of the UV-irradiation are important for controlling the in vitro apatite-forming ability of anatase layer. (C) 2009 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.mseb.2009.11.013

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A micro-chemical process was applied to prepare nanometer-size hydroxy apatite (HA) particles with various shapes and sizes so as to provide high surface activities, where solutions of reagent-grade calcium nitrate tetrahydrate and diammonium hydrogen phosphate were introduced in a micro reactor. The particles were characterized by X-ray diffractometry, transmission electron microscopy, or inductively coupled plasma photometry. Particle size and shape were dependent on not only pH and concentration of the mixing solutions but also the flow rate. Dilute solutions containing 3 mM Ca(II) and 5 mM P(V) yielded spherical HA particles, whose average particle size increased from about 3 nm to 40 nm as the flow rate increased from 0.3 to 3 ml·min-1, where pH and the temperature of the reaction system were respectively maintained at 10 and at 40°C. Concentrated solutions with 50 mM Ca(II) and 30 mM P(V) yielded rectangular plate-like HA particles, 300 nm long and 50 nm wide, when pH was kept at 8, while agglomerations of smaller HA particles of about 20-50 nm were obtained when pH was kept at 10.

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Effects of nanometer-scale surface roughness of titanium oxide layer on the adhesion and proliferation of osteoblast-like cell were examined. The nano-structured titanium oxide layer was prepared on titanium substrates by chemical treatment and heat-treatment. The anatase or rutile phase of titanium oxide was formed on the titanium substrates. The surface roughness of titanium oxide layer depended on the chemical treatment time or the heat-treatment time. The average roughness (Sa) was controlled in the range from 10 to 70 nm. The cell metabolic activity increased on the substrate with limited surface roughness. It is found that cell proliferation is affected by nanometer-scale surface roughness of titanium oxide layer.

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Although decayed/fractured teeth can be reconstructed minimally invasively and nearly invisibly using adhesive technology, the clinical longevity of dental composite restorations is still too short. Water sorption is thought to be the principal cause of destabilization of the biomaterial-tooth bond. However, the actual mechanisms of interfacial degradation are far from understood. Here we report how nano-controlled molecular interaction at the biomaterial-hard tissue interface can improve bond durability. The use of functional monomers with a strong chemical affinity for the calcium in hydroxyapatite is essential for long-term durability. Correlative X-ray diffraction and solid-state nuclear magnetic resonance disclosed a time-dependent molecular interaction at the interface with stable ionic bond formation of the monomer to hydroxyapatite competing in time with the deposition of less stable calcium phosphate salts. The advanced tooth-biomaterial interaction model gives not only an insight into the mechanisms of bond degradation, but also provides a basis to develop functional monomers for more durable tooth reconstruction. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2010.03.024

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Pure titanium pieces were air-oxidized and autoclaved at 121 degrees C for 20 min before aligning various pairs of specimens in the GRAPE (R) set-up, i.e., two pieces of rectangular substrates were aligned parallel to each other with optimum gap width (spatial design). Then, they were soaked in Kokubo's simulated body fluid (SBF) for 7 days to clarify how the autoclaving is to affect the in vitro apatite-forming ability on the substrates under the specific spatial design. Autoclaved specimens deposited a larger number of apatite particles, and showed stronger apatite X-ray diffraction than the specimen only heated in air. X-ray photoelectron spectroscopy (XPS) analysis indicated that the amount of chemically adsorbed OH and Ti-OH groups on the thermally oxidized titanium specimens increased by autoclaving. These results lead to the conclusion that the increase of Ti-OH groups and OH(s) and H2O groups on the surface enhanced the in vitro apatite-forming ability on spatial design. (C)2010 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.118.483

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A new type of hyperthermia or magnetic resonance imaging materials with bone-bonding ability was explored within the framework of magnetic-bone mineral composite ceramics. That is, hydroxyapatite (HAp) nanoparticles, hybridized with ferrous (Fe2+) and ferric (Fe3+) ions (Fe(II) and Fe(III)), were synthesized through the wet chemical procedure, and characterized in terms of crystal structures, magnetic properties and protein adsorption properties. The as-synthesized particles derived from precursor solutions with FeCl2 consisted of hydroxyapatite (JCPDS 09-0432) (20-30 nm in size) and magnetite (JCPDS 19-0629) (2-5 nm in size). They showed super-paramagnetic behavior, yet their saturation magnetization increased with the content of Fe(II) in the solutions up to 4.3 emu/g. From TEM observations, the HAp particles were rod-like, by which the magnetite particles that seemed spherical rather than showing cubic morphology, were surrounded. The particles from the solutions with Fe(III) gave only HAp, and hence Fe(III) was considered to form an amorphous phase. Moreover, Fe(III) incorporation suppressed HAp crystal growth.

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Silica particles and their derivatives with meso-structure attracted much attention, but they were synthesized through complicated multi-step procedure. Considering biomedical application, no surfactants, used in almost all cases above, should be employable due to fear of their toxicity. The present study explored one-step sol-gel preparation of silica particles with biomedical functionalities, starting from Stöber-type systems, and characterized by Transmission Electron Micrograph or 29Si MAS NMR spectroscopy. The Ca-containing particles, derived from the precursor system tetraethoxysilane (TEOS)-H2O-C2H5OH (EtOH)-CaCl 2-NH4OH, consisted of primary particles of - IO nm, and were spherical in shape with the diameter of - 1000 nm, where Ca bridged Si-O- on the opposite particle surface. In contrast, the Ca-free particles were smaller with 400-500 nm in size due to the absence of such bridging effects. In addition, the Ca-containing ones deposited petal-like apatite within one week in Kokubo's simulated body fluid (SBF), which was interpreted in terms of the Ca release from the particles. Amino-modified silica particles were derived from the sol-gel precursor system aminopropyltriethoxysilane (APTES)-TEOS-H 2O-EtOH where APTES behaved not only as the catalyst but also a reactant; i.e., this was a self-catalyzed sol-gel system. Hydrogen bonding among the amino group of APTES on one particle surface and with Si-O- on the other was suggested to work in agglomeration of the primary particles. Bovine serum albumin was covalently fixed on the APTES-silica surface, suggesting their applicability of proteins or other growth factor delivery.

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記述言語：英語   出版者・発行元：ROYAL SOC CHEMISTRY  

Organosilica hybrid particles were derived for the first time from a catalyst-free neutral sol-gel system of vinyltrimethoxysilane, tetramethoxysilane, ethanol, and water and consisted of T species (CH(2) = CH-Si(-O-Si)(n)(OH, OCH(3))(3-n), n = 2 and 3) and Q species (Si(-O-Si)(n)(OH, OCH(3))(4-n), n = 2, 3, and 4). After combined with poly(methylmethacrylate) and CaCl(2), they induced deposition of bioactive apatite in the Kokubo's simulated body fluid and are applicable for bone regeneration.

DOI： 10.1039/c0jm01546f

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記述言語：英語  

Ca-Sr-Zn-Si glasses have demonstrated excellent biocompatibility both in vitro using the MTT assay with L929 mouse fibroblast cells, and in vivo using healthy and ovariectomized female Wistar rats. However, the biological evaluation of the materials was performed on glass granules that were autoclaved, rather than γ-irradiated; the sterilisation procedure required prior to implantation of these materials in the human body. Given the fact that when a glass is exposed to ionizing radiation changes in its physical properties can take place, it is imperative to determine whether the structure of such glasses will be altered as a result of exposure to the typical amounts of γ-irradiation required to sterilise such materials prior to implantation. This paper examines the structure of Na-Ca-Sr-Zn-Si glasses using 29Si MAS-NMR, XRD and DTA and to evaluate the effect of 30 kGy γ-irradiation on their structure. The 29Si MAS-NMR results indicate that the peak maxima for each glass remains between -74 ppm and -79 ppm; a chemical shift for 29Si associated with Q1 units in silicate glasses, and that the local environment around the 29Si isotope remains unaltered as a result of exposure. Additional analysis (DTA and XRD) showed that the onset of the glass transition temperature, Tg (in the range 553 °C-619 °C depending on composition) typically remains unchanged, as a result of exposure to the ionizing radiation, as do the XRD diffractograms for each glass. Therefore it can be concluded that the use of 30 kGy γ-irradiation does not effect the local environment of the 29Si isotope in the glasses, nor does it significantly alter the XRD diffraction patterns or the Tg values for CaO-SrO-NaO-ZnO-SiO2 described in this work. © 2009 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jnoncrysol.2009.07.014

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記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

The pore structure of hard carbon samples made from two kinds of phenolic resins by heating between 1073 and 1473 K was investigated by Xe-129 NMR. The difference of porous structure of hard carbon samples by heat treatment temperature, which was difficult to analyze precisely by general gas adsorption methods, could be evaluated by XeNMR at an equilibrium state of xenon gas adsorption. Carbon samples produced by heating precursors under a 0.1 MPa xenon atmosphere showed stronger NMR signals than carbon heated at reduced pressure, despite their almost identical powder X-ray diffraction (XRD) patterns. Applying this method, the dependence of NMR spectra on heating temperature between 1073 and 1473 K was examined. A carbon sample consisting of smaller particles showed almost constant shift values at about 102 ppm, while the peak of another sample with larger particles shifted between 118 and 82 ppm depending on the heating temperature. Then, almost all entrances of each sample closed above 1273 K. Using NMR with the improved heat-treatment by xenon gas, we evaluated pores in hard carbon that were hard to access from the outer surface of the hard carbon.

DOI： 10.1246/bcsj.82.1232

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記述言語：英語   出版者・発行元：WILEY-BLACKWELL PUBLISHING, INC  

Agglomerated amino-modified silica nanoparticles were prepared from a novel Stober-like precursor system consisting of aminopropyltriethoxysilane (APTES), tetraethoxysilane (TEOS), ethanol, and water where the molar ratio APTES/TEOS was 0, 0.1, 1.0, and 2.0, and the molar ratio H(2)O/-SiOC(2)H(5) was about 20 to 60, or great excess amounts of H(2)O were employed. APTES catalyzed the hydrolysis and condensation of both silanes. (29)Si magic angle spinning nuclear magnetic resonance spectra confirmed that the particles consisted of Q(n) species (Si(OSi)(n)(OH)(4-n); n=2, 3, 4) and T(n) species (NH(2)(CH(2))(3)-Si(OSi)(n)(OH)(3-n); n=2, 3). The APTES content in the precursor solutions controlled the agglomerating spherical particle size and morphology: 0.1 in the ratio APTES/TEOS led to almost independent spheres of 300-400 nm, while the larger ratios 1 and 2 led to similar to 250 and similar to 150 nm spheres, respectively, that were largely agglomerated and some were fused to look like peanut-shells. When soaked in Kokubo's simulated body fluid, those amino-modified particles deposited apatite. The mechanisms of particle formation and apatite deposition were discussed in terms of an intraparticle hydrated layer.

DOI： 10.1111/j.1551-2916.2009.03135.x

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Fabrication of nano- or micro-structured scaffolds to mimic structural and three-dimensional details of natural bone or teeth has been the subject of much interest, and this study proposes a new strategy for self-assembling one-dimensional hydroxyapatite (HAp) nanorods into organized superstructures. A nanometer-scale rod array of HAp having preferred orientation to the c-axis was successfully prepared simply by soaking calcium-containing silicate glass substrates in Na(2)HPO(4) aqueous solution at 80 degrees C for various periods. Those HAp rods grew perpendicularly to the glass surface, and the crystallites covered the glass surface uniformly, resulting in a "dental enamel-like" rod array structure consisting of "pine-leaf-like" structure units. (C) 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2009.02.018

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

Nuclear magnetic resonance (NMR) has been used for a detailed investigation of the borate incorporation in apatitic biomaterials prepared by high-temperature solid-state reaction sintering. The NMR data clearly show that crystalline hydroxyapatite (HAp) does exist, but it contains only about 30% of the entire phosphate content of the sample. The main phosphate content of about 70% forms a disordered calcium phosphate phase (BCaP) that accommodates the borate units in two structurally different trigonal BO(3)(3-) groups besides some minor linear BO(2)(-) units. The average chemical composition of BCaP was estimated from the NMR spectra. Furthermore, a structural model of these particles is proposed, where HAp forms the crystalline core of these crystals covered by the disordered BCaP, suggesting that the BCaP phase is responsible for the adhesion properties of organic molecules like proteins and not HAp that is the only significant crystalline phase (XRD). Furthermore, the presence of an interface between HAp and BCaP is discussed based on various NMR experiments, including a triple-resonant (11)B-(31)P cross-polarization edited (31)P NMR spectrum with subsequent (31)P{(1)H} REDOR (Rotational Echo DOuble Resonance) dephasing,

DOI： 10.1021/cm900204q

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE SA  

Multilayer anatase films were coated by sol-gel technology on various substrates such as stainless-steel, alumina, and glass, respectively. Their in vitro apatite-forming ability was examined by immersion in Kokubo's simulated body fluid (SBF; pH 7.4, 36.5 degrees C). Although on anatase layer on alkali-free glass apatite was deposited within 7 d, no apatite was found on anatase deposited onto stainless steel, alumina or glass substrates within 7 d to prove they were bioinert. X-ray photoelectron spectroscopy was able to detect chromium, aluminum, or sodium on the surface of the anatase films. This indicated that these ions possibly inhibited the in vitro apatite-forming ability. (C) 2009 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.surfcoat.2009.02.001

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記述言語：英語   出版者・発行元：SAGE PUBLICATIONS LTD  

We investigated synthetic conditions for the fabrication of bioactive hybrid gels from monomers of 2-hydroxyethylmethacrylate ( HEMA) and 3-methacryloxypropyltrimethoxysilane (MPS) in combination with CaCl2, at a starting molar ratio of HEMA: MPS: CaCl2 of 9:1:1. Hydroxyapatite formation, essential to show bone bonding, was observed on the HEMA-MPS-CaCl2 hybrid gels with the added catalysts NH3 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.

DOI： 10.1177/0885328208094262

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Amino-modified TiO2 particles were derived from precursor mixtures of tetraethylorthotitanate and aminopropyltriethoxysilane (APTES) that both were dissolved in ethanol/water solution. Size, morphology, crystalline structures, and formation mechanism of the particles were discussed in terms of the APTES amount and the pH value in the solution. The addition of APTES resulted in amorphous amino-modified TiO2 particles. The low crystallinity in the final particles was attributed to the polar amino groups. (C) 2009 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.117.537

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

We report on the effect of using a spatial gap on heterogeneous nucleation on the surface of thermally oxidized titanium substrates. Induction of heterogeneous nucleation of bone-like hydroxyapatite (BHAp) was evaluated in the spatial gaps between substrates that were thermally oxidized at temperatures of 100-800 degrees C on exposure to a simulated body fluid (SBF). After soaking in a SBF for 7 d, BHAp spontaneously deposited inside the gap on the surface of samples that were thermally oxidized at temperatures above 400 degrees C, but not on samples that were thermally oxidized at temperatures of 300 degrees C or less. Among the substrates studied, BHAp particles were most readily deposited inside the gap on the surface of the samples that were thermally oxidized at 400 degrees C after soaking in an SBF. A smaller gap led to a higher number of BHAp particles being deposited on the surface of the samples that were thermally oxidized at 400 or 500 degrees C. Our results suggest that the formation of BHAp in a SBF is dependent on the temperature during thermal oxidization, and also on the spatial gap between the samples. The ease of formation of BHAp on thermally oxidized titanium increases with increasing thickness of the rutile phase and the number of Ti-OH groups, which are produced during the thermal oxidization process. In addition to the surface structure of the substrates, the spatial gap is regarded as an important parameter for enhancing the deposition of BHAp. Since the formation of BHAp allows osteoconduction to occur after implantation in a bony defect, it is possible to design titanium-based implants with a high biological affinity to bone by processing using an appropriate spatial design of the substrate. (C) 2009 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.117.515

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The incorporation of ions in the lattice of hydroxyapatite alters significantly its structure. Particularly, if anions such as trigonal borate units are accommodated in the lattice severe distortions must occur around the substitution site because of different geometric shape, electric charge and anion size. Solid-state NMR has been used to investigate this problem in detail for a hydroxyapatite sample synthesized by high temperature solid state reaction. The results clearly verify the existence of network distortions. Indeed, only about 1/3 of the total phosphate content forms crystalline hydroxyapatite (also found in XRD) whereas the residual amount is contained in two different phosphate sites with 31P chemical shifts of 5.5 ppm and 2.3 ppm, but broad resonances lines suggesting disorder. Furthermore, a novel proton signal at -0.6 ppm was found which is directly associated with the borate incorporation. No specific correlation of the two structurally different borate units with the two phosphate groups is found.

DOI： 10.4028/0-87849-353-0.205

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

We attempted to prepare chitosan-silicate hybrid for use in a medical application and evaluated the physico-chemical properties and osteocompatibility of the hybrids as a function of gamma-glycidoxypropyltrimethoxysilane (GPTMS) concentration. Chitosan-silicate hybrids were synthesized using GPTMS as the reagent for cross-linking of the chitosan chains. Fourier transform infrared spectroscopy, (29)Si Cp- MAS NMR spectroscopy and the ninhydrin assay were used to analyze the structures of the hybrids, and stress-strain curves were recorded to estimate their Young's modulus. The swelling ability, contact angle and cytocompatibility of the hybrids were investigated as a function of the GPTMS concentration. A certain fraction of GPTMS in each hybrid was linked at the epoxy group to the amino group of chitosan, which was associated with the change in the methoxysilane group of GPTMS due to hybridization. The cross-linking density was around 80% regardless of the volume of GPTMS. As the content of GPTMS increased, the water uptake decreased and the hydrophilicity of the hybrids increased except when the content exceeded amolar ratio of 1.5, when it caused a decrease. The values of the mechanical parameters assessed indicated that significant stiffening of the hybrids was obtained by the addition of GPTMS. The adhesion and proliferation of the MG63 osteoblast cells cultured on the chitosan-GPTMS hybrid surface were improved compared to those on the chitosan membrane, regardless of the GPTMS concentration. Moreover, human bone marrow osteoblast cells proliferated on the chitosan-GPTMS hybrid surface and formed a fibrillar extracellular matrix with numerous calcium phosphate globular structures, both in the presence and in the absence of dexamethasone. Therefore, the chitosan-GPTMS hybrids are promising candidates for basic materials that can promote bone regeneration because of their controllable composition (chitosan/GPTMS ratio). (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2008.07.022

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Apatite formation on the surface of titanium and its alloys is effective for inducing osteoconductivity when implanted in bony defects. The aim of this study was to investigate the effects of thermal oxidation on apatite formation in macro-grooves on Ti-15Zr-4Ta-4Nb. Thermal oxidation at 500 and 600 degrees C in air led to modification of the Ti-15Zr-4Ta-4Nb surface to rutile phase titanium oxide. Ti-15Zr-4Ta-4Nb thermally oxidized at 500 degrees C in air showed no changes in metallographic structure, but not at 600 degrees C. After soaking in a simulated body fluid for 7 days, the formation of apatite could be observed on the internal surfaces of macro-grooves 500 mu m deep and wide on Ti-15Zr-4Ta-4Nb thermally oxidized at 500 and 600 'C in air. These results indicate the potential for osteoconductivity of Ti-15Zr-4Ta-4Nb without changing its metallographic structure, by fabricating only the macro-grooves, i.e., spatial design, and by performing thermal oxidation at 500 degrees C. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2008.07.014

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Bioactive porous silica particle coatings were fabricated on the stainless steel substrates as bone repairing implants to enhance the apatite deposition. The particles were prepared from tetraethoxysilane (TEOS) and cetyltrimethylammonium bromide (CTAB) via the sol-gel method and then calcined at 600°C for 2 h to produce the porous structure. Subsequently, the clean substrates were sequentially soaked in the chitosan, silica and calcium alginate solutions to obtain the chitosan/silica/calcium alginate coatings via the charged layer-by-layer deposition technique. The treated substrates deposited bioactive apatite when soaked in the Kokubo's simulated body fluid (SBF) and exhibited bioactivity. Thus, such bioactive porous silica coatings are applicable to the reservoirs for storing and releasing the bone factors.

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We have shown that the combination of advanced solid state NMR experiments [7] and ab initio calculations of NMR parameters can lead to a novel description of substituted HAp structures. In the case of silicate substitution, the anions located within the structure are unambiguously characterized by selective 1H → 29Si CP transfer and 31P → 29Si experiments can edit the 29Si MAS spectra in terms of 31P/29Si dipolar interaction. 2D heteronuclear interactions will be performed in a near future. In the case of carbonate substituted HAp, the study of the 1H → 13C dynamics allowed to fully characterize the various 13C sites. By combining NMR calculations starting from DFT models and experiments, distributions of A-, B- and A/B sites were clearly characterized.

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Nano- and micrometer-scale rod array structure of HAp having preferred orientation was successfully prepared by soaking calcium-containing borosilicate glass substrates in Na2HPO4 aqueous solution at 80°C for 7 days. Nano-scale HAp rods grew up perpendicularly to the glass surface, and the crystallites were arranged on the glass entire surface uniformly with preferred orientation to the c-axis.

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Carbonate- and Si-involving hydroxyapatite (C-HA, Si-HA) as well as hydroxyapatite (HAp) was prepared through wet chemical processes. Magic angle Spinning (MAS) NMR spectroscopy was applied together with Cross-Polarization (CP) techniques to study chemical environments around the guest oxo-anions. C-HA involved at least four carbonate sites, but the one for ∼168 ppm was left unassigned. In Si-HA, only Q0 (SiO44-) replaced the phosphate ion site but other Si atoms were polymerized and present on the surface or in the grain boundary of the Si-HA particles. The 31P MAS and CP-MAS spectra indicated the absence of HPO42- in the lattice, and suggested the presence of an amorphous phosphate phase on the particle surface.

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記述言語：英語   出版者・発行元：SPRINGER  

Prepared via Stober-type sol-gel routes were three types of silica particles of < 1 mu m in size: pure silica, Ca-involving silica, and chitosan/alginate-coated silica with a polymershell-silica core structure. Calcium ions were impregnated in the organic layers of the polymer-coated silica particle. The sol-gel procedure was applied to tetraethoxysilane dissolved in an ethanol/water mixture, while Ca-silica was derived from CaCl(2)-containing ethanol/water solutions. Scanning and transmission electron micrograph analyses indicated that those silica particles consisted of similar to 10 nm primary particles, the Ca-silica particles (similar to 500 nm) were larger than the Ca-free ones (similar to 200 nm) and that their size increased with the Ca concentration in the precursor solutions. From (1)H- and (29)Si- magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectra and (29)Si cross-polarization NMR spectra, the mechanism of primary particle agglomeration and degradation of the secondary particles in saline were discussed in terms of the content of H(2)O molecules and > Si-OH as well as hydrogen bonding interactions among them. In addition, the Ca-silica and core-shell silica deposited apatite in Kokubo's simulated body fluid. Thus, the present Ca-silica and polymer-coated silica particles were suggested to be applicable to injectable bone fillers for bone generation.

DOI： 10.1007/s10971-008-1823-z

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記述言語：英語   出版者・発行元：CHEMICAL SOC JAPAN  

Amino-functionalized silica nanoparticles smaller than 200 nm in diameter were directly prepared from precursor mixtures of tetraethoxysilane and aminopropyltriethoxysilane in ethanol/water solutions via a novel one-pot sol-gel procedure.

DOI： 10.1246/cl.2008.1170

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Nano-scale rod arrays of titania were fabricated on titanium surface by a glass phase topotaxy growth (GPT) method, which was featured by an interfacial reaction between sodium tetraborate coating and the preheated metallic titanium at elevated temperature. The samples were characterized by thin-film X-ray diffraction (XRD), scanning electron microscope (SEM), profilometer and contact angle measurement. Thin-film XRD analysis indicated that the nano-rod arrays were composed of pure rutile titania phase. SEM images showed that these rutile rods were 100-200 nm wide and 1-2 μm long. The nano-rod arrays had significantly higher average roughness (P < 0.05) and greater hydrophilicity (P < 0.05) compared to the control. Human embryonic palatal mesenchymal (HEPM) cells were grown to evaluate in vitro cell responses to the nano-rod array structures in terms of cell attachment and proliferation. An equivalent high attachment rate of 94% was observed after 4-h incubation, but a lower proliferation rate was observed on the nano-rod array after 12-day culture compared to the control (P < 0.05). © Springer Science+Business Media, LLC 2008.

DOI： 10.1007/s10856-008-3396-3

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Titania (anatase) gel powders were prepared by peptizing commercially available titania sols and heating them at temperatures up to 700 degrees C, as candidates for bilirubin adsorbents for blood purification therapy. Those titania particles were in contact with a protein solution containing bilirubin and bovine serum albumin that mimics the blood of bilirubinemia patients. The amount of free or direct bilirubin in the solution insignificant. Indirect bilirubin or a bilirubin complex with albumin was adsorbed on the anatase powders, the primary particle size of which was as large as or larger than the size of an albumin molecule. The surface charge and surface charge density were only minor factors in controlling the indirect bilirubin adsorption. The present results indicated that the size of primary particles and hydrophobicity were significant for the sol-derived anatase in terms of bilirubin adsorption, and both were controllable by the heating temperature and the time period. (C) 2008 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2008.02.024

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記述言語：英語   出版者・発行元：BENTHAM SCIENCE PUBL LTD  

In the brain after infarction or trauma, the tissue becomes pannecrotic and forms a cavity. In such situation, a scaffold is necessary to produce new tissue. In this study, we implanted a new porous gelatin-siloxane hybrid derived from gelatin and 3-(glycidoxypropyl) trimethoxysilane (gelatin-GPTMS) scaffolds into a brain defect, and investigated whether it makes a new brain tissue. In addition, vascular endothelial growth factor ( VEGF) was added on gelatin-GPTMS scaffolds and its effect on tissue regeneration was examined. At 30 days after the implantation, the marginal territory of the scaffolds became occupied by newly formed tissue. Immunohistochemical analysis revealed that the new tissue was constituted by endothelial, astroglial and microglial cells, some of which were labeled for bromodeoxyuridine (BrdU). Addition of VEGF promoted numbers of these cells. Thus, combination of gelatin-GPTMS scaffolds and VEGF is preferable for brain regeneration.

DOI： 10.2174/156720208784310204

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS LTD  

Silicon-substituted hydroxyapatite (Si-HAp) has shown promising properties such as high-bone remodeling around implants. So far, the techniques used for the structural characterization of the Si-HAp have given indirect evidence of the presence of silicon inside the structure (by X-ray and neutron diffraction). In this paper, we focus on Si-HAp derivatives obtained by a precipitation method (widely described in the literature). We demonstrate here by solid-state NMR spectroscopy that only a fraction of the silicon atoms are incorporated into the HAp lattice in the form of Q(0) (SiO44-) species, for 4.6 wt% Si-HAp. A large amount of silicate units are located outside the HAp structure and correspond to silica-gel units. All results were established through Si-29 MAS, H-1 -> Si-29 CP MAS and T1 rho(H-1) edited H-1 -> Si-29 CP MAS experiments. This last pulse scheme acted as a powerful editing sequence, leading to unambiguous spectroscopic conclusions, concerning the location of the SiO44- moieties. Copyright (C) 2008 John Wiley & Sons, Ltd.

DOI： 10.1002/mrc.2109

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE SA  

Chitosan-silicate hybrids with 3D porous structures were prepared with freeze-drying precursor solutions derived from chitosan and gamma-glycidoxypropyltrimethoxysilane (GPTMS). They were formed easily in any shape, such as sheets, pellets, disks, granules, and even roll-cakes. The pore size was strongly dependent on the freezing temperature: lower freezing temperature resulted smaller pores, about 110 mu m for the hybrids frozen at -20 degrees C, and about 50 mu m for those at -85 degrees C. The pore size was little dependent on the GPTMS content. In contrast, the GPTMS content affected porosity a littlie: similar to 80% for chitosan, and similar to 90% for the GPTMS-containing hybrids. Thus, their porous microstructure was controllable due to the freezing temperature and composition. MG63 osteoblastic cells were cultured up to 7 days on the porous hybrids. The cells adhered on the pore walls, proliferated, and migrated deep into the pore structure. It was thus concluded that the present chitosan-silicate hybrids were promising for tissue engineering scaffold applications. (C) 2007 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cej.2007.10.012

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記述言語：英語   出版者・発行元：WILEY-LISS  

Surface properties of implants are the keys for ensuring their long-lasting anchorage to the tissue. This study aims to develop a novel implant surface microstructure with high biocompatibility and ability of guided tissue formation. By a photolithography method, gold (Au) grids (1 X 1 mm(2) square lattices, 10 pm in grid-line width) were deposited on titanium substrates. They were oxidized with H2O2 solution to yield titania (anatase) layer, and the Au grid formed channels due to larger molar volume of anatase than Ti. L-Cysteine and type I collagen were then immobilized on them to yield the target substrates, CHT-Au-cys-col. Apatite deposited within 3 days when they were soaked in Kokubo's simulated body fluid, regardless of the protein coating, but not on the bottom of the Au channel. Osteoblast-like MC3T3-E1 cells were cultured on the CHT-Au-cys-col substrates, showing that (1) the cysteine-collagen coating promoted cell attachment and proliferation, and (2) the Au channels were filled with the cells which were aligned along the channel direction and were connected to the neighboring cells as well as attached to the channel wall with cytoplasmic extensions. The results thus ensured filopodial guidance for the substrates. (C) 2007 Wiley Periodicals, Inc.

DOI： 10.1002/jbm.a.31426

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記述言語：英語   出版者・発行元：JAPAN INST METALS  

Hydroxyapatite formation on the surface of materials in the body is an essential condition for demonstrating osteoconduction after implantation in bony defects. This paper reports a technique for providing hydroxyapatite formation properties to titanium metals by using specially designed surface topography followed by thermal oxidation. Two pieces of titanium thermally oxidized at 400 degrees C were set together in a V-shape with varied mouth opening. They showed the formation of hydroxyapatite on both facing surfaces after exposure to a simulated body fluid (SBF), when the gap height was approximately less than 600 mu m. Moreover, pure titanium specimens with macro-grooves less than 1000 pm in depth and 800 mu m in width were able to form hydroxyapatite deposits in SBF within 604.8 ks, after they were thermally oxidized at 400 degrees C for 3.6 ks. Hydroxyapatite also formed on the internal surfaces of macro-grooves made in Ti-15-Zr-4Ta-4Nb within 604.8 ks of soaking in SBF, after the sample was thermally oxidized at 500 degrees C for 3.6 ks, whereas it was not deposited on alloy made of Ti-6Al-4V extra low interstitial processed in the same way. These findings indicate that titanium and its alloys can be conferred with hydroxyapatite-forming ability, i.e. osteoconduction, within a controlled spatial gap and thermal oxidation. We conclude that bioactive titanium substrate showing osteoconduction can be produced by using a specially designed surface topography followed by thermal oxidation at an appropriate temperature.

DOI： 10.2320/matertrans.MBW200711

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Apatite formation on the surface of materials in body environment is an essential condition to show osteoconduction after implantation in bony defects. This study reports the novel technique for providing the apatite-forming ability to titanium metals by only controlling the spatial gap and thermal oxidation. Two pieces of titanium thermally oxidized at 400°C were set together like V-letter with varied mouth opening. They showed the formation of apatite on both facing surface after exposure to a simulated body fluid (SBF) proposed by Kokubo and his colleagues, when the gap was less than approximately 600 μm. Moreover, specimens with micro-grooves of 500 μum in depth and 200-1000 μm in width was able to form apatite in SBF with in 7 days, after they were thermally oxidized at 400°C These results indicated that the titanium metals were provided with apatite-forming ability, i.e. osteoconduction, due to controlled gap with thermally oxidized surface. Hence, we conclude that bioactive titanium substrate showing osteoconduction can be produced by designed machining followed by thermal oxidation at an appropriate temperature.

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Previous in vitro studies confirmed an improved cytocompatibility of chitosan-silicate hybrid membranes over chitosan membranes. The main goal of this study was to assess the in vivo histocompatibility of both membranes through subcutaneous implantations at different time periods, 1 week, 1, 2 and 3 months, using a sheep model. Chitosan membranes elicited an exuberant inflammatory response and were consequently rejected. The hybrid chitosan membranes were not rejected and the degree of inflammatory response decreased gradually until the third month of implantation. Histological evaluation also showed that these membranes can be resorbed in vivo. This study demonstrates that the incorporation of silicate into the chitosan solution improves its histocompatibility, indicating that the hybrid chitosan-silicate membranes are suitable candidates to be used in clinical applications.

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Porous chitosan-silicate hybrids were prepared by freeze-drying the precursor sol solutions synthesized from chitosan and 3- glycidoxypropyltrimethoxysilane (GPTMS). Degradability of and the release of cytochrome C in to phosphate buffer saline solution (PBS) were examined as a function of the GPTMS content. The hybrids were less degradable with larger GPTMS contents, and the cytochrome C release profile was so controllable as to give either burst release or slow one due to the GPTMS content. Thus, the present porous chitosan-silicate hybrids were considered applicable to drug delivery systems.

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Novel hybrid gels in the system gelatin-GPTMS-TEOS were prepared via a sol-gel route, and their ability to release Si(TV) was examined using MG63 osteoblast-like cell culture. The amount of Si released and the release rate were controllable by changing the mixing ratio of GPTMS and TEOS. In addition, the hybrids had biocompatible surfaces. It is expected that the hybrids will be utilized for the investigation of the effect of Si on cell differentiation and tissue regeneration.

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Boron-containing hydroxyapatite (BHAp) particles were synthesized by the wet chemical processing method and subsequent thermal treatment at the temperature ranging from 700-1200°C, and examined the effect of boron introduction on the microstructure of BHAp. The local structure around boron and phosphorus in the BHAp was analyzed by solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The heat-treatment above 700°C induced the thermal decomposition of HAp to β-TCP and then the chemical reaction between HAp and B(OH)3 was induced above 900°C, resulting in the formation of boron-substituted HAp particles accompanied by the formation of β-TCP and its transformation to α-TCP above 1200°C.

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Ultraviolet (UV) light was irradiated in air for 1 h on titania (anatase) films sol-gel derived on Ti, stainless steel, alumina, and glass slide substrates, coded as C5Ti, C5SUS, C5Al2O3 and C5GS, respectively. They were then soaked in a simulated body fluid (SBF, Kokubo solution) and their apatite-forming ability (bioactivity) was evaluated. UV light irradiated C5SUS deposited bone-like apatite within 7 days whereas C5SUS did not within 7 days. Moreover, the apatite was deposited faster on UV light irradiated C5Ti than on C5Ti without UV light irradiation, whereas UV light irradiated C5GS, C5A12O3 and C5GS did not apatite within 7 days. Therefore, the ultraviolet light irradiation was confirmed to enhance in vitro apatite-forming ability of the sol-gel derived titania films on various substrates, but the effect depended on substrates.

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Hydroxyapatite (HAp) and Si-containing hydroxyapatite (SiHAp) particles were synthesized by a wet chemical method. Local structures around Si, P and H in the hydroxyapatites were analyzed by solid-state magic-angle spinning nuclear magnetic resonance spectroscopy. In vitro solubility of those SiHAp particles was evaluated by soaking them in acetic acid/acetate buffer solution (pH=4.0) at 36.5°C. As the Si content increased, the in vitro solubility of the SiHAp particles increased, while their crystallite size changed little.

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Nano-crystalline Mg-containing hydroxyapatite (MgHAp) were prepared by a wet chemical method, for which selective adsorption of proteins was examined, taking bovine serum albumin (BSA) and a pathogenic protein β2- microglobulin (β2-MG) as the model proteins. Increase in the Mg content led to smaller crystallites and larger specific surface area (SA) of MgHAps as well as zeta potential, while the amount both of BSA and β2-MG adsorption on MgHAp particles. It is thus concluded that the adsorption of BSA and β2-MG on Mg·HAp was associated with surface charges.

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記述言語：英語  

Sol-gel preparation of few organic-inorganic hybrids have been reviewed briefly as well as their behaviors under contact with blood plasma using a simulated body fluid (SBF) of the Kokubo recipe mimicking plasma. The starting resources of the hybrids included not only such silanes as poly(dimethylsiloxane) (PDMS), 3-glycidoxypropyltrimethoxysilane (GPTMS), tetraethoxysilane (TEOS), and titanium tetra-isopropoxide, but gelatin and chitosan. Apatite deposition in SBF was examined for the solid hybrids or membranes, and cell compatibility was assessed on proliferating osteoblastic cells (MC3T3E1, MG63). In addition, 3-dimensional interconnected pore structure was established for those hybrids, for which the possibility for scaffold and bioreactor applications was examined in terms of cell proliferation of human hepatocytes or keratinocytes. Gelatin-GPTMS and PDMS-TEOS scaffolds were implanted in brain defects to see no inflammation. Nerve cell tissue regeneration was observed, which was enhanced by the impregnation of growth factors, like bFGF and VEGF. With observing those empirical data, the silane based organic-inorganic hybrids have been considered very promising for tissue regeneration scaffolds. © 2008 Trans Tech Publications.

DOI： 10.4028/0-87849-395-6.167

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記述言語：英語   出版者・発行元：Elsevier Inc.  

DOI： 10.1533/9781845694227.1.53

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

Ultraviolet (UV) light was irradiated in air for 1 h on titania (rutile) films prepared by thermal oxidation of titanium substrates from 300°C up to 800°C, coded as HT300UV, HT400UV, HT500UV, HT600UV, HT700UV, and HT800UV, respectively. All samples were then soaked in a simulated body fluid (SBF, Kokubo solution) and their in vitro apatite-forming ability was evaluated. It was found that bone-like apatite particles were deposited on HT500UV, HT600UV, and HT700UV within 7 d whereas that was not the case with others during the same period. Moreover, the apatite particles were deposited more on HT500UV than on the others. Therefore, the ultraviolet light irradiation enhanced the in vitro apatite-forming ability of the thermally oxidized titanium. ©2008 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.116.530

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記述言語：英語   出版者・発行元：IOS PRESS  

Among the clinical treatments of Familial Hyper cholesterolemia patients to reduce the concentration of low density lipoprotein (LDL), blood purification therapy is most suitable in which a blood-compatible adsorbent is employed. In the present study, alumina powders were prepared via a sol-gel route to develop a LDL-adsorbent Aluminum tri2-propoxide was hydrolyzed and subsequently calcined up to 1200 degrees C. Surface charge density and pore size distribution were measured, and the phases were identified. The alumina calcined above 400 degrees C had excellent blood compatibility in terms of endogenous clotting parameters, i.e., partial thromboplastin time: (PTT), prothrombin time: (PT), and the amount of fibrinogen: (Fib). The amount of LDL-adsorption (Delta W-LDL) increased with the calcining temperature, showing a good linear correlation to surface charge density. The 1200 degrees C sample consisted only of a-alumina, and was greatest in Delta W-LDL. All samples involved pores smaller than 20 nm but not the pores large enough to accommodate LDL molecules (20-25 nm). From those results, it was concluded for the present alumina particles that the surface charge density was the primary factor and that the chemical activity of a-alumina also contributed to the excellent LDL-adsorption for the 1200 degrees C sample, while entrapping LDL in the pores was not an active mechanism.

DOI： 10.3233/BME-2008-0519

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The local structure around hydrogen atoms, phosphate ions and carbonate ions in nano-crystalline nonstoichiometric hydroxy-carbonate apatite was investigated in this study. The use of C enriched precursors allowed to perform 1D and 2D CP MAS HETCOR (HETeronuclear CORrelation) experiments with 13C as a target spin. 2D triple resonance experiments involving the 1H/13C/31P spins were also performed. All these experiments led to the partial editing of the corresponding projection spectra and revealed fine structural details for the corresponding material. At least four 13C peaks, corresponding to carbonate ions in A-sites (OH) and B-sites (PO43-) were evidenced. © 2007 Materials Research Society.

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Background: Injury of the central nervous system (CNS) of mammals may cause irreparable damage due to the limited regeneration capacity of the tissue. In order for the CNS tissue to regenerate, to supply a scaffold for the newly produced cells to adhere is necessary. Application of biodegradable polymers such as collagen, gelatin, fibrin and alginates has been investigated for organ damage other than the CNS. In this context, we recently produced a novel biomaterial from polydimethylsiloxane (PDMS) and tetraethoxysilane (TEOS). We added the most potent angiogenic factor vascular endothelial growth factor (VEGF) and observed the difference in brain regenerative process in the PDMS-TEOS scaffold. Methods: Male Wistar rats of 12 weeks old were anesthetized and placed in a stereotaxic apparatus. A piece of bone over the right frontal cortex was excised, and 2 x 5 mm defect in the brain was made by cutting and aspiration. The defect was positioned from 1.0 mm anterior to 4.0 mm posterior of the bregma and 2.0 to 4.0 mm lateral to the midline. The depth of the lesion was 2.0 mm from the brain surface. The block of PDMS-TEOS scaffold, with or without VEGF, was placed into the lesion immediately after making the defect. The animals were sacrificed at 30 days after PDMS-TEOS scaffold implantation. For histological analysis of the newly formed tissue, the sections were stained with HE. In order to identify cell types in the newly formed tissue, we performed immunohistochemical analysis for glial fibrillary acidic protein (GFAP), an astrocyte marker, and N-acetylglucosamine oligomer (NAGO), an endothelial cells marker. In order to determine whether the cells in PDMS-TEOS scaffold were under mitosis, we carried out double fluorescent study for cell phenotype markers and Ki67. Result: The PDMS-TEOS scaffold remained at the implanted site for 30 days and kept the integrity of brain shape (Fig. A and B). HE staining showed that a small number of cells infiltrated into the PDMS-TEOS scaffold even without VEGF at 30 days after the implantation, but that addition of VEGF significantly increased the number of infiltrated cells NAGO staining showed only a few positive cells in the PDMS-TEOS scaffold without VEGF, but significant increase of endothelial cells with VEGF was confirmed. Immunohistochemical study for GFAP demonstrated that only a few astrocytes were found in the PDMS-TEOS scaffold without VEGF, which was again significantly increased with VEGF. Double staining with proliferation maker Ki67 demonstrated that VEGF significantly increased newly formed astrocytes and endotheial cells, indicating that addition of VEGF accelerated tissue restoration and angiogenesis. Conclusions: The present study showed that a new porous PDMS-TEOS is a good candidate biomaterial for brain tissue restoration. Endothelial as well as glial cells successfully infiltrated into this biomaterial. Addition of VEGF further promoted new tissue formation.

DOI： 10.1016/j.brainres.2006.09.117

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Background: For brain tissue regeneration, a scaffold for migrated or transplanted cells with vessels is important if the tissue become pannecrotic. The present study was designed to determine whether the implantation of porous gelatin-siloxane hybrids can serve as a scaffold for brain tissue regeneration. Methods: We used male Wistar rats of 12-weeks old. A new porous gelatin-siloxane hybrid derived from the integration of gelatin and 3-(glycidoxypropyl) trimethoxysilane (GPSM) was implanted into a defect of the cerebral cortex, which was located at 3.0 mm anterior to 2.0 mm posterior of the bregma (5 mm in length) and 2.0-4.0 mm (2 mm in width) lateral to the midline, and the depth of the lesion was approximately 2.0 mm below the skull surface. The block of GPSM was presoaked in basic fibroblast growth factor (bFGF) and epidermal growth factor (EGF) or only vehicle, and the time of implantation was just after or at 30d of brain defect making. The animal was decapitated and the frozen sections were prepared. In order to identify the cell types in the newly formed tissue, immunohistochemical analysis was performed for N-acetylglucosamine oligomers (NAGO), an endothelial cell marker, GFAP, ionized calciumbinding adapter molecule-1 (Iba1), NeuN and bromodeoxyuridine (BrdU). Additionally, in order to determine whether BrdU-labeled cells differentiate into vascular endothelial, astroglial and microglial cells, double immunofluorescent studies were performed for BrdU and NAGO, GFAP or Iba1. Furthermore, we observed axonal growth into the scaffold by double staining for BrdU and MAP2. Results: The control brain showed distortion of the cerebral cortex and enlargement of the ipsilateral lateral ventricle (Fig.1 A, C). On the other hand, the GPSM implanted into the lesion remained at the same site for 60 days, kept integrity of the brain shape, and attached well to the surrounding brain tissues (Fig.1 B, D). Marginal cavities of the scaffolds were occupied by newly formed tissue (Fig.1 E), where newly produced vascular endothelial, astroglial and microglial cells were found with BrdU positivity. The numbers of those cells were dose-dependently increased with bFGF and EGF. Extension of dendrites was also found from the surrounding cerebral cortex to the newly formed tissue, especially with addition of bFGF and EGF. Conclusion: The present study showed that GPSM had biocompatibility. It can thus serve as a potential scaffold for cell migration, angiogenesis and dendrite elongation with dose-dependent effects of bFGF and EGF.

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記述言語：英語   出版者・発行元：SPRINGER  

Low-temperature deposition of crystalline titania films on intrinsically bioinert materials to induce the bioactivity is of practical interest, not only because it meets the demand of providing organic biomaterials with bioactivity, which cannot tolerate high-temperature thermal treatments, but also because it reserves abundant Ti-OH groups facilitating the apatite deposition. In this paper, rutile films with thickness varied from 0.1 mu m to 1.7 mu m were deposited on commercially available pure titanium substrates from 1.5 M titanium tetrachloride aqueous solution kept at 60 degrees C for 3-60 h. The rutile films grew to give a preferred (101) crystalline plane in the X-ray diffraction pattern. After soaking in a simulated body fluid of the Kokubo solution (SBF) for 2 days, the rutile films with thickness over 0.6 mu m were covered with a layer of apatite. All the films with various thickness induced apatite deposition in SBF after soaking for 5 days. The bioinert polytetrafluoroethylene (PTFE) was also found to exhibit remarkable in vitro bioactivity as to induce apatite deposition from SBF within 2 days, after depositing the rutile film on the surface.

DOI： 10.1007/s10856-006-0115-9

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記述言語：英語   掲載種別：研究発表ペーパー・要旨（国際会議）   出版者・発行元：WICHTIG EDITORE  

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記述言語：英語   出版者・発行元：SPRINGER  

Anatase/rutile dual layers were deposited on titanium and polyethylene substrates when they were soaked in TiOSO4/H2O2 solution and aged in hot water: The dense bottom layer predominantly consisted of rutile, while the upper layer consisted of loosely packed aggregation of anatase particles. The titania deposition was the results of compromise among three conflicting processes: (1) hydrolysis of TiOSO4 to yield either soluble titania-H2O2 complexes or titania, (2) dissolution of the titania layer under the presence of H2O2, and (3) corrosive reactions between titanium substrates and H2O2 to yield similar complexes or compounds. The dissolution-deposition equilibrium was found associated with pH of the sulfate solution and changed with soaking time. Thus, proper pH value and soaking time in the treating solution were the two key factors to control the formation of dense titania layers. The resulted titania layers were easily covered with fine apatite particles when soaked in a solution supersaturated with its component ions.

DOI： 10.1007/s10853-006-1220-3

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記述言語：英語   出版者・発行元：John Wiley and Sons  

DOI： 10.1002/9783527610495.ch8

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記述言語：英語   出版者・発行元：BLACKWELL PUBLISHING  

Zinc-containing hydroxyapatite particles (Zn/HAp) were prepared by an ion exchange reaction process involving hydroxyapatite (HAp) particles with aqueous solutions containing various amounts of zinc nitrate. The Zn2+ ion was partially substituted for the Ca2+ ion position in the HAp lattice, and hence, the obtained samples had changed little in crystallinity, particle size, and specific surface area. Adsorption of bovine serum albumin (BSA) and beta(2)-microglobulin (beta(2)-MG) in solutions containing both BSA and beta(2)-MG was examined. As the Zn2+ ion content in the apatites increased, the adsorbed amount of BSA was almost constant, whereas that of beta(2)-MG increased.

DOI： 10.1111/j.1551-2916.2006.01396.x

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE BV  

In the brain after infarction or trauma, the tissue eventually becomes pannecrotic and forms a cavity. In such situations, a scaffold is necessary for the implanted or migrated cells to produce new tissue. In this present study, therefore, we attempted to restore brain tissue using a novel biomaterial, polydimethylsiloxane-tetraethoxysilane (PDMS-TEOS) hybrid with or without vascular endothelial growth factor (VEGF), which is crucial for new vessel formation. When PDMS-TEOS scaffold was implanted into the artificial brain defect, it remained at the implanted site and kept the integrity of the brain shape. At 30 days after the implantation, the marginal territory of PDMS-TEOS scaffold became occupied by newly formed tissue. Immunohistochemical analysis revealed that the new tissue was constituted by astrocytes and endothelial cells. Addition of VEGF increased the newly produced tissue volume, and the immunohistochemical analysis showed that the numbers of astrocytes and endothelial cells were increased. Double staining with proliferation maker Ki67 demonstrated that VEGF significantly increased newly formed astrocytes and endothelial cells, indicating that addition of VEGF accelerated tissue restoration and angiogenesis. These findings show that implantation of PDMS-TEOS scaffold with VEGF might be effective for treating old brain infarction or trauma. (c) 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.brainres.2006.09.117

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Porous & rubbery organic-inorganic hybrids were synthesized from tetraethoxysilane (TEOS) and polydimethylsiloxane (PDMS) through a sol-gel route using sieved sucrose granules as a porogen. The porous hybrids with a high content of PDMS behaved like polymer sponge. The porosity was over 90% irrespective of the hybrid composition and the pore diameter ranged from 100 to 500 μm. In the three-dimensional cell culture, mammalian cells were well cultured in the porous hybrids. The present results indicate that the hybrids may be a promising scaffold for developing such functional culture methods.

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Rutile films were deposited on polyethylene terephatalate (PET), polytetrafluoroethylene (PTFE), Silicone, poly6-caprolactam (Nylon6), polyhexamethylene adipamide (Nylon6,6) and Nylon fiber substrates using 0.03 M TiOSO4 and 0.03 M H2O2 aqueous solution at 80°C for 24 h. The rutile films exhibited excellent in vitro bioactivity as they induced apatite deposition in a simulated body fluid (SBF).

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Titania layer was fabricated on the titanium substrates with chemical treatment with 20ml or 40ml of hydrogen peroxide solution and subsequent heat treatment at 400°C, coded as CHT20 and CHT40, respectively. CHT20 spontaneously deposited apatite on the surface in a simulated body fluid (SBF), while CHT40 did not. TF-XRD patterns showed that the diffraction intensity of anatase of CHT20 was higher than that of CHT40. It was suggested that the thicker titania layer indicated in vitro apatite forming ability. The cell proliferation of CHT20 and CHT40 were lower than NT and HT. Since the surface of titania layers became hydrophobic after autoclaving, we can suppose that the cell proliferation on CHT20 and CHT40 were lower than NT and HT due to their surface hydrophobicity.

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Rutile films were deposited on poly-1-lactide (PLLA) substrates using 0.5 M titanium tetrachloride aqueous solution at 40°C for 72 h. The rutile films exhibited excellent in vitro bioactivity as they induced apatite deposition in a simulated body fluid (SBF) within 3 days. This simple treatment provided an effective route to synthesize bioactive and biodegradable scaffolds.

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Titania films were coated by means of sol-gel method on various substrates such as titanium, titanium alloy, silicon wafer, stainless-steel, alumina, and glass slide where they coded as C5Ti, C5Ti6Al4V, C5Si, C5SUS, C5Al 2O3 and C5GS, respectively. Their in vitro apatite-forming ability was examined with the Kokubo's simulated body fluid (SBF; pH 7.4, 36.5°C). C5Ti, C5T16Al4V and C5Si deposited apatite particles on their surface within 7 days, whereas, C5SUS, CSAl2O3 and C5GS did not. These results implied that the in vitro apatite-forming ability of the titania films indirectly depended on the chemical or physical properties of the substrates.

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Zn-substituted apatites with homogeneous Zn distribution in the particles (ZnΦHAp) and those with graded distribution (Zn/HAp) were prepared via a conventional wet chemical synthesis and soaking the Zn-free apatite particles in zinc nitrate solutions: X-ray photoelectron spectra of the apatites confirmed such Zn distribution. Physical and chemical properties such as particle size, specific surface area, or zeta-potential and were correlated to adsorption of β2-microglobulin (β2-MG) and bovine serum albumin (BSA). Adsorption of β2-MG on both apatites increased with the Zn content, whereas more β2-MG was adsorbed on Zn/HAp than on ZnΦHAp. The amount of BSA adsorbed on ZnΦHAp reached a maximum at about 1.5%, while it remained constant for Zn/HAp. From the results, it was suggested that Zn-substituted sites had better affinity against β2-MG and favored β2-MG adsorption. Surface charge on the particles was one of the factors to explain the suppressed adsorption of BSA by both apatites.

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記述言語：英語   出版者・発行元：SPRINGER  

Titania consisting of rutile and anatase was precipitated on and inside of cotton fibrils when cotton was soaked in an aqueous solution of 30 mM TiOSO4 and 30 mM H2O2 kept at 80 degrees C for 24 h. As the resultant titania-cotton fibrils were soaked in a simulated body fluid (Kokubo solution), apatite was deposited on the fibrils to yield cotton-titania-apatite composites within 1 d. Thus, the present study provided a simple technique to prepare titania-apatite composites and coatings on organic materials at low temperature.

DOI： 10.1007/s10971-006-8759-y

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記述言語：英語   出版者・発行元：NATURE PUBLISHING GROUP  

For brain tissue regeneration, any scaffold for migrated or transplanted stem cells with supportive angiogenesis is important once necrotic brain tissue has formed a cavity after injury such as cerebral ischemia. In this study, a new porous gelatin-siloxane hybrid derived from the integration of gelatin and 3-(glycidoxypropyl) trimethoxysilane was implanted as a three-dimensional scaffold into a defect of the cerebral cortex. The porous hybrid implanted into the lesion remained at the same site for 60 days, kept integrity of the brain shape, and attached well to the surrounding brain tissues. Marginal cavities of the scaffolds were occupied by newly formed tissue in the brain, where newly produced vascular endothelial, astroglial, and microglial cells were found with bromodeoxyuridine double positivity, and the numbers of those cells were dose-dependently increased with the addition of basic fibroblast growth factor (bFGF) and epidermal growth factor (EGF). Extension of dendrites was also found from the surrounding cerebral cortex to the newly formed tissue, especially with the addition of bFGF and EGF. The present study showed that a new porous gelatinsiloxane hybrid had biocompatibility after implantation into a lesion of the central nervous system, and thus provided a potential scaffold for cell migration, angiogenesis and dendrite elongation with dose-dependent effects of additive bFGF and EGF.

DOI： 10.1038/sj.jcbfm.9600275

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Zn/HAp particles were prepared by soaking hydroxyapatite (HAp), derived through a wet chemical method, into aqueous solutions containing various amounts of zinc nitrate. Obtained samples were characterized by inductively coupled plasma emission spectroscopy, X-ray diffraction (XRD), Brunauer-Emmett-Teller surface area analysis (SA), and transmission electron microscopy. Their zeta potential was also measured. The analyzed Zn content was almost proportional to the content in the aqueous solutions. The Zn 2+ ions were partially replaced the Ca 2+ ions in the apatite, and hence, little change was observed in crystallinity, particle size and SA. Adsorption of bovine serum albumin (BSA) and ß 2-microglobulin (ß 2-MG) in the solutions containing both BSA and ß 2-MG was examined. As the Zn 2+ ion content in the apatites increased, the adsorbed amount of BSA was almost constant, whereas that of ß 2-MG increased. Thus, the Zn incorporation increased the selectivity, and it is suggested that the Zn-substituted site should be the active ones for ß 2-MG adsorption.

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Nano-scale rods of titania and tungsten oxide were fabricated on metallic titanium and tungsten substrates by heat-treatment in vucuo. The surface structure and morphology were characterized by Thin-film X-ray diffraction analysis (TF-XRD) und scanning electron microscopy. The TF-XRD analysis indicated that the thermal treatment in vacuo (6.7 × 10-2 Pa) gave TiO2 (rutile; PDF#21-1276) and WO3 (PDF#20-1324) nano-scale rod arrays. The mechanism of the nano-scale rod array formation was explained by the structure matching due to topotaxy and the crystal growth habit.

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The selective protein adsorption property and the local structure around carbonate ions of nanocrystalline hydroxy-carbonate apatite were examined in this study. Considerable change in the selectivity in the adsorption of BSA and β2-MG was observed due to the incorporation of the carbonate ions in hydroxyapatite lattice. Since the protein adsorption property seems to be related to the surface charge density of hydroxyapatite due to the carbonation, the chemical states of the incorporated carbonate ions were examined by the 31C CP-MAS NMR spectroscopy. At least four peaks assignable to carbonate ions in A-site(OH-) and B-site(PO 43-) were observed in 13C CP-MAS NMR spectrum. Thus, we must take into consideration that the surface charge distribution and the decrement of polar groups such as OH- groups due to the distribution of carbonate ions in both A- and B-sites of the hydroxyapatite lattice are particularly favorable for β2-MG adsorption rather than for BSA adsorption.

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Titania films with various thickness (about 100 nm to 300 nm) were prepared on titanium substrate by means of sol- gel method. Their surface energy was derived and in vitro apatite-forming ability was studied. The thickness of titania films of the sample coded C1, C3 and C5 was 98 nm, 204 nm, and 302 nm, respectively. Titania films of C5 showed smoother and more hydrophilic. The surface free energy of C5 was the highest of all. In vitro apatite-forming ability showed the titania films of C5, only. It was thus suggested that the titania films with more hydrophilic and higher surface free energy favored apatite-formation than those with smaller surface free energy.

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Rutile films were deposited on polytetrafluoroethylene (PTFE) substrates using 1.5 M titanium tetrachloride aqueous solution at 60 °C. The rutile films exhibited excellent in vitro bioactivity as they induced apatite deposition in a simulated body fluid (SBF) within 2 days. Chlorine incorporated in the rutile films did not inhibit apatite deposition.

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Anatase films with various morphologies were formed on Ti surface through different approaches using hydrogen peroxide solutions. A porous anatase surface was found to favor apatite deposition in SBF, or in vitro bioactivity. Thicker films with wider crack gaps also showed enhanced in vitro bioactivity. However, the most predominant effect was the abundance of Ti-OH functional groups incorporated in the anatase films.

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This work reports the structure of two glass ceramics prepared in the calcium phosphate system, MK5B and MT13B, using 31P MAS-NMR technique. The results obtained showed that the network of MK5B consisted mainly of Q1 and Q2 groups. Besides these two groups, MT13B material also present Q3 units. The Qn groups detected in both glass ceramics seem to be correlated to the crystalline phases present in their microstructure.

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記述言語：英語   出版者・発行元：SAGE PUBLICATIONS LTD  

Two MK5 (45CaO-45P(2)O(5)-5MgO-5K(2)O, in mol%) and MT13 (45CaO-37P(2)O(5)-5MgO-13TiO(2), in mol%) glasses are prepared in the meta- and pyrophosphate regions and crystallized to obtain MK5B and MT13B, respectively. MK5B was obtained by controlled crystallization, and MT13B by powder sintering. As a result of these heat treatment processes, the crystalline phases precipitated in the glassy matrix are KCa(PO3)(3), beta-Ca(PO3)(2), beta-Ca2P2O7 and Ca4P6O19 phases for MK5B and CaTi4(PO4)(6), TiP2O7, alpha- and beta-Ca2P2O7 phases for MT13B. To assess the in vivo biological behavior of these glass ceramics, a mixed granulometry in the range 250-355 mu m and 355-425 mu m with a ratio of 1/1 was implanted for 2, 4, and 12 weeks in the tibiae of Japanese white rabbits. The results showed that the in vivo behavior was strongly affected by their solubility. All implanted materials, MK5B and MT13B, and beta-tricalcium phosphate (beta-TCP) as control material, showed signs of degradation in vivo. However, the levels of degradation were quite different throughout the implantation periods. The highest degradation was observed for MK5B glass ceramic and the lowest for MT13B with beta-TCP in-between. All implanted materials allow for new bone formation in the bone defect area. At the longest implantation period (12 weeks), the MT13B and beta-TCP materials were almost completely surrounded by new bone tissue, whereas MK5B showed some unfilled spaces. This behavior is discussed in terms of the high degradation observed in previous studies.

DOI： 10.1177/0885328206052466

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Nano-crystalline Zn-containing hydroxyapatite (ZnHAp) was prepared by the wet-chemical method and the selective adsorption of essential proteins was examined, taking bovine serum albumin (BSA) and pathogenic protein such as β2-microglobulin (β2-MG) as model proteins. Transmission electron microscopy observation and X-ray diffraction analysis indicated that the increase of Zn content led to smaller crystallites and their specific surface area of ZnHAps increased with increasing Zn content, accordingly. Furthermore, the amounts of BSA adsorption on ZnHAp particles decreased with increasing Zn content in spite of the increase in the specific surface area. It is thus concluded that nano-crystalline ZnHAps had a highly selective adsorption property with regard to β2-MG. © 2005 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.actbio.2005.09.002

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

γ-Methacryloxypropyltrimethoxysilane (γ-MPS) was grafted on a silicone elastomer by emulsion polymerization in order to improve cytocompatibility. The wettability of the grafted surface was evaluated with a contact angle toward distilled water. By grafting within 30 min at 60°C, the contact angle was reduced from 110° to about 70° while it remained almost constant for longer grafting. A larger number of osteoblastic cells (MC3T3-E1) and fibroblast cells (1929) proliferated on the surface modified with γ-MPS compared with the original silicone surface. After culturing for 7 d, the cells completely covered the grafted surface and even formed a cell layer.

DOI： 10.2109/jcersj.114.72

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記述言語：英語   出版者・発行元：SAGE Publications Inc.  

Among functional monomers used in contemporary dental adhesives, 10-methacryloyloxydecyl dihydrogen phosphate (MDP) has been found to interact chemically with hydroxyapatite (HAp) most intensively and stably. This effect was thought to be the basis of the superior bonding effectiveness of MDP-based self-etch adhesives to enamel/dentin. To elucidate fully the chemical interaction and reactivity of MDP with HAp, we used 31P CP-MAS NMR spectroscopy and powder x-ray diffraction. In an aqueous ethanol solution, Ca ions were leached from HAp to form, at short term, a MDP-calcium salt (CaMHP2) layered structure on the HAp surface. When MDP was allowed to interact for longer time (&lt
24 hrs), CaHPO4·2H 2O precipitated on top of this MDP-calcium salt layered structure. In conclusion, the intense chemical interaction of MDP with HAp must be ascribed to superficial dissolution of HAp induced by the MDP adsorption and subsequent deposition of MDP-calcium salt with a solubility lower than that of CaHPO 4·2H2O.

DOI： 10.1177/154405910608501014

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

Titania layers were deposited on titanium substrates in titanylsulfate solutions under varied concentration (0.01 and 0.03M), pH (0.67-1.27) and temperature (60 and 80°C). They were rinsed and subsequently aged in water at 80°C for 3d. The layers consisted of only rutile or rutile with trace anatase, depending on the conditions. The X-ray diffraction intensity indicates that the rutile particles grew preferably in (101) plane, regardless of being aged or not. When aged, the anatase diffraction intensity increased, and anatase newly grew in the layer consisting only of rutile. When soaked in a simulated body fluid (SBF) of the Kokubo recipe, the rinsed layer with only rutile was weakly active to deposit apatite within 5 d, while the other two exhibited no deposition. The aging improved activity. Although anatase is reported in the literature to be more active than rutile, the present study indicates that the rutile layer is more active. Thus, it is concluded that topotaxy or epitaxy would not work well but other issues like the presence of Ti-OH affect apatite deposition.

DOI： 10.2109/jcersj.114.253

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記述言語：英語   掲載種別：書評論文，書評，文献紹介等   出版者・発行元：Ceramic Society of Japan  

Silica-hybridized hydroxyapatite powder was prepared from a calcium hydroxide and phosphoric acid together with a tetra-n-butyl orthosilicate as the silica source in order to apply it as a gas adsorbent. According to the X-ray diffraction patterns, all peaks were assigned to the hydroxyapatite. No secondary phases, such as calcium hydroxide and silicon oxides, were observed. Moreover, the transmission electron microscope observations indicated that the crystallite size hardly changed by increasing the silicon oxide content. However, the adsorption areas of nitrogen, water and benzene were remarkably dependent on the silicon oxide content. In this paper, in order to explain the change in the adsorption areas, the lattice structure of the silica-hybridized hydroxyapatite is discussed based on the results obtained by the 29Si and 31P magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR).

DOI： 10.2109/jcersj.114.769

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Chitosan-silicate hybrid membranes were prepared using γ- glycidoxypropyltrimethoxysilane (GPSM) through a sol-gel process. The amino groups of chitosan chains were reacted with the epoxy groups of GPSM and GPSM have a function as the agent to cross-link the chitosan chains. The cross-linking degree of the hybrid membranes was determined by ninhydrin assay. Fourier-transform infrared (FT-IR) spectroscopy and29Si cross-polarization (CP) magic-angle spinning (MAS)-NMR spectroscopy were used to assess the structure of the hybrid membranes. The biodegradability of the hybrid membranes in phosphate-buffered saline solution or lysozyme solution was investigated as a function of the GPSM concentration.

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The structural change of bovine serum albumin (BSA) was analyzed by means of ultraviolet (UV) and circular dichroism (CD) spectroscopy due to in contact with ceramics powders such as Al2O3, SiO2, TiO2, ZrO2, hydroxyapatite and β-tricalcium phosphate. The absorbance of the UV spectra increased for the BSA solution in contact with TiO2, ZrO2 and Al2O3, that is, the BSA solution clouded. This indicated the aggregation of BSA after contact with those ceramics powders. The CD spectroscopy showed that the ordered secondary structure of BSA was diminished on contact with TiO2 and ZrO2. We discussed the protein adsorption property of ceramics on the basis of the magnitude of the interaction forces between proteins and the bioceramics.

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Organic-inorganic hybrids involving Ti-O bonds were coated on stainless-steel (SUS316L) substrates. Tetraisopropoxide and titanium methacrylate triisopropoxide were employed as the major starting chemicals to provide TiO2-polydimethylsiloxane (PDMS) layers or organotitanium molecular thin layers, respectively. Fourier transform infrared spectra indicated that each layer contained Ti-O bonds in their structure. The obtained hybrid layers had little effects on the blood-clotting times such as active partial thromboplastin time and pro thrombin time. In addition, the number of adhered platelet on the TiO2-PDMS layers depended on the composition, while the organotitanium molecular thin layers suppressed fibrinogen adsorption compared with coating-free SUS 316L substrate.

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記述言語：英語   出版者・発行元：ROYAL SOCIETY  

gamma-Methacryloxypropyltrimethoxysilane (gamma-MPS) was grafted to high-density polyethylene, polyamide and silicone rubber substrates by the emulsion polymerization procedure in order to provide these organic polymers with in vitro apatite-forming ability. The contact angles towards distilled water of the gamma-MPS-grafted specimens were lower than those of the original organic polymer specimens, indicating that the grafted substrates were more hydrophilic. The in vitro apatite formation in a simulated body fluid (Kokubo solution) was confirmed for several of the gamma-MPS-grafted specimens.

DOI： 10.1098/rsif.2005.0048

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We proposed a new approach on preparing titania or titanate nano- or micro-rod arrays on metallic titanium (α-Ti) surfaces by coating a layer of sodium tetraborate or potassium metaborate on titanium substrates and subsequent thermal treatment. Thin-film X-ray diffraction analysis indicated that the sodium tetraborate gave rutile (TiO2: PDF# 21-1276) micro-rod array. The potassium metaborate, in contrast, yielded a potassium titanate (K2Ti6O13: PDF# 40-0403) nano-rod array. The rods in the arrays grew almost perpendicular to the substrate surface.

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

A titania layer with ordered nanostructures is expected to be of high photocatalytic activity due mainly to its high specific surface area. In the present work, large-area films with ordered titania nanorods were deposited on titanium substrates through a solution approach, The nanorods, with the phase composition of a mixture of anatase and rutile, grew on top of a condensed anatase interlayer along mainly the rutile [001]-axis. The photocatalytic activity was evaluated by decomposing rhodamine B in water and compared with the general sol-gel derived titania films and a commercial DP-25 titania coating. It is found that the as-deposited titania nanorods exhibited extremely high initial photocatalytic activity but declined to a poor value after the consumption of beneficial oxidative peroxo complexes coordinated to Ti(IV). A subsequent thermal treatment eliminated such complexes but at the same time improved the crystallinity of the titania nanorods. The photocatalytic activity of the thermally treated titania nanorods was stable and significantly higher than that of the sol-gel derived film and commercial DP-25 coating.

DOI： 10.1021/la0500272

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Much interest has recently been shown in the potential utility of bioartificial liver (BAL) as a bridge support for patients and as a module for experimental purposes. A radial-flow bioreactor (RFB), one of the perfused bed/scaffold-type bioreactors, enables a highly functional three-dimensional culture as BAL. The functional capacity of bioreactors depends not only on their mechanistic structures but also on scaffolds packed in them. In the present study, we examined the possible utility of a new porous organic-inorganic-hybrid scaffold in an RFB. The scaffold was made from tetraethoxysilane (TEOS) and polydimethylsiloxane (PDMS) by a sol-gel method using sieved sucrose particles as a porogen. In the porous TEOS-PDMS hybrid scaffold, human hepatocellular carcinoma cells (HepG2) proliferated actively and formed cell clusters more efficiently than they did in a polyvinyl-alcohol scaffold. When cultivated in PDMS-TEOS, HepG2 cells secreted a similar tothree-fold greater amount of albumin than that secreted in a monolayer culture. For potential application of BAL to pharmacological studies and future clinical use, it is essential to develop a method to propagate liver cells that maintain highly specific functions. The present results indicate that PDMS-TEOS may be a promising scaffold for developing such functional culture methods. (C) 2004 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.biomaterials.2004.07.012

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Chitosan-silicate hybrids were synthesized using gamma-glycidoxypropyltrimethoxysilane (GPSM) as the agent for cross-linking the chitosan chains. CaCl2 was introduced in the hybrids in expectation that it would improve cell adhesion and differentiation of the hybrid surfaces. Fourier-transform infrared (FT-IR) spectroscopy and Si-29 CP-MAS NMR spectroscopy were used to analyze the structures of the hybrids. Cytocompatibility of the hybrids was investigated in terms of proliferation of an osteoblastic cell line, MG63. The adhesion and proliferation of the osteoblastic cells cultured on the Surface of a chitosan-GPSM hybrid without calcium were similar to those on a control Culture plate, and were better than those on a chitosan membrane. The ALP activity of the cells cultured on this hybrid was higher than that on the chitosan membrane. Contrary to expectations, the incorporation of calcium ions into the hybrids did not improve cell attachment and proliferation on their surfaces. (C) 2004 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.biomaterials.2004.02.056

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記述言語：日本語   出版者・発行元：Ceramic Society of Japan  

Hydroxyapatite powders (HAp
Ca10(PO4) 6(OH)2) hybridized with 0-5 mass % Al2O 3 were prepared from calcium hydroxide and di-aminonium hydrogenphosphate by a wet chemical synthesis. Ethylacetoacetate Aluminum Diisopropoxide (Al(OC3H7)2(C6H 9O3)) was used as a source for aluminum oxide. The obtained powders were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) specific surface area measurement, and magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR). The X-ray diffraction patterns showed no Al2O3-peaks irrespective of Al2O3 content, suggesting that the Al2O 3-hybridized HAp powders were single phase. The Al2O 3-hybridized HAp powder had larger specific surface area. According to MAS-NMR analysis, it was considered that the aluminum element existed as aluminum oxide, it was not substituted for the Ca2+, PO 4 3-, or OH- ions.

DOI： 10.2109/jcersj.113.241

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記述言語：英語   出版者・発行元：MATERIALS RESEARCH SOCIETY  

Titania submicron-scale rod arrays were fabricated on metallic titanium (alpha-Ti) surfaces by coating a layer of sodium tetraborale on titanium substrates and subsequent thermal treatment. Thin-film X-ray diffraction analysis indicated that the sodium terraborate gave rutile (TiO2: PDF# 21-1276) submicron-scale rod arrays. The rods in the arrays are parallel to each other in the grain of metallic titanium surface. The titania submicron-scale rod arrays deposited apatite within 7 days after being soaked in a simulated body fluid, indicating that the rod arrays exhibit in vitro bioactivity.

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The formation of hydroxyapatite on and inside of cotton fibrils with an oxysulfate solution was investigated. A titania layer consisting of rutile was observed to be deposited on cotton fibrils after treating in above solution. It was observed that bonelike apatite was successfully formed on entirety of cotton fibrils in SBF at 36.5°C within only 2d. It was found that rutile induces apatite deposition in SBF at 36.5 °C just as well as anatase.

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The protein adsorption on the alginic acid layers covalently immobilized on stainless-steel and titanium was examined by Fourier transform infrared spectroscopy using a reflection adsorption method (FT-IRRAS). The relationship between platelet adhesion and protein adsorption was also investigated. The contact angle measurement and FT-IRRAS spectra confirmed the successful immobilization of γ-APS and alginic acid onto stainless-steel and titanium substrates. The result shows that less protein adsorption leads to blood-compatible surface on the alginic acid-immobilization.

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記述言語：英語  

Bioactivity has been exhibited by a limited range of ceramics since the invention of Bioglass®. Recently, some bioactive polymeric organic-inorganic hybrids were introduced, including not only organically modified silicates (Ormosils) synthesized from polydimethylsiloxane (PDMS) and tetraethoxysilane but also those with gelatin and 3-glycidoxypropyl-tremethoxysilane. Preparation of the bulk and porous hybrids and their polymeric structures analyzed by Si NMR spectroscopy were presented. In vitro bioactivity or apatite deposition in a simulated body fluid of the Kokubo recipe were also described for those hybrids. Freeze-drying techniques introduced porosity (up to 90%) and pores extending in a preferred direction. © 2004 Kluwer Academic Publishers.

DOI： 10.1007/s10971-004-5789-1

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE BV  

We prepared an organotitanium molecular layer on stainless-steel (SUS316L) substrates, and evaluated its blood compatibility in terms of blood-clotting time and fibrinogen adsorption properties. Titanium methacrylate triisopropoxide (TMT) was used as the organotitanium molecule. The surface was characterized by contact angle measurement toward distilled water and Fourier transform infrared spectroscopy using a reflection absorption method (FT-IRRAS). The obtained organotitanium molecular layer had little effects on the blood-clotting times such as active partial thromboplastin time (PTT) and prothrombin time (PT). Bovine fibrinogen adsorption on the layer was examined from the absorbance of amide I peak in FT-IRRAS spectra. The organotitanium molecular layer reduced the amount of adsorbed fibrinogen compared with stainless-steel. (C) 2004 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.msec.2004.08.035

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記述言語：英語   出版者・発行元：KLUWER ACADEMIC PUBL  

PDMS- TiO2 hybrid coating sols were prepared from silanol- terminated polydimethylsiloxane and titanium tetraisopropoxide through sol- gel process. The coating sols were developed on stainless steel substrate with dip- coating technique. The surface structure of the hybrid coating was characterized by Fourier transform infrared ( FT- IR) analysis, contact angle, and surface free energy on the hybrid coating. Blood compatibility was also evaluated in terms of blood clotting time and platelet adhesion. The hybrid coatings have high contact angles and low surface free energies compared to coating- free metal surface. The blood clotting properties were not affected by the hybrid coatings but the platelet adhesion was depressed to less than 1/ 20 as much as that for the coating- free substrate.

DOI： 10.1023/B:JSST.0000048002.65187.3a

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

The correlations between titanium oxide layers on oxidized titanium (Ti) substrates and platelet adhesion were examined. Ti substrates were prepared by three different oxidation methods: the first one was treated with hydrogen peroxide (H2O2) solution, the second one was heated in air at moderate temperatures, and the third one was processed with both H2O2 and heating. The titanium oxide layers formed on the Ti substrates were characterized by wettability, chemical composition, thickness, and crystal phase. The platelet adhesion on these oxide layers was examined and correlated to the characterizations of the surface layers. The number of adhesive platelets seemingly correlated with the contact angle towards distilled water, because the number increased close to 70-80degrees of the contact angle. The effect of surface oxidation on platelet adhesion was examined in detail and it was found that the composition and thickness of the oxide layer influenced platelet adhesion rather than wettability. Thick titanium oxide layers formed on Ti substrates by heating displayed less platelet adhesion than thin oxide layers on untreated Ti substrates. The largest number of adhesive platelets was found on H2O2-oxidized substrates; the substrates found on amorphous titanium oxide contained the Ti-peroxide radical species. The number of platelets, on the other hand, could hardly be observed on Ti substrates treated with H2O2 and subsequently heated above 300 degreesC. The titanium oxide layer on the substrate was thick and we found it to consist of only a few radical species. That is, the effect of heat treatment accelerates the growth of the oxide layer, and decomposes or decreases the number of radical species. Ti substrates with H2O2 and heat treatment above 300 degreesC held the least number of platelets, and were concluded to be the most inhibitory for platelet adhesion. (C) 2003 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.biomaterials.2003.10.070

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記述言語：英語   出版者・発行元：WILEY-LISS  

We examined the blood compatibility and protein adsorption on hydroxyapatite and hydroxy-carbonate apatite. Those apatites were synthesized under a 0, 5, or 15% CO2-containing N-2 atmosphere by a wet-chemical method with a strong ammonia alkali solution of calcium nitrate and diammonium hydrogen phosphate (5:3 in molar ratio) and subsequent calcination in the range of 105-700degreesC. From infrared (IR) analysis, the carbonate ions substituted both phosphate ions and hydroxyl ions in the hydroxyapatite lattice; the intensities of IR bands assignable to phosphate ions and hydroxyl ions were reduced on calcinations. The specific surface areas of synthesized apatites decreased with increasing calcination temperature. Blood-clotting properties were evaluated in terms of active partial thromboplastin time, prothrombin time, and the amount of fibrinogen for the plasma in contact with the apatites, indicating that all the apatites barely influenced the blood clotting system. The apatites were in contact with a solution containing both bovine serum albumin (BSA) and beta(2)-microglobulin (beta(2)-MG), and the amounts of those proteins adsorbed on them were examined: the amount of absorbed BSA and beta(2)-MG gradually increased with the calcination temperature below 500degreesC, while it showed a sudden increase when more than 600degreesC. Hydroxy-carbonate apatite synthesized under a 15%, CO2-containing N-2 atmosphere and calcined below 400degreesC had the greatest selectivity in adsorbing beta(2)-MG. Thus, a higher selectivity for beta(2)-MG adsorption was empirically correlated to carbonate ions incorporated in the hydroxyapatite lattice. (C) 2004 Wiley Periodicals, Inc.

DOI： 10.1002/jbm.a.30039

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記述言語：英語   出版者・発行元：SOC GLASS TECHNOLOGY  

CaO-P2O5 glass ceramics with small additions of MgO and TiO2 were prepared in the ortho and pyrophosphate regions by powder sintering and crystallisation through heat treatment at different temperatures determined from, differential thermal analysis (DTA). The glass ceramics were analysed by x-ray diffraction (XRD) and it was observed that alpha- and beta-Ca2P2O7 were the first phases to precipitate in the parent glass matrix at a temperature of 681degreesC, followed by CaTi4(PO4)(6) and TiP2O7 at temperatures between 703 and 725degreesC The beta-Ca2P2O7 and CaTi4(PO4)(6) phases are usually considered as biocompatible and bioactive and, therefore, these glass ceramics seem to show good potential for bone regeneration applications.

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Chitosan-silicate hybrids were synthesized using γ-glycidoxypropyltrimethoxysilane (GPSM) as the agent to cross-link the chitosan chains. Fourier-transform infrared (PT-IR) spectroscopy was used to analyze the structures of the hybrids. The swelling ability and the cytocompatibility of the hybrids were investigated as a function of the GPSM concentration. The swelling of the hybrids was suppressed by addition of GPSM. MG63 human osteoblastic cells were cultured on the hybrids. The adhesion and proliferation of the MG63 cells cultured on the chitosan-GPSM hybrid surface were improved comparing to that on chitosan membrane, regardless the GPSM concentration.

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We prepared titanium substrates with sub-micron scale pores and without sub-micron scale pores by means of chemical treatments with hydrogen peroxide and subsequent thermal treatments. Sub-micron scale pores were observed on the surface of the titanium substrate treated with 3 mass% H2O 2 at 90°C for 1 h(H1) by scanning electron microscopy. On the other hand, the sub-micron scale pores were not observed on the substrate treated with 3 mass% H2O2 at 90°C for 72 h(H72). The surface roughness, Ra of H1 and H72 substrates was 27 and 14 nm, respectively. Both substrates showed high in vitro apatite-forming ability in simulated body fluid (SBF of Kokubo's recipe). The apatite-forming ability of H72 substrate with low Ra value was higher than that of H1 with high Ra value.

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Titania films were prepared from interaction of Ni-Ti shape memory alloy with hydrogen peroxide solution followed by heating at 400°C. The titania films consisted of crystalline phase of TiO2 (anatase). The in vitro platelet adhesion property of the titania films was examined, The titania films on Ni-Ti alloy substrates adhered less platelets than Ni-Ti alloy substrate without treatment. This indicates that the titania film can suppress the adhesion of platelet. The present chemical modification process with hydrogen peroxide solution is applicable to prevent the Ni-Ti shape memory alloy materials from platelet adhesion when in contact with blood.

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This study was concerned with blood compatibility of titanium oxide layers on stainless steel. The titanium oxide layers were prepared through sol-gel process by dip-coating of tetraethyltitanate solution and heated at 500°C. The crystal phase, thickness and wettability of the oxide were characterized. The blood compatibility was evaluated in term of platelet adhesion using human platelet rich plasma. Consequently, with increase in the thickness of the titanium oxide layers, the number of platelet adhered on the stainless steel coated with titanium oxide layer decreased rapidly, When the thickness of titanium oxide layers on stainless steel grew more than 150 nm, the number of adherent platelets decreased less than 10% in comparison with that on non-coated stainless steel. The titanium oxide layers indicated to be more hydrophilic than non-coated stainless steel. In conclusion, the thicker and more hydrophilic titanium oxide layer on stainless steel appears to inhibit platelet adhesion.

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記述言語：英語   出版者・発行元：American Ceramic Society  

Surface modification of titanium and its alloys to induce apatite deposition within a short period is of practical importance in clinical applications. In this study, titanium substrates were treated with hydrogen peroxide solutions at low temperatures to yield titania layers consisting of anatase and rutile. Those titania layers, regardless of the fraction of anatase and rutile, were bioactive to induce deposition of apatite in Kokubo's simulated body fluid within 24 h. The bioactivity was attributed to both the epitaxial effect and the abundant Ti-OH group of the titania layer.

DOI： 10.1111/j.1551-2916.2004.01635.x

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

A novel approach to fabricating highly-oriented, nm-scale potassium titanate K2Ti6O13 rod arrays on titanium substrates was demonstrated. The fabrication process was template-free, and simply involved coating the titanium substrates with pulverized potassium metaborate and its derivatives, and subsequent heating at 700°C for 5 h. When the samples were soaked in hot water, the coating layers were readily removed, leaving an array of titanate crystallites on the titanium substrates. Even the slightest change in the composition of the potassium borates resulted in various microstructures, while K2O·1.03B2O 3 yielded highly-oriented nanorod arrays of K2Ti 6O13. Bioactivity of the as-achieved nanorod arrays was proved by the deposition of apatite in simulated body fluid (SBF: Kokubo solution). When soaked in SBF, the K2Ti6O13 nanorod arrays deposited apatite within one day accompanying the release of potassium ions from the crystallites into SBF and the arrays were covered with apatite layers in three days. Ion exchange between the potassium ions in the crystal and calcium ions in SBF is proposed as the mechanism operative to favor the deposition of apatite.

DOI： 10.2109/jcersj.112.634

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

A novel approach to fabricate sub-μm scale arrays is demonstrated with the growth of rutile TiO2 on titanium substrates. The fabrication process is template-free, simply involving coating of the titanium substrate with sodium tetraborate glass, Na2O · 2B2O 3: when the glass coating was removed by dissolution in distilled water at 80°C for about 5 h, random or well-ordered submicron-scale rod arrays of rutile were left on the substrate. A glass phase topotaxial (GPT) nucleation and growth mechanism is thought to operate in the crystal growth process.

DOI： 10.2109/jcersj.112.567

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

A new approach is presented to prepare a rutile layer on titanium substrates. According to this approach, pulverized glass, composed of 3CaO·4B2O3·3TiO2, is first developed on the substrate, heated up to 700 to 850°C, and then removed by soaking in hot water. During the heating process, rutile grew at the glass coating-substrate interface to form nano-sized crystallites. The rutile layer induced apatite formation within 3 d when soaked in simulated body fluid of the Kokubo recipe. Such in vitro bioactivity was attributed to many Ti-OH groups on the crystallite surface derived from hydrolysis of bonds at the crystallite-flux (matrix) interface like (rutile) -Ti-O-B or Ti-O-Ca-(the borate matrix).

DOI： 10.2109/jcersj.112.452

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記述言語：英語   出版者・発行元：KLUWER ACADEMIC PUBL  

A simple and versatile treatment was developed to provide various metallic biomaterials such as Ti, NiTi, Ta and SUS 316L stainless steel with in vitro bioactivity or ability to deposit carbonate-incorporated apatite in a simulated body fluid (Kokubo solution). A well-crystallized anatase layer deposited on the metallic biomaterials surfaces after soaking them at 60degreesC for 24 h in an aqueous solution of titanium tetrafluoride (40 mM) whose pH was adjusted to 1.9 with HCl;. The as-coated anatase layers did not deposit apatite. When heated at 300degreesC they were so bioactive as to deposit apatite within 5 day(s) in the Kokubo solution. The trace amount of fluorine weakly bound in the as-coated anatase layers was suggested to be one of the factors that suppressed the bioactivity. (C) 2003 Kluwer Academic Publishers.

DOI： 10.1023/B:JMSM.0000003998.37583.d7

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

By application of a special specimen set-LIP, thermally oxidized titanium specimen pairs were found able to deposit apatite oil the contact surfaces after soaking for 7 days in the simulated body fluid (SBF) of Kokubo's recipe. The specimens oxidized at 400degreesC and 500degreesC showed the highest ability of apatite deposition. Both increase and decrease in oxidation temperature front this range caused the apatite deposition ability to decrease. The specimen without treatment failed to deposit any apatite. Specimens anodically oxidized in electrolytes of H3PO4, H2SO4 and acetic acid exhibited very low ability of apatite deposition. Furthermore, the specimen thermally oxidized at 400degreesC was even able to help the surfaces of PTFE and silicone deposit apatite in the PTFE-Ti and silicone-Ti pairs. This in vitro experimental results indicated that the difference in apatite deposition among various titanium oxides does exist and can be distinguished by applying the present specimen set-up. The mechanism of the apatite deposition on the contact surfaces was discussed in relation to the passive dissolution of titanium in SBF. The release of titanium hydroxide and OH- ions from the titanium surfaces and their accumulation inside the confined space between the two contact surfaces were suggested to be responsible for the apatite deposition. (C) 2003 Elsevier Ltd. All rights reserved.

DOI： 10.1016/S0142-9612(03)00357-0

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE SA  

Thin titania film consisting of anatase and rutile was deposited on Ti substrates when soaked in a TiOSO4/H2O2 solution and aged in hot water. H2O2 corroded the Ti substrates, yielded a porous surface, and kept the solution from peptization. Thicker titania layers were formed in favor of both a greater supersaturation of Ti(IV) in the solution and a higher concentration of hydrated Ti(IV) derived by the corrosion of Ti and the hydrolysis of TiOSO4. The effects of aging in hot water were accounted for as they caused structural relaxation of the surface layer involving a rearrangement of Ti-OH and eliminating residual species like peroxide ions. Those titania layers were thus favored to deposit apatite when the Ti substrates were placed under a body environment, i.e. soaked in a simulated body fluid of Kokubo's recipe. (C) 2003 Elsevier B.V. All rights reserved.

DOI： 10.1016/S0040-6090(03)00913-1

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

This study is concerned with the blood compatibility of alginic acid layers immobilized on gamma-aminopropyltriethoxysilane (gamma-APS)-grafted stainless-steel (SUS316L). The surfaces were characterized with contact angle measurement and X-ray photoelectron spectroscopy (XPS). The blood compatibility was evaluated in terms of platelet adhesion and blood clotting time. Ail in vitro platelet adhesion assay indicated that only a small number of platelets adhered to substrate surfaces modified with gamma-APS and subsequently with alginic acid. Moreover, alginic-acid-immobilized SUS316L substrates had little effect on the blood clotting time. This indicated that alginic-acid-immobilized SUS316L substrates do not adsorb some blood-clotting proteins or factors, or stimulate them. (C) 2003 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0142-9612(03)00127-3

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The bioactive fixation between bone substitutes and their surrounding tissues is mostly studied in the nearest decade. The key of bioactive fixation is the high bioactivity of the biomaterials. To coat the titanium surface with a layer of bioceramics through physical deposition, sol-gel, electrochemical deposition, biomimetic process, etc. can promote the bioactivity of titanium effectively. Another approach to obtain a bioactive titanium surface is the chemical modification of titanium with sodium hydroxygen or hydrogen peroxide solution to induce titanium dioxide films on the surface. The titanium dioxide films derived by the surface modification should be abundant in Ti-OH functional groups, and also, in crystalline structure, which may effectively induce the epitaxial growth of hydroxylapatite nuclei. This paper provides a brief review of various techniques and their corresponding mechanisms for obtaining a titanium surface with bioactivity.

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γ-Aminopropyltriethoxysilane (γ-APS) was grafted on stainless-steel and titanium substrates, and subsequently alginic acid layer was immobilized on them. Their surfaces were characterized with X-ray photoelectron spectroscopy (XPS) and contact angle measurement. Blood compatibility of thus obtained substrates was evaluated in terms of both the number of the adhered platelets and blood clotting factors for plasma contacted with the substrates such as active partial thromboplastin time (PTT), prothrombin time (PT), and amount of fibrinogen (Fib). The steel and titanium substrates with alginic acid layer did not affect blood clotting factors. In vitro platelet adhesion assay indicated that those substrates adhered less number of platelets than non-treated substrates. Hence the alginic acid immobilization leads to blood compatible surfaces.

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We examined blood compatibility of titanium oxide layer on stainless-steel (SUS316L). The oxide layers with varied thickness were yielded on SUS316L plates by dip-coating of sol-gel solution starting from tetraethyltitanate. The blood compatibility was evaluated in term of platelet adhesion using platelet rich plasma. With increase in the thickness of the oxide layer, the number of adherent platelets decreased rapidly, reached minimum around 150nm. This indicated that the thickness of titanium oxide layer affected platelet adhesion.

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Bioactive TiO2 films were deposited on Ti substrates by two-step treatment near room temperature. A well-crystalline TiO2 gel film was obtained on Ti by soaking in TiF4+ H2O2 solution at 60° C for 24 h. Subsequent cathode polarization precipitated calcium hydroxide. Calcium carbonate appeared after samples soaking in a Kokubo simulated body fluid due to the reaction between calcium hydroxide and bicarbonate ions. Calcium hydroxide dissolved into SBF, supersaturated with calcium ions, favored apatite nucleation. Apatite thus deposited without heating the Ti substrates. This method was applicable to substrates other than Ti.

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γ-Methacryloxypropyltrimethoxysilane (γ-MPS) molecules were grafted on silicone elastomer by emulsion polymerization. Fibroblast and osteoblastic cells were cultured to examine cytocompatibility of the grafted surface. A greater number of cells grew on the grafted silicone, even forming a cell layer, than on the original silicone. Moreover, the cultured cells were agglomerated on the latter though they adhered well. Thus the γ-MPS grafting was concluded to improve cytocompatibility of silicone.

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Titanium substrates were provided with ability of biomimetic apatite deposition in a simulated body fluid by means of chemical treatment and subsequent thermal treatment. Examined were the effects of the chemical treatment time, the concentration and pH conditions of the H2O2 solutions on formation of bioactive titania gel layer and in vitro bioactivity. The optimum process consist of 6 mass% H2O2 treatment at 60 °C for 3-6 h and subsequent thermal treatment at 400 °C for 1h. Reactions between the titanium substrates and H2O2 involved titania gel formation and Ti (IV) dissolution. Each reaction rates well related with the concentration and pH of the H2O2 solutions.

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Organically modified silicate gels were synthesized starting from ploy(dimethylsiloxane), tetraethoxysilane, calcium nitrate, and colloidal silica through sol-gel processing. In vitro apatite deposition on the colloidal silica containing hybrids in a simulated body fluid of the Kokubo recipe was confirmed, indicating they were bioactive. Cell proliferation for the hybrid gels with the colloidal silica was better than the colloidal silica free gels. The cells cultured for 7 days on the hybrid gels with colloidal silica expanded their pseudopodium and were well attached. In contrast, the cells were hardly observable on the colloidal silica free gels. Thus, the hybrids with colloidal silica are cytocompatible as well as bioactive.

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Effects of tantalum on the low-temperature deposition of bioactive crystalline titania films were studied. Crystalline titania films (anatase and rutile) with excellent in vitro bioactivity were deposited through interactions of titanium and hydrogen peroxide solutions containing Ta(V) ions under a low temperature of 80 °C. It was found that Ta(V) ions favor the low-temperature crystallization and the formation of rutile.

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The deactivation of active oxygen species except NO was discussed. The deactivation was observed in the presence of some blood compatible metals used in clinical fields by simple colorimetry. The blood compatibility was evaluated clinically in terms of partial thromboplastin time (PTT), prothrombin time (PT) and amount of fibrinogen. It was found that the stainless steel (SUS316) and Ti were inert against most of the active oxygen species.

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The in vitro bioactivity, in terms of apatite-forming ability, of calcium silicate glasses containing 10 mol% fluoride ions in the NaF-CaO-SiO2system was examined by soaking in Kokubo's simulated body fluid (SBF) at 36.5°C for 7 d. The surface structure of the glasses was examined by thin-film X-ray diffraction (TF-XRD) and Fourier transform infrared reflection spectroscopy (FT-IR) in order to confirm the apatite deposition. The structure of the calcium silicate glasses was examined by29Si magic angle spinning-nuclear resonance spectroscopy (MAS-NMR) and X-ray photoelectron spectroscopy (XPS). Three calcium silicate glasses containing 10 mol% fluoride ions had different apatite-forming abilities. In the case of CaO/SiO2=1, the apatite-forming ability of 10NaF·45CaO·45SiO2was lower than that of 50CaO·50SiO2. This indicated that the addition of fluoride ions suppressed the apatite-forming ability, irrespective of the structural similarity of the silicate network based on the ratio of CaO/SiO2between the glasses.

DOI： 10.2109/jcersj.111.762

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記述言語：英語   出版者・発行元：KLUWER ACADEMIC PUBL  

Cytotoxicity and cytocompatibility of porous gelatin-siloxane hybrids were evaluated due to osteoblastic cell (MC3T3-E1) proliferation, ALP activity, or their responses to the hybrids and their extracts. The hybrids were found intoxic, and appropriate incorporation of calcium ions stimulated proliferation and differentiation in vitro. Cells were seeded into the porous hybrids and the cell morphology was studied. The hybrids involving calcium ions favored osteoblast growth and differentiation.

DOI： 10.1023/A:1020775227716

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記述言語：英語  

Polydimethylsiloxane (PDMS) and tetraethoxysilane (TEOS)-based porous organically modified silicates (ORMOSILs) for biomedical applications were synthesized through a sol-gel process, using sucrose particles as templates. These materials were characterized by 29Si CP-MAS NMR spectroscopy, thin film X-ray diffraction, and scanning electron microscopy. Their bioactivity was evaluated using a simulated body fluid (SBF) of Kokubo recipe. These materials had a bimodal porous structure with pores of 300-500 μm and 10-50 μm in diameter. NMR showed that the silanol groups of the PDMS chain cross-linked to silica derived from the hydrolysis and condensation of TEOS. The samples containing Ca(II) exhibited apatite deposition on the pore walls within 3 days in SBF.

DOI： 10.1023/A:1020772521781

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記述言語：英語   出版者・発行元：AMER CERAMIC SOC  

Kokubo's simulated body fluid (SBF) has been extensively used for screening to distinguish bioactive materials. The present study examined the effects of organic acids and albumin in the SBF on apatite formation on glass and titanium substrates. Titanium substrates were subject to a H2O2 treatment and subsequent heating to prepare bioactive titania layers. Apatite formation was then examined after soaking the substrates in both SBF and modified SBF containing organic components such as succinic acid, tartaric acid, citric acid and albumin. Calcium-chelate formation due to the organics reduced free calcium ion concentration. The induction time of apatite nucleation on the titania surface was delayed in SBF containing the organic acids. The reduction in the free calcium ion concentration suppressed the apatite nucleation.

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記述言語：英語   出版者・発行元：AMER CERAMIC SOC  

Hydroxy-carbonate apatite (CAp) compositions containing carbonate ions from 0 to 10.9 wt% were synthesized by a wet chemical method. Infrared analysis revealed that carbonate ions were substituted both PO43- and OH- sites. The introduction of CO32- ion into the hydroxyapatite lattice led to an increase in specific surface area and surface charge density. Blood clotting properties were not affected by the contact with CAp samples. The adsorption behavior of proteins was investigated by contacting CAp with model saline containing bovine serum albumin (BSA) and beta(2)-microglobulin (beta(2)-MG). The selectivity against beta(2)-MG increased with increase in the amount of carbonate ions. As surface charge density increased with increase in the amount of carbonate ions, surface charge density played an important role in selective adsorption of beta(2)-MG, but not a sole factor.

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

Synthesized were organically modified silicate (ORMOSILs) hybrids containing colloidal silica as an ingredient, starting from poly (dimethylsiloxane) (PDMS), tetraethoxysilane (TEOS) and calcium nitrate through sol-gel processing. The effects of pre-hydrolysis of TEOS on mechanical strength and viscoelasticity were examined. A sample of composition PDMS/TEOS = 0.60 (molar ratio) with pre-hydrolysis of TEOS showed about 65% maximum failure strain. Thus obtained hybrid exhibited a peak at around -75°C in the storage modulus-temperature curve of the hybrid, due to transverse movements of the PDMS chains. This hybrid, heated at 200°C deposited apatite within 1 d in the simulated body fluid of the Kokubo recipe.

DOI： 10.2109/jcersj.111.318

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

This study concerns with the adsorption of pathogenic substances on highly blood-compatible titania and the adsorption mechanism. Titania was prepared through a sol-gel procedure by hydrolyzing tetraethylor-thotitanate and calcining up to 705°C for 3 h. Pore size distribution and surface charge density were measured as a function of calcining temperature. Adsorption of bilirubin, as a typical pathogenic substance, as well as albumin on the titania powder was studied. Bilirubin was adsorbed either in 4 to 8-nm pores or on the surface with a higher positive charge. Thus, either entrapping bilirubin in the pores or electrostatic interaction between bilirubin and titania surface was effective for the adsorption of bilirubin. The titania powder adsorbed a greater amount of bilirubin than the anion-exchange resin used in clinics, hence they have potential for blood purification therapy.

DOI： 10.2109/jcersj.111.645

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記述言語：英語   出版者・発行元：AMER CERAMIC SOC  

Bioactive titania gel was derived from chemical treatment of Ti substrate with dilute H2O2 solutions and subsequent thermal treatments. We examined the effects of the chemical treatment time and the concentration and pH of the H2O2 solutions on both formation of titania gel and in vitro deposition of apatite or bioactivity. The optimum treatments consisted of 6 mass% H2O2 treatment at 60 degreesC for 3-6 h and subsequent thermal treatment at 400 degreesC for 1 h. Reactions between the titanium substrates and H2O2 involved the oxidation of titanium, titania gel formation and Ti dissolution.

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

Synthesized through sol-gel processing were Ormosil type hybrid gels containing varied mass fractions of colloidal silica, poly (dimethylsiloxane) (PDMS), tetraethoxysilane (TEOS) and calcium nitrate. Viscoelasticity, mechanical strength and 29Si MAS NMR spectra were measured, and in vitro apatite deposition in a simulated body fluid (SBF) of the Kokubo recipe was examined. The relative height of a Tg peak at about - 100°C in tan δ versus temperature curves grew with the colloidal silica content. This peak growth was accounted for the relative increase in PDMS-colloidal silica interactions. As the increase in the compressive strength followed the increase in colloidal silica content, the number of PDMS-silica bonds and hydrogen bond of colloidal silica increased due to the NMR spectra and tan δ curve. Thus, mechanical strength was dependent on PDMS-silica bonds and the hydrogen bond of colloidal silica. On the other hand, as the relative PDMS content increased, the number of PDMS-silica bonds was little influenced while PDMS chain structure increased. The gel (with a molar ratio TEOS:PDMS:H2O:HCl:Ca (NO3)2·4H2O = 1:0.48:5.0:0.9:0.10) containing 14 mass% colloidal silica (CS14P0.48Ca0.10) exhibited the highest maximum failure strain (about 70%) among all samples. Thus, the relative content of PDMS chain structure depending on PDMS content influenced the maximum failure strain. CS14P0.48Ca0.25 could not deposit apatite within 7 d after soaking in SBF, while PDMS/TEOS = 0.24 (molar ratio) could deposit apatite within 3 d. The increase in PDMS content restrained the dissolution of Ca ions.

DOI： 10.2109/jcersj.111.247

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE SA  

Well-crystallized anatase films were deposited on commercially available pure titanium substrates from an acid titanium tetrafluoride aqueous solution kept at 60 degreesC for 24 h. The anatase films consisted of dual layers that were different in topography: a dense inner layer strongly adhered to the Ti substrate and a porous outer layer. In vitro bioactivity of such films was evaluated by soaking them in a simulated body fluid (SBF) of the Kokubo solution to observe their ability to induce apatite deposition. The anatase films with a subsequent thermal treatment at a temperature range of 300-700 degreesC induced apatite deposition within 5 days. Apatite particles were also found to deposit within 7 days on the anatase films being heated at 800 degreesC, which involved much rutile due to direct air oxidation of the titanium substrate. When the heating temperature is lower than 200 degreesC, no apatite deposited on the films even after 10 days of soaking in the SBF solution. The improved in vitro bioactivity of the films subsequently heated over 300 degreesC was attributed to the elimination of fluorine. (C) 2002 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0040-6090(02)00498-4

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We synthesized organically modified silicate (ORMOSILs) gels with colloidal silica (CS) (AEROSIL®) starting from polydimethylsiloxane (PDMS), tetraethoxysilane (TEOS) and calcium nitrate (Ca(NO3)2·4H2O) through sol-gel processing. Dynamic mechanical analysis indicated that relative height of the tanδ peak at about - 100 °C increased with an increase in the relative content of the inorganic components. This peak growth was accounted for by the relative increase in PDMS-colloidal silica particle interactions. The colloidal silica could control the mechanical behavior of the hybrids. The gel of a specific composition could deposit apatite within 3 days of soaking in the simulated body fluid (SBF), since it included many calcium ions on the surface. © 2002 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0928-4931(02)00032-2

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記述言語：英語   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

Titania films with crystal structures of anatase or a mixture of anatase and rutile were prepared through a soft solution approach. The crystalline titania film resulted from crystallization of the previously deposited amorphous gel in an acidic solution. A low pH value of the solution favored the formation of rutile. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S1359-6462(02)00056-8

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

An amorphous titania gel layer was formed on the titanium surface after the titanium specimen was treated with a H2O2/0.1 M HCl solution tit 80degreesC. The thickness of the get layer increased almost linearly With the period of the treatment. A Subsequent heat treatment above 300degreesC transformed gradually the amorphous gel to the anatase crystal structure and the rutile started to appear after heat treatment at 600degreesC. Meanwhile, the densification of the gel occurred significantly after heat treatment above 700degreesC. e Similar to the sol-gel derived titania gel coatings, titania gel layers obtained in the present study exhibited in vitro apatite deposition C ability after the gel layers exceeded a minimum thickness (0.2 mum) and was subsequently heated in a proper temperature range (400-600degreesC). (C) 2002 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0142-9612(01)00254-X

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記述言語：英語   出版者・発行元：AMER CHEMICAL SOC  

Crystalline titania film and powders with crystallite size in the range of nanometers are of great interest in the fields of optical devices, gas sensors, catalysts, and biomaterials. This paper reports a soft solution approach to prepare crystalline titania. After Ti was soaked in hydrogen peroxide solutions containing 3.0 mM tantalum chloride at 80 degreesC for 3 days, crystalline titania films consisting of anatase and rutile were deposited on Ti substrates. While Ti was soaked in tantalum-free hydrogen peroxide solution followed by aging in hydrogen peroxide solution containing tantalum ions, titania films with well-crystallized anatase were obtained. The crystalline titania resulted from crystallization of the previously deposited amorphous gel. Addition of tantalum ions in hydrogen peroxide solutions helps to obtain the crystalline titania and favors especially the formation of rutile phase.

DOI： 10.1021/cg015535y

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We examined the effects of the thermal treatment temperature and Ta(V) species on in vitro apatite forming-ability of titania due to chemical treatment of titanium substrates. The formation of peroxo Ta(V) species (Ta(V)O2) in the H2O2 solution at 60°C effectively promoted not only the decomposition and the elimination of the peroxo and hydroperoxide groups, such as Ti-OOH and Ta-OOH in the titania gel but also the decomposition of H2O2 compared with the formation of peroxo Ti(IV) species (Ti(IV)O2), resulting in enhanced ability of apatite deposition in spite of thermal treatment at the lower temperature such as 100°C. The combined chemical and thermal treatments were applicable for providing both pieces of Ti and Ti mesh with bioactivity.

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Hydroxyapatite (HAP) and carbonate-hydroxy apatite (CAP5 and CAP15) were synthesized under the flow of N2 containing 0%, 5%, or 15% CO2 by wet chemical method, and subsequently calcined at 105-700°C. Infrared analysis showed that carbonate ions substituted PO43- and OH- sites. The clotting characteristics for the fresh mixed plasma contacted with the samples indicated that CAP had better blood compatibility than HAP. The protein adsorption activity was evaluated by contacting with the model saline containing bovine serum albumin (BSA) and β2-microgloburin (β2-MG). CAP15 calcined below 600°C adsorbed the lowest fraction of BSA (9%) whereas it adsorbed the highest fraction of β2-MG (47%). It was concluded that the selective adsorption activity against β2-MG was related to the carbonate ions incorporated in hydroxyapatite.

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Treatment with a hydrogen peroxide solution containing tantalum chloride followed by heating provided titanium with bioactivity where a titania gel layer derived on surface played the essential role. Effects of surface roughness and gel thickness on in vitro bioactivity were examined using the Kokubo solution. In vitro evaluation suggested enhanced interfacial bond strength between bone and Ti implants by obtaining thinner titania layer on rougher Ti surface.

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The organic-inorganic hybrid gels were synthesized starting from poly (dimethylsiloxane)(PDMS), tetraethoxysilane (TEOS), colloidal silica and calcium nitrate (Ca(NO3)2·4H2O) through sol-gel processing. The effects of heating on the mechanical properties and microstructure of the synthesized samples were investigated. The compressive strength of the synthesized samples increased by heating. The dynamic mechanical analysis of the synthesized samples showed increase of storage modulus and decrease of the loss factor, tanδ. It was suggested that the mobility of PDMS chain was restricted with the increase of PDMS-silica interaction by heating.

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記述言語：英語   出版者・発行元：PERGAMON-ELSEVIER SCIENCE LTD  

Anatase films with sub-micron porous structure were deposited homogeneously on Ti substrates by simply soaking in 15 wt.% hydrogen peroxide solution at 80 degreesC for 1 h followed by heating at 300 degreesC for 1 h in air. Deposition of the porous titania film was not sensitive to substrate morphology, whilst affected readily by the reaction rate. (C) 2002 Acta Materialia Inc. Published by Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S1359-6462(01)01207-6

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

Anatase of good crystallinity has been developed on titanium substrates by soaking in a 30 mass% hydrogen peroxide solution at 80°C for 8 h, soaking in distilled water at ambient temperature for 12 h, and subsequently aging in distilled water at 80°C for 3d. The anatase layers exhibit good bioactivity as inducing apatite deposition in Kokubo's simulated body fluid within 2d.

DOI： 10.2109/jcersj.110.78

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記述言語：英語  

Porous and bioactive gelatin-siloxane hybrids were successfully synthesized by using a combined sol-gel processing, post-gelation soaking, and freeze-drying process to provide a novel kind of materials in the developments and optimization of bone tissue engineering. The pore sizes of the hybrids can be well controlled by varying the freezing temperature. The scaffolds were soaked in a simulated body fluid (SBF) up to 14 days to evaluate the in vitro bioactivity. The Ca2+-containing scaffolds showed in vitro bioactivity as they biomimetically deposited apatite, but the Ca2+-free scaffolds failed. Cytotoxicity and cytocompatibility of those scaffolds and their extracts were monitored by the MC3T3-E1 cell responses, including the cell proliferation and the alkaline phosphatase activity. It was demonstrated that appropriate incorporation of Ca2+ ions stimulated osteoblast proliferation and differentiation in vitro. © 2002 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0142-9612(02)00226-0

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記述言語：英語   出版者・発行元：ELSEVIER SCI LTD  

Apatite formation on implants is important in achieving a direct bonding to bone tissue. We recently showed that titanium metal chemically treated with a hydrogen peroxide solution containing tantalum chloride has the ability to form a hydroxyapatite layer in simulated body fluid which had inorganic ion composition similar to human blood plasma. In this study, a pure titanium cylinder (4.0 mm in diameter. 20.0 mm in length) treated with this method was implanted into a hole (4.2 mm in diameter) in a rabbit's tibia. After implantation for predetermined periods up to 16 weeks. the specimens were extracted with bone tissue, and were examined by push-out test to evaluate the shearing force between the implant and bone tissue. The results were compared with those of non-treated pure titanium. Eight weeks after surgery. the shearing force of the treated titanium implanted in the 4.2 mm-hole was significantly higher than that of non-treated titanium. although the surface roughness was not changed after the treatment. Scanning electron microscopic (SEM) observation and energy-dispersive X-my (EDX) microanalysis showed that the bone comes very close to the surface of the treated titanium. Moreover, the shearing force was higher for the implanted sample in the 4.0 mm-hole than that in the 4.2 mm-hole. Thus. it is confirmed that the treatment with hydrogen peroxide solution containing tantalum chloride provides higher bonding ability on titanium implants in vivo. (C) 2001 Elsevier Science Ltd. All rights reserved.

DOI： 10.1016/S0142-9612(01)00036-9

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記述言語：英語   出版者・発行元：JOURNAL MATER SCI TECHNOL  

Several gelatin-silicate composites, with or without incorporation of Ca2+ ions, were synthesized through set-gel processing starting from gelatin and 3- (glycidoxypropyl) trimethoxysilane. The structure around the Si atoms was similar for all the samples. The measurement of viscoelastic properties indicated that the glass transition temperature and activation energy decreased with the incorporation of Ca2+ ions. The Ca2+ ion-containing composites were bioactive as they spontaneously deposited apatite when soaked in a simulated body fluid of the Kokubo recipe.

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記述言語：英語   出版者・発行元：JOHN WILEY & SONS INC  

Commercially pure titanium specimens are subjected to three different treatments, and their bioactivity are evaluated by immersing the specimens in a simulated body fluid (SBF, Kokubo's recipe) for various periods up to 7 days, with particular attention being paid to the differences in apatite deposition between surfaces open to SBF and surfaces in contact with the container's bottom. The treatment with a H2O2/HCl solution at 80 degreesC for 30 min followed by heating at 400 degreesC for 1 h produces an anatase titania gel layer on the specimen surface. This gel layer deposits apatite both on the contact and on open surfaces, and apatite deposition ability does not change with pre-staking in distilled water. The treatment with a NaOH solution at 60 degreesC for 3 days produces a sodium titanate gel layer. This gel layer can deposit apatite only on the contact surface, and the apatite deposition ability is completely lost after 1 day of pre-staking in distilled water. It is concluded, therefore, that the bioactivity of the titania gel originates from the favorable structure of the gel itself while the bioactivity of the sodium titanate gel depends heavily on ion release from the gel. The third treatment, a simple heat treatment at 400 degreesC for 1 h, produces a dense (not porous) oxide layer on the specimen surface. The specimens can deposit apatite on the contact surface after only 3 days of staking in SBF, but they cannot deposit apatite on the open surface for up to 2 months of staking. The implications of such apatite deposition behavior have been discussed in relation to the environments of titanium implants in bone as well as to the methodology of the SBF staking experiment. (C) 2000 John Wiley & Sons, Inc.

DOI： 10.1002/1097-4636(200102)54:2<172::AID-JBM3>3.0.CO;2-#

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Apatite formation on artificial materials in a body environment is prerequisite for bioactivity or tissue-material bonding. A specific hydrated silica or titania gel has the ability of apatite deposition in body environment. Electrochemical preparation of such a bioactive titanium oxide layer on titanium (Ti) is reported. Ti was kept at 9.5 V for 1 hour for oxidation and subsequently kept at -2.0 V for 10 min for adsorbing calcium hydroxide on the surface. The specimens subject to the electrochemical treatments were found so bioactive as to deposit apatite within 12 hours in a simulated body fluid. Calcium hydroxide precipitated on the bioactive surface favored spontaneous deposition of apatite in the fluid. We examined the effect of autoclave sterilization considered in vivo experiment. It slightly reduced the ability of apatite deposition.

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We examined blood compatibility and superoxide dismutase (SOD) activity of titania gels yielded on Ti substrate due to the treatment with H2O2 solutions. They were correlated to the titania gel surface characteristics. Ti subjected to the chemical treatment with H2O2(H2O2-Ti) had high blood compatibility or hardly coagulated, and showed higher SOD activity than Ti without the chemical treatment. Ti treated with a hydrogen peroxide containing TaCl5(H2O2/Ta-Ti) had little lower blood compatibility than H2O2-Ti, and the SOD activity for H2O2/Ta-Ti were lower than that for any other Ti (Ti, H2O2-Ti). Thus the decrease in SOD activity for the plasma contacted with H2O2/Ta-Ti was in part caused by the Ta ions on the titania gel.

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Biomimetic deposition of calcium phosphate (apatite) on Ti substrates air-oxidized at various temperatures was studied after they were soaked in a simulated body fluid (Kokubo solution, SBF), and the deposition behavior of the surface open to SBF (open surface and the surface facing to the bottom of the container that held SBF and the specimen (contact surface) was compared. The contact surface deposited apatite in 7 days whereas the open surface could not in 2 months. The greatest ability of depositing apatite was provided by oxidation at 400°C. Moreover, apatite deposited on PTFE or silicone plate facing to the 400°C-treated Ti substrate with the tapered spacing of 0 to 0.15 mm. The mechanism of the apatite deposition on the contact surfaces was discussed in relation to the passive dissolution of titanium in SBF. The release of titanium hydroxide and OH ions from the titanium surface was considered responsible for the apatite deposition.

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Protein adsorption characteristics and blood compatibility of the sol-gel derived titania has been examined by measuring activity of adsorbing bilirubin and protein in plasma as well as plasma clotting properties. It was suggested that the important factors for the specific protein adsorption activity were acid-base characteristics and pore size distribution of the gel due to the coexistence of anatase/rutile phases.

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

Several gelatin-siloxane hybrids incorporating Ca2+ ions were synthesized through a sol-gel process starting with gelatin, 3-(glycidoxypropyl) trimethoxysilane (GPSM), and Ca(NO3)2. Amino acid analysis, 29Si NMR spectroscopy, Fourier-transform infrared (FT-IR) spectroscopy, and dynamic mechanical thermal analysis were used to assess the hybrid structure. It has been indicated that the grafting degree of epoxy groups of GPSM to gelatin and the extent of polymerization of methoxysilane end groups of GPSM strongly depended on the fraction of GPSM (fG) in the hybrids, but not on incorporation of Ca2+ ions. Hence, the hybrids with the same fG value, independent of incorporation of Ca2+ ions, had a similar cross-link density. However, the glass transition temperature (Tg) and storage modulus (E′) around Tg decreased with incorporation of Ca2+ ions. Through the deconvolution of amide I bands of FT-IR spectra, flexibility may be interpreted by that the percentage of gelatin having a random structure increased with incorporation of Ca2+ ions. The Ca2+-containing hybrids can spontaneously deposit apatite when they were soaked in a simulated body fluid of the Kokubo recipe, showing their bioactivity.

DOI： 10.2109/jcersj.109.1269_406

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記述言語：英語   出版者・発行元：American Ceramic Society  

The structures of M2O3-TeO2 (M = Al and Ga) glasses have been investigated by means of 125Te, 27Al, and 71Ga NMR spectroscopies. The structural units of respective cations in M2O3-TeO2 glasses were quantitatively analyzed. The fractions of TeO4 trigonal hipyramid. AlO6 and GaO6 octahedra decreased and those of TeO3 trigonal pyramid, AlO4, AlO5, and GaO4 polyhedra increased with increasing M2O3 content. Based on the local structures around Te, Al, and Ga atoms, the structure models of M2O3-TeO2 glasses were proposed.

DOI： 10.1111/j.1151-2916.2001.tb00749.x

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記述言語：英語   出版者・発行元：KLUWER ACADEMIC PUBL  

We examined blood compatibility of titania gels prepared through a sol-gel processing or yielded on titanium substrates by treating with hydrogen peroxide or simple heating. The blood compatibility was evaluated in terms of blood clotting time and correlated to the crystalline phases, roughness, specific surface area, and wettability. The sol-gel derived titania gel heated above 200 degreesC had good blood compatibility. Ti substrate treated with hydrogen peroxide and subsequently heated at 550 degreesC showed the best blood compatibility among the Ti substrates with or without the chemical treatment and heat-treatment. The specimen consisted of rutile and anatase phases, and had hydrophilic surface.

DOI： 10.1023/A:1011269802356

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記述言語：英語   出版者・発行元：KLUWER ACADEMIC PUBL  

A new type of inorganic-organic hybrid materials incorporating gelatin and 3-(glycidoxypropyl) trimethoxysilane (GPSM) was prepared through sol-gel processing. A solid-state Si-29 NMR analysis indicated that all the methoxy silane groups of GPSM were polymerized to yield -Si-O-Si- bridging bonds. An amino acid analysis confirmed grafting reactions of GPSM against gelatin chains. The increasing GPSM/gelatin ratio stimulated gel formation, phase separation, and the density of GPSM-crosslinking of the gelatin chains as well as it changed the micro- and macro- structures and the viscoelastic properties of the final products.

DOI： 10.1023/A:1011226104173

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記述言語：英語  

Ca(II) containing porous hybrids of gelatin and 3-(glycidoxypropyl)trimethoxysilane (GPSM) were prepared using a sol-gel process, post-gelation soaking, and freeze-drying. The porosity and pore size of the hybrids could be well controlled by the freezing temperature and the pH value of the soaking solution. The pore characteristics were related to the structure change during the soaking treatment. A second soaking of the porous hybrids introduced a binary-pore distribution. The rate of biodegradation in a trishydroxymethylaminomethane (Tris) buffer solution decreased with an increased GPSM content. A bone-like apatite layer was able to form in the Ca(II) containing porous gelatin-siloxane hybrids upon soaking in a stimulated body fluid (Kokubo recipe). These hybrid materials are proposed to find application as novel bioactive and biodegradable scaffolds in bone tissue engineering. © 2001 Elsevier Science B.V.

DOI： 10.1016/S0022-3093(01)00441-0

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記述言語：英語   出版者・発行元：KLUWER ACADEMIC PUBL  

Organically modified silicates containing calcium ion have a potential to bond to bone via an apatite layer deposited on their surfaces in the body environment. In this study, we examined the relationship between apatite deposition and the microstructure of the organically modified silicates synthesized from tetraethoxysilane (TEOS) and poly (dimethylsiloxane) (PDMS) with a different amount of calcium nitrate tetrahydrate (Ca(NO3)(2). 4H(2)O) and hydrochloric acid (HCl). Apatite deposition was evaluated in vitro using a simulated body fluid (Kokubo solution). Copolymerization was confirmed between TEOS and PDMS even if PDMS free from -SiOH termination are used as one of the starting materials. The porosity and Ca content incorporated in the structure depended on the amount of HCl, whereas analysis of Si-29 MAS NMR spectra indicates that it caused few effects on the local structure around Si atoms. Apatite-forming ability is enhanced by optimal amounts of HCl and Ca (NO3)(2). 4H(2)O. The difference in apatite-forming ability among the hybrid gels was attributed to both Ca(II) contents in the structure and aggregation states of the Si-OH groups. Better bioactivity of the hybrid gels is achieved by the release of Ca(II) ions trapped in structure at gelation and the formation of hydrated silica rich in Si-OH.

DOI： 10.1023/A:1011217818285

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記述言語：英語   出版者・発行元：Ceramic Society of Japan  

Nucleation and crystal growth mechanism of apatite formation on porous silica gel derived by a sol-gel procedure was investigated by the use of several simulated body fluids (SBF's) that had different concentrations of Ca(II), P(V), and OH- but had the same degree of supersaturation for hydroxyapatite. Induction time of apatite crystallization in SBF's was evaluated by thin film X-ray diffractometry. The effect of each ion on the induction time increased in the order: Ca(II)-rich SBF &lt
P(V)-rich SBF ≪ OH--rich SBF, while that for the rate of initial crystal growth of apatite increased in the order: P(V)-rich SBF &lt
Ca(II)-rich SBF &lt
OH--rich SBF. It suggested that amorphous calcium phosphate (ACP) deposited as the precursor of apatite and ACP transformed into apatite nuclei by the incorporation of OH-. Moreover, the transformation was accelerated by large amount of ACP and was assisted by the rearrangement of silicate units in the gel surface. Ca(II) was richer in ACP deposited in Ca(II)-rich SBF and OH--rich SBF than that deposited in P(V)-rich SBF. Ca(II)-rich ACP was favorable for crystal growth.

DOI： 10.2109/jcersj.109.1269_412

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Apatite formation on artificial materials in a body environment is the prerequisite condition for showing bioactivity i.e. bone-bonding ability. A specific hydrated silica or titania gel has the ability of apatite deposition in body environment. We electrochemically prepared such a bioactive titanium oxide layer on titanium(Ti) with a cell consisting of Ti as the working electrode, Pt as the counter one, Ag/AgCl as the reference one, and an aqueous solution of 0.1 mol/L Ca(NO3)2 as the electrolyte solution. Ti was kept at 9.5V for 1 hour for oxidation(denoted as Ca9.5). Ti was subject to cathodic polarization at -3.0V for 10 min(Ca-3.0).: calcium ions were expected to be adsorbed on its surface. On treatment Ca9.5-3.0 Ti was first oxidated at 9.5V for 1 hour and subsequently kept at -3.0V for 10 min. The specimens of Ca9.5-3.0 and Ca-3.0 were found so bioactive as to deposit apatite within 12 hours and 1 day, respectively, in a simulated body fluid(Kokubo solution) whereas those due to Ca9.5 could not deposit apatite within 7 days. Calcium hydroxide and calcium carbonate detected on the bioactive surface caused no harmful effects on spontaneous deposition of apatite in the fluid.

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Ca(II) containing porous hybrids of gelatin and 3-(glycidoxypropyl) trimethoxysilane (GPSM) were prepared with sol-gel processing and freeze-drying techniques. The freezing temperature could control porosity and pore size of the hybrids. The biodegradation rate of the hybrids in a Tris buffer solution decreased with an increase in GPSM content. The bone-like apatite layer could form on the Ca(II) containing porous gelatin-silicate hybrids when they were soaked in a stimulated body fluid (SBF), hence they were applicable to be the bioactive scaffolds for bone tissue engineering.

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記述言語：英語  

Bioactive organic-inorganic hybrids were synthesized through sol-gel processing starting from γ-methacryloxypropyltrimethoxysilane. NMR-spectroscopic studies showed the presence of silanol groups (Si-OH) and Si-O-Si bonds. In vitro tests of the hybrids for bioactivity with a simulated body fluid (Kokubo solution) indicated that only calcium-containing hybrids could form apatite on their surfaces. Thus the presence of calcium ions was no less important to deposit apatite than the formation of silanol groups or Si-O-Si bonds.

DOI： 10.1023/A:1008795629804

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記述言語：英語   出版者・発行元：John Wiley &amp; Sons Inc  

Commercially pure titanium was treated with a H2O2/3 mM TaCl5 solution at 80°C for various periods and a titania gel layer was formed on the surface. This gel remained amorphous when heating for 1 h below 200°C and transformed to anatase after heating between 300°and 600°C. The anatase titania gel layers were found to be bioactive as to deposit carbonate ion- incorporated apatite within 1 day of immersion in the Kokubo solution, whereas the amorphous layers did not deposit apatite within 7 days. The apatite particles were found to nucleate preferentially inside the cracks prevailing in the thicker gel layers of 1-h chemically treated specimens. After immersing for 2 days, the titanium specimens were almost completely covered by apatite. Elimination of peroxide radicals from the titania gel and formation of anatase upon subsequent heating are considered to be responsible for the enhanced ability of apatite deposition. (C) 2000 John Wiley and Sons, Inc.

DOI： 10.1002/1097-4636(200010)52:1<171::AID-JBM22>3.0.CO;2-O

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記述言語：英語   出版者・発行元：ELSEVIER SCIENCE BV  

P-31 magic-angle-spinning (MAS) NMR spectra were measured for several oxides, such as Al2O3, SiO2, TiO2 and Ta2O5 which were treated with TaCl5-free H2O2 solutions and TaCl5-containing H2O2 solutions and soaked in a simulated body fluid (Kokubo solution; pH = 7.4) for 7 days. The chemical states of phosphate anions deposited on these oxides were determined. A P-31 MAS-NMR peak at a chemical shift ca. 3 ppm was observed in the spectra of Ta2O5 and for the other oxides when they were treated with the TaCl5-containing H2O2 solution. Without the treatment with the TaCl5-containing H2O2 solution no P-31 MAS-NMR peaks were observed in the spectra of the oxides. The P-31 chemical shift, ca. 3 ppm, indicated that orthophosphate anions? PO43- as found in hydroxyapatite and a cortical bone (rabbit) were adsorbed on the oxides. The surface of Ta2O5 particles and the oxides treated with the TaCl5-containing H2O2 solution induced the deposition of apatite. We concluded that the surface Ta(V) species supported on the oxides induced a bone-like apatite nucleus, even though the base oxides did not deposit apatite. (C) 2000 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0022-3093(99)00649-3

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記述言語：英語   出版者・発行元：IOP PUBLISHING LTD  

The structures of V2O5-TeO2 glasses are investigated by means of Te-125 and V-51 static NMR spectroscopies and the local structures around the Te and V atoms are discussed in detail from the respective NMR spectra. The fraction of TeO3 trigonal pyramids increases and that of TeO4 trigonal bipyramids decreases with increasing V2O5 content. The structures of V2O5-TeO2 glasses are quite different from those of tellurite glasses containing network-modifying oxides. The fraction of VO4 tetrahedra increases and that of VO5 trigonal bipyramids decreases with increasing V2O5 content. Both chains consisting of tellurite structural units and those consisting of vanadate structural units contribute to the formation of the glass network in V2O5-TeO2 glasses.

DOI： 10.1088/0953-8984/12/12/302

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X-ray photoelectron (XPS) and 29Si magic angle spinning (MAS)-NMR spectroscopy have been used to examine the chemical states of fluorine, oxygen, silicon and lead atoms in the glasses of composition xPbF2 · (100-y-x)PbO· ySiO2 (x = 0, 5, 10, 15, 20, 30 mol%, y = 30, 50, 60 mol%). The analysis of the F Is spectra indicated that Pb2+ and F- ions are preferentially located among the Si-O skeleton forming ionic Pb-F clusters. The fraction of the bridging (BO) and non-bridging oxygen (NBO) atoms was derived from the O 1s spectra. The network of the fluorine-containing glasses was concluded to depend on the ratio PbO/SiO2; when the ratio PbO/SiO2 was lower than 0.5, not only Pb atoms but also F atoms play a role as network modifiers, while when the ratio PbO/SiO2 is higher than 1.33, part of Pb atoms plays a role as a glass network former. © 2000 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0022-3093(00)00233-7

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Ca(II) containing porous hybrids of gelatin and 3-(glycidoxypropyl) trimethoxysilane (GPSM) were prepared with sol-gel processing and freeze-drying techniques. The freezing temperature could control porosity and pore size of the hybrids. The biodegradation rate of the hybrids in a Tris buffer solution decreased with an increase in GPSM content. The bone-like apatite layer could form on the Ca(II) containing porous gelatin-silicate hybrids when they were soaked in a stimulated body fluid (SBF), hence they were applicable to be the bioactive scaffolds for bone tissue engineering.

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記述言語：英語   出版者・発行元：Elsevier  

AM1 molecular orbital (MO) calculations were made for various cluster models of silica and for fluorinated silica. Calculations were made on clusters containing up to 12SiO4 units. On the basis of the relative position and relative intensity of the theoretical vibrational spectra of fluorine-free silica clusters with different sizes and fluorinated silica clusters, the effects of the replacement of OH groups by fluorine on the vibrational spectra of the silica clusters were established. In ring-type silica clusters the absorption around 640-720 cm-1, assignable to the ring vibration within the ring plane, could be seen in the three-membered ring. The intensity of absorption around 500-600 cm-1, assignable to the O-Si-O bending vibration, decreased with increasing size of rings and by the replacement of hydroxyl groups (OH-) by fluorine (F-). In block-type silica clusters all absorption peaks shifted to higher frequencies than those in ring-type silica clusters. The absorption peaks in AM1 calculated vibrational spectra correlated with the experimental IR spectra except for the stretching vibration of Si-F bonds. © 2000 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0022-3093(99)00664-X

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Hydrated silica rich Si-OH and Si-O- groups serve in a body environment as sites for nucleation of apatite, and are known as an essential chemical species for bioactive materials. Organic polymers having surface modified with the hydrated silica will show bioactivity: bone tissues grow toward the apatite layer and bond to materials. Thus MOPS-M (3-methacryloxypropyltrimethoxysilane) was grafted under emulsion polymerization procedure to high density polyethylene (HDPE), poly (vinyl chloride) (PVC) and polyamide (PA) substrates to examine in vitro deposition of apatite (bioactivity) after soaking in a simulated body fluid (Kokubo solution). Bioactivity was confirmed for the grafted PVC and PA substrates and discussed in terms of contact angle and relative amount of grafted silane molecules.

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29Si and 31P magic-angle-spinning nuclear magnetic resonance (MAS-NMR) spectra were used to analyze 20Na2O·80SiO2 glass particles before and after soaking in a simulated body fluid (SBF; Kokubo solution, pH 7.4) for various periods (up to 14 d). The structure of the bulk glass and the glass surface, as well as the chemical states of the calcium phosphates adsorbed on the glass surface, were examined. The bulk glass before soaking in the SBF showed two 29Si MAS-NMR resonances, at -100 and -110 ppm, which were attributable to Si(OSi)3ONa and Si(OSi)4 units, respectively. A new -105 ppm peak, which was due to Si(OSi)3OH units, appeared after soaking in the SBF and grew as the soaking period increased. Thus, in the SBF, the glass network was degraded and hydrolyzed; that is, dissolution of the Na+ ions from the glass network and the formation of Si-O- groups occurred. After soaking for 1 d, a 31P MAS-NMR resonance peak of orthophosphate (PO43-) ions that were deposited on the glass surface appeared at approx. 3.0 ppm and grew as the soaking period increased. The chemical shift shows that the local structural environment of phosphorus atoms and ions was very similar to that of hydroxyapatite or rabbit cortical bone. Inductively coupled plasma atomic emission spectroscopic analysis confirmed the adsorption of calcium phosphates on the glasses and the close relationship between the dissolution of the NaPLU ions and the precipitation of the calcium phosphates. It was concluded that the layer of hydrated silica gel, which was composed of Si(OSi)3O- units, provided the negatively charged sites that induced or promoted the precipitation of calcium phosphates, which led to apatite nucleation and crystallization.

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記述言語：英語  

DOI： 10.2109/jcersj.107.395

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

The structure of MO-TeO2 (RI Mg Zn, Sr, Ba and Pb) glasses has been studied by means of Te-125 static NMR technique. The fraction of TeO4, trigonal bipyramid (tbp), N-4 decreased and that of TeO3 trigonal pyramid (tp), N-3 increased almost linearly up to 33.3 mol% MO and rapidly in the range of 33.3 to 40 mol% MO, with increasing MO content, It was found that the glasses containing MO in the range of 40 to 45 mol% MO consisted only of TeO3 tp. On the basis of the structural model proposed in a previous paper, the fractions of TeO4 tbp without a non-bridging oxygen (NBO) atom, TeO4/2 (N-4(0)), TeO4 tbp with an NBO atom, O-3/2 Te-O- (N-4(-)) and TeO3 tp with two NBO atoms, O1/2Te(= O)-O- (N-3(-)) were calculated. The structural change for MO-TeO2 glasses in the range of 0 to 33.3 mol% MO could be well represented by the model previously proposed for alkali tellurite binary glasses. A new model which represents the structural change for MO-TeO2 glasses containing more than 33.3 mol% MO has been proposed.

DOI： 10.2109/jcersj.107.395

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記述言語：英語   出版者・発行元：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

The structure of MO-TeO2 (RI Mg Zn, Sr, Ba and Pb) glasses has been studied by means of Te-125 static NMR technique. The fraction of TeO4, trigonal bipyramid (tbp), N-4 decreased and that of TeO3 trigonal pyramid (tp), N-3 increased almost linearly up to 33.3 mol% MO and rapidly in the range of 33.3 to 40 mol% MO, with increasing MO content, It was found that the glasses containing MO in the range of 40 to 45 mol% MO consisted only of TeO3 tp. On the basis of the structural model proposed in a previous paper, the fractions of TeO4 tbp without a non-bridging oxygen (NBO) atom, TeO4/2 (N-4(0)), TeO4 tbp with an NBO atom, O-3/2 Te-O- (N-4(-)) and TeO3 tp with two NBO atoms, O1/2Te(= O)-O- (N-3(-)) were calculated. The structural change for MO-TeO2 glasses in the range of 0 to 33.3 mol% MO could be well represented by the model previously proposed for alkali tellurite binary glasses. A new model which represents the structural change for MO-TeO2 glasses containing more than 33.3 mol% MO has been proposed.

DOI： 10.2109/jcersj.107.395

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The structure of MO-TeO2(M=Mg, Zn, Sr, Ba and Pb) glasses has been studied by means of125Te static NMR technique. The fraction of TeO4trigonal bipyramid (tbp), N4decreased and that of TeO3trigonal pyramid (tp), N3increased almost linearly up to 33.3 mol% MO and rapidly in the range of 33.3 to 40 mol% MO, with increasing MO content. It was found that the glasses containing MO in the range of 40 to 45 mol% MO consisted only of TeO3tp. On the basis of the structural model proposed in a previous paper, the fractions of TeO1tbp without a non-bridging oxygen (NBO) atom, TeO4/2(N40), TeO4tbp with an NBO atom, O3/2Te-O-(N4-) and TeO3tp with two NBO atoms, O1/2Te(=O)-O-(N3-) were calculated. The structural change for MO-TeO2glasses in the range of 0 to 33.3 mol% MO could be well represented by the model previously proposed for alkali tellurite binary glasses. A new model which represents the structural change for MO-TeO2glasses containing more than 33.3 mol% MO has been proposed.

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125Te static and magic-angle spinning (MAS) NMR spectra of tellurite crystals with known crystal structures have been measured to determine the isotropic chemical shift δiso, the chemical shift anisotropy Δδ and the asymmetry parameter η. On the basis of structural unit, tellurite crystals are classified for convenience into TeO3 type (isolated TeO3 and terminal TeO3 type), TeO3+1 type and TeO4 type (α-TeO2 and β-TeO2 type). As a result, the following relations were found: TeO3 ≥ TeO3+1 ≈ β-TeO2 &gt; α-TeO2 in δiso(MAS), β-TeO2 ≥ α-TeO2 &gt; TeO3+1 &gt; terminal TeO3 ≥ isolated TeO3 in |Δδ| and TeO4 ≥ TeO3+1 ≥ TeO3 in η. It was also found that the combination of |Δδ| and η, namely, the relative values of δ1, δ2 and δ3, can elucidate the local structure around Te atoms more definitely than δiso. This diagram is useful for examining the structures of tellurite crystals and glasses. (Glasses are discussed in another paper.) © 1999 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0022-3093(98)00811-4

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記述言語：英語  

The structure of TeO2 and M2O-TeO2 (M - Li, Na, K, Rb and Cs) glasses has been investigated by means of 125Te static and magic-angle spinning (MAS) NMR spectroscopies. On the basis of the relationship between the local structures around Te atoms and the NMR parameters obtained by 125Te NMR spectra of various tellurite crystals, the local structures around Te atoms in TeO2 and M2O-TeO2 glasses were examined. The spectral simulation of static NMR spectra enabled us to discriminate between TeO3 trigonal pyramid (tp) and TeO4 trigonal bipyramid (tbp) and to estimate the fractions of TeO3 tp (N3) and TeO4 tbp (N4). It was concluded that in TeO2 glass TeO4 tbps are connected by sharing their corners as in α-TeO2 crystal. N3 increased and N4 decreased with increasing M2O content. On the basis of a previous structural model, the fractions of TeO4 tbp without a non-bridging oxygen (NBO) atom, TeO4 tbp with an NBO atom, and TeO3 tp with two NBO atoms were calculated. A new model which presents the structural change for M2O-TeO2 glasses has been proposed. © 1999 Elsevier Science B.V. All rights reserved.

DOI： 10.1016/S0022-3093(98)00812-6

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