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The surfaces of commercially available pure titanium (cpTi) and Ti6Al4V alloy specimens were modified to form highly ordered rutile nanorod arrays by chemical treatment and subsequent aging treatment. The densities of the rutile rods were (1.04 +/- 0.06) x10(3) and (0.70 +/- 0.10) x10(3) mu m(-2) for the cpTi and Ti6Al4V alloy specimens, respectively. Both the rutile nanorod arrays on the cpTi and Ti6Al4V alloy specimens deposited apatite particles when soaked in simulated body fluid (SBF) for one day. After soaking for various other periods, scanning electron microscopy images and thin-film X-ray diffraction patterns of these specimens showed that the cpTi specimens exhibited a superior rate of apatite nucleation and favored the formation of numerous apatite particles with larger diameter. This superior apatite-forming ability of the cpTi specimens can be attributed to the dense, thick titania layers with higher rutile nanorod density on their surfaces.

Although autoclaving is a common sterilization method for biomedical devices, the ability to induce deposition of apatite particles on hydrothermally treated titanium is still not fully realized. This is because the induction ability is too weak to be evaluated via in vitro apatite formation in Kokubo's simulated body fluid (SBF) by the conventional immersion method, i.e. using samples with open and smooth surface. This study reports on the surface structure of hydrothermally treated titanium and the ability to induce deposition of apatite particles on the surface of parallel confined spaces separated by sub-millimeter gaps in Kokubo's SBF. Thin-film X-ray diffraction and analyses using Fourier transform infra-red (FT-IR) spectroscopy and Raman spectroscopy revealed that a nano-crystalline anatase-type titanium oxide layer was formed on titanium substrates after hydrothermal treatment at 150 degrees C for 2 h. When growth of the titanium oxide layer was moderately suppressed, the hydrothermally treated titanium surface exhibited a characteristic interference color, silver or gold, which does not impair the esthetic appearance of the titanium-based implant. The ability to induce deposition of apatite particles on hydrothermally treated titanium was remarkably amplified by parallel alignment of substrates separated by sub-millimeter gaps.

Current apheresis or blood purification practices depend primarily on polymer systems that enable filtering and adsorbing pathogenic substances in blood: the latter consist of base polymer-based carriers and active ligands. However, some ceramic materials, such as silica, titania, and hydroxyapatite, are known to be blood compatible. The research on their use for apheresis is very small in comparison to the polymer systems, but the ceramic-based materials have been steadily discussed until now. This article aims to provide some feasible ideas and strategies together with their microstructures for further apheresis applications. After blood clotting pathways and apheresis practice, several blood-compatible materials in the form of particles, coatings (layers), and macrospheres are introduced. In addition, the materials for stent applications are also mentioned because the highest blood compatibility is demanded. Examples of bilirubin, b2-microglobulin (B2M), bovine serum albumin (BSA), and lysozyme (LYZ) adsorption on titania gel particles, Zn-substituted hydroxyapatite, and so-gel derived silica macrospheres are presented.

This study presents a new strategy for preparing highly oriented nanorod array of divalent ion substituted hydroxyapatite (HAp) and factors controlling the rate of glass conversion. HAp nanorod arrays were prepared on a series of alkali/alkaline-earth silicate glasses in the Na2O–CaO–SrO–SiO2 system in phosphate aqueous solutions with different pH values via a glass conversion process. The effects of the substitution of Sr2+ for Ca2+ and the network connectivity (NC) of the silicate glasses on the degree of crystal orientation of the nanorod array of HAp crystals, the crystallite size, and the partial substitution of Sr2+ for Ca2+ in the HAp crystal lattice were investigated using X-ray diffraction, 29Si magic angle spinning nuclear magnetic resonance (NMR) spectroscopy, and field-emission scanning electron microscopy. Sr-free Na2O–CaO–SiO2 glass was converted into HAp nanorod arrays highly-oriented toward the c-axis, whereas the increase in the NC of the glass led to a decrease in the rate of the conversion process from glass to HAp, which resulted in the reduction of the degree of c-axis orientation of the nanorod array of the HAp crystals. However, the rate of the conversion process was remarkably promoted in alkaline phosphate solutions, resulting in an increase of the degree of c-axis orientation of the nanorod array. The Sr/(Sr + Ca) molar fraction of silicate glasses determined the molar fraction of substituted Sr2+ in HAp crystal lattice.

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.

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.

Trehalose forms a glass that can be used to preserve labile substances under desiccation. The crystallization characteristics, namely crystallization temperature (Tcry) and isothermal crystallization behavior of amorphous trehalose, dried from alcohol (methanol, ethanol), was analyzed and the results were compared with those for the amorphous trehalose freeze-dried from water. The use of alcohol as a solvent lowered the Tcry from 184 ± 6 °C for the case of an aqueous solvent to 103 ± 5 °C/methanol and 120 ± 8 °C/ethanol. The formation of multiple forms of crystals and partial melting were suggested by the thermal analysis. Isothermal crystallization experiments showed that the alcohol-originated amorphous trehalose was eventually exclusively converted into β-form crystals. The induction period (tind) before the start of isothermal crystallization was markedly shortened when alcohol was used as the solvent compared to water. The tind values for various amorphous sugar samples including the alcohol-originated ones could be correlated with difference between Tcry and the sample temperature.

Natural calcium phosphates derived from fish wastes are a promising material for biomedical application. However, their sintered ceramics are not fully characterized in terms of mechanical and biological properties. In this study, natural calcium phosphate was synthesized through a thermal calcination process from salmon fish bone wastes. The salmon-derived calcium phosphates (sCaP) were sintered at different temperatures to obtain natural calcium phosphate bioceramics and then were investigated in terms of their microstructure, mechanical properties and biocompatibility. In particular, this work is concerned with the effects of grain size on the relative density and microhardness of the sCaP bioceramics. Ca/P ratio of the sintered sCaP ranged from 1.73 to 1.52 when the sintering temperature was raised from 1000 to 1300 &deg, C. The crystal phase of all the sCaP bioceramics obtained was biphasic and composed of hydroxyapatite (HA) and tricalcium phosphate (TCP). The density and microhardness of the sCaP bioceramics increased in the temperature interval 1000&ndash, 1100 &deg, C, while at temperatures higher than 1100 &deg, C, these properties were not significantly altered. The highest compressive strength of 116 MPa was recorded for the samples sintered at 1100 &deg, C. In vitro biocompatibility was also examined in the behavior of osteosarcoma (Saos-2) cells, indicating that the sCaP bioceramics had no cytotoxicity effect. Salmon-derived biphasic calcium phosphates (BCP) have the potential to contribute to the development of bone substituted materials.

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 α-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 µm. 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.

Nanometer scale Ca-deficient hydroxyapatite (nanoapatite) 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 nanoapatite must depend on the microstructure. The purpose of this study is the preparation of nanoapatite particles and their structural characterization by using X-ray diffraction (XRD) and solid-state NMR spectroscopy. The nanoapatite 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 nanometer 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.

Mechanochemically activated graphite (Gp) and iron particle surfaces were prepared, and the Gp/iron composite interfaces were elucidated to utilize new functions. Activated iron particles with the oxygen atoms prepared by a milling under oxygen atmosphere were shown. Alternately, the Gp particles activated by the milling under argon atmosphere easily agglomerated because of the dangling bonds on the edge surfaces. In the composites, the interfacial bonds (e.g., Fe–O–C) between the Gp and iron oxides on the iron were clearly induced while preserving the carbon atom six-ring structures. Furthermore, the molecular orbital calculations suggested that the activated oxygen atoms in the iron oxides effectively abstract hydrogen atoms from the C–H groups of the Gp edge, resulting in the active bare carbon atoms which can form the interfacial bonds; therefore, the interfacial Fe–O–C bonds for a higher adhesive strength were successfully prepared.

B-type carbonate apatite (B-CAp) powders were prepared by a wet method using Ca(OH)2 suspension and H3PO4 solution including NaHCO3 as a carbonate source, and porous B-CAp ceramics with two different amounts of carbonate contents were fabricated by sintering freeze-dried mixtures of the powders and gelatin composite. The porous B-CAp ceramics prepared had three-dimensionally interconnected pores. The sinterability of B-CAp ceramics was dependent on the chemical composition, especially sodium content and vacancy of OH site, and the carbonate contents did not directly influence the dissolution rate of porous B-CAp ceramics.

Mechanochemically activated iron oxide formation on α-iron (Fe) microparticles for the efficient reaction with methane (CH4) was investigated using a simple milling process to successfully clarify ...

The mechanochemical surface functionalization of iron oxides with disordered lattices on bare iron (Fe) particles was investigated using simple milling processes to clarify the formation mechanism of the oxide layer and investigate the near-surface models with different states. The homogeneous α-Fe particles at the milling equilibrium were first prepared under an argon atmosphere. After the subsequent milling reaction of the particles with oxygen molecules, the surface analyses by X-ray diffraction and Raman and X-ray photoelectron spectroscopies revealed that the near-surface layers consisted of two iron oxide phases (α-Fe2O3 and Fe3O4) through oxygen atom diffusion, and the α-Fe2O3 was dominantly grown on the near surface. During the initial reaction, the signals from an electron spin resonance suggested the dangling bond formation on α-Fe2O3. The oxygen atoms effectively induce disordered lattices in the local area to form oxidized Fe3+ clusters, and the geometric distortion formed the dangling bonds, ...

The purposes of this study were to fabricate porous carbonate-substituted apatite (CAp) ceramics and characterize important properties such as compressive strengths and dissolution rates for an artificial bone. Porous A-type CAp (A-CAp) with uniaxial pores was fabricated by sintering porous hydroxyapatite green bodies at 1000°C in carbon dioxide gas atmosphere. B-type CAp (B-CAp) nanocrystals prepared by a wet method were mixed with an organic binder, freeze-dried and heated at 800°C in air, and AB-type CAp (AB-CAp) was fabricated by heating B-CAp porous bodies including the organic binder at 1100°C in carbon dioxide gas atmosphere. From the morphological observations with a scanning electron microscope, the porous A-CAp had uniaxially oriented pores of 104±33 μm in diameter, while the porous B-CAp and AB-CAp had large pores of 143±48 μm and 181±46 μm in diameter, of which pores were interconnected with small pores of 31±11 μm and 45±17 μm in diameter. The dissolution rates of CAps were apparently larger than that of HAp; the calcium concentrations increased in the order of AB-CAp > B-CAp > A-CAp > HAp. This is mainly attributed to carbonate content although it could be partialy depended on the different porous structures and diameters.

Luminescent europium(III)-doped nanoporous silica spheres (Eu:NPS) were synthesized, and folic acid derivative (FA: folate N-hydroxysuccinimidyl ester) as targeting ligand for cancer cells was immobilized on the sphere through a mediation of 3-aminopropyltriethoxysilane (APTES). The ordered nanopores were preserved with the immobilization. The surface area decreased only with the APTES immobilization, suggesting that the FA was immobilized only on the outer surface of the nanopores. The photoluminescence of the spheres showed the characteristic peak due to interactions between the FA and Eu3+, and further the luminescence can be clearly detected by a fluorescent microscopy. The spheres were highly dispersed stability in cell culture medium to exhibit the nontoxic in the proliferation stage of Hela cancer cells and NIH3T3 fibroblasts, and specifically bindto the Hela cells. The binding and uptake spheres showed the intense luminescence. Thus, the luminescent FA-immobilized Eu:NPS spheres will exhibit the targeting and imaging abilities for cancer cells.

Calcium phosphates films were deposited onto pipes and stents of nitinol alloys by an electrolytic deposition (ELD) method. Monocalcium phosphate (Ca (H2PO4)2·H2O) solutions were used as the electrolyte, and electric depositions were carried out at the constant cathode current of 1.59 mA/cm2 at 65°C for 60 min. From the deposition on nitinol pipes, deposition rates were changed in 15 minutes and the precipitates were identified to be octacalcium phosphate (Ca8H2(PO4)6·5H2O) and dicalcium phosphate anhydrous (CaHPO4). The electrolytic depositions on the nitinol alloys were useful for the formation of calcium phosphates films on the complex shape of stents.

This study is concerned with multilayered protein adsorption on carbonate apatite (CAp) that is measured with a quartz crystal microbalance (QCM) technique. A carbonate apatite-deposited QCM sensor was prepared by electrophoretic deposition (EPD). On the CAp-deposited QCM sensor, fibrinogen adsorption followed by thrombin adsorption was investigated. The adsorption of fibrinogen on CAp led to a clear decrease in the resonance frequency of the sensor, which means that fibrinogen adsorbed on the CAp-deposited QCM sensor. The adsorbed amount of fibrinogen was larger on CAp than on a pristine sensor (Au). Although successive thrombin adsorption occurred on fibrinogen adlayers on both CAp and Au, the adsorbed amount and its conformation were different depending on the surface.

Collagen fibril membranes (CFMs) with a high mechanical property were fabricated with a lateral face evaporation method, in which type I atelocollagen extracted from tilapia scales was used. The density and thickness of the CFM obtained were 0.51 ± 0.04 mg/cm 3 and 50 ± 5 μm. The collagen fibrils in the CFM had a similar periodic stripped pattern of 67 nm with native collagen fibrils. The CFM was crosslinked in gaseous glutaraldehyde for different duration in order to increase the mechanical property. The crosslinking degrees of the CFMs analyzed by free amino groups gradually increased to 70.3 % against the exposure duration until 6 hours, and reached a plateau. The denaturation temperatures of the CFMs with the crosslinking degrees at 20.4 % to 43% were linearly increased from 49°C to 75°C. The tensile strength of the CFMs was slightly improved until the crosslinking degree at 33.3 % and then the tensile strength rapidly increased to be 68 MPa. It was suggested that a percolation phenomenon took place in the CFMs by crosslinking of collagen fibrils with polymerized GA molecules.

The fabrication of copper–graphite composites by a milling process was investigated using a centrifugal ball mill. The copper particles were homogeneously milled in a graphite vessel, and the reaction time was varied. Scanning electron microscopy images clearly revealed that a fragment of graphite ground by the copper particle adheres to the copper particle surface, indicating the formation of a copper–graphite composite. The composite graphite amount per 1 g of copper particles increased to 0.46 mg at the milling time 5 min, and subsequently decreased to 0.25 mg at 60 min, indicating the suitable milling-time for the interfacial adhesion. When using only the copper particles, the naturally oxidized layer on the surface decreased with milling. On the other hand, when using only the graphite, the characteristic graphite structure is disrupted and the defect structure increased with milling. Thus, the new copper surface generated by milling strongly reacts with the defect structure of the graphite. It is suggested that the interfacial bonding between the copper and graphite was attributed to a Van der Waals attraction and/or binding force due to oxygen atoms located at the interface.

The fabrication of iron–graphite composites was investigated using a milling process. Based on the milling time of the process, the average particle size of the host iron particles decreased to 10 µm. The size of the graphite particles decreased to a nanometer scale, resulting in the graphite strongly adhering to the iron surfaces. Raman spectra revealed that the graphite aromatic ring structure disappeared and the iron near-surface layer was changed to iron oxide phases. The dangling bond of the fragmented graphite combined with the oxidized iron surface by interfacial binding to efficiently form the interfacial composites.

Europium (III) (Eu(3+))-doped nanoporous silica spheres were synthesized, and the states of Eu(3+) ions in the silica framework structure were investigated. The ordered nanopores were preserved with the doping at the Eu(3+) molar concentration to Si up to 10 mol%, and the O-Si-O and Si-OH groups in the structures were clearly rearranged with the doping, indicating the interaction of Eu(3+) with the O atoms. The significant morphological changes in the spheres were observed with the doping. The photoluminescence spectral shapes due to the transitions of (5)D(0)-(7)F(1) and (5)D(0)-(7)F(2) were indicative of the presence of the Eu(3+) in an environment of a low symmetry. It was found that the Eu(3+) was located inside the silica framework to electrostatically interact with the environmental O atoms, which would prevent the aggregation among Eu(3+) ions to show the efficient luminescence. Therefore, the interactions between the Eu(3+) ions and silica framework structures in the spheres were successfully clarified.

The discovery that supporting electrolytes can be effectively confined in typical organic solvents in a c-Hex-based multiphase electrolyte solution has led to the development of a novel heterogeneous continuous flow synthetic system. PTFE fiber functions as a separation filter that can efficiently isolate the c-Hex phase from multiphase electrolyte solutions. This system has demonstrated both electrochemical solvating and carbon–carbon bond forming reactions. Hydrophobic substrates can be introduced into the reactor as c-Hex solutions, which are then electrochemically transformed into the target hydrophobic products that pass through the PTFE fiber as c-Hex solutions.

Europium (III) (Eu 3+ )-containing nanoporous silicas were successfully synthesized by two different loading methods (adsorption or doping), and the states of the Eu 3+ in the structure were investigated. The Eu 3+ -adsorption indicated that the Eu 3+ interacts with hydroxyl groups on the pore surface and H 2 O molecules to enhance the quenching, whereas the Eu 3+ -doping indicated that the Eu 3+ was located inside the structure framework that produced the efficient luminescence. The interaction between the Eu 3+ and silica structure depended on the loading method.

A quartz crystal microbalance with dissipation (QCM-D) technique was employed to detecting the protein adsorption and subsequent osteoblast-like cell adhesion to hydroxyapatite (HAp) nanocrystals. The interfacial phenomena with the preadsorption of three proteins (albumin (BSA), fibronectin (Fn), and collagen (Col)), the subsequent adsorption of fetal bovine serum (FBS), and the adhesion of the cells were investigated. The QCM-D measured the frequency shift (Δf) and dissipation energy shift (ΔD), and the viscoelastic properties of the adlayers were evaluated using ΔD-Δf plot and Voigt-based viscoelastic model. The Col adsorption significantly showed higher Δf, ΔD, elasticity, and viscosity values as compared to the BSA and Fn adsorption, and the subsequent FBS adsorption depended on the preadsorbed proteins. The ΔD-Δf plot of the cell adhesion also showed a different behavior depending on the surfaces, and the Fn- and Col-modified surfaces showed the rapid mass and ΔD changes by forming the viscous interfacial layers with cell adhesion, indicating that the processes were affected by the cellular reaction through the extracellular matrix (ECM) proteins. The confocal laser scanning microscope images of adherent cells showed a different morphology and pseudopod on the surfaces. The cells adhered to the surfaces modified with the Fn and Col had significantly uniaxially expanded shapes and fibrous pseudopods, and those modified with the BSA had a round shape. Therefore, the different cell-protein interactions would cause the arrangement of the ECM and the cytoskeleton changes at the interfaces, and these phenomena were successfully detected by the QCM-D and Voigt-based model.

Because cartilage has limited potential for self-repair, tissue engineering is expected to replace the present therapies for damaged cartilage, such as total knee arthroplasty. However, scaffolds suitable for cartilage tissue engineering have not been established. We synthesized a novel porous scaffold, a collagen sponge incorporating a hydroxyapatite/chondroitinsulfate composite (pCol-HAp/ChS), containing materials which resemble extracellular matrices in bone and cartilage tissues, which needs high compressive strength for clinical use. HAp/ChS had smaller crystals and a larger total surface area than HAp. SEM images showed pCol-HAp/ChS to have the roughest surface compared with pCol and pCol-HAp. The mechanical properties suggest that pCol-HAp/ChS and pCol/HAp are similar, and superior to pCol. Seeding experiments showed a uniform distribution of mesenchymal stem cells (MSCs) in pCol-HAp/ChS and pCol/HAp. Safranin O, Toluidine blue and Alcian blue staining after 2 weeks of culture revealed pCol-HAp/ChS to be the most chondrogenic in each case. In addition, MSCs in pCol-HAp/ChS produced more glycosaminoglycans, a cartilage matrix, than those in pCol-HAp. Further, pCol-HAp/ChS regenerated 15 times more cartilaginous tissue than pCol. From these results, pCol-HAp/ChS is expected to be a candidate for a scaffold for cartilage tissue engineering in place of collagen sponge.

Adsorption behavior of fetal bovine serum (FBS) onto hydroxyapatite (HAp) was analyzed in situ in phosphate buffer saline (PBS), minimum essential mediums (αMEM or DMEM), and different carbonate-concentrated buffers by using a quartz crystal microbalance with dissipation (QCM-D) technique. Although the adsorption behaviors of FBS onto gold showed no dependence on the solvents, those onto HAp clearly depended on the adsorbed ions in the solvents (PBS or MEMs). The amount and viscoelasticity of FBS adsorbed onto HAp in PBS were approximately two times larger than those in MEMs. The adsorption amounts of carbonate ions on HAp in the carbonate buffers increased with increasing carbonate concentrations, which inhibited the adsorption of FBS and decreased the viscoelastic property of the adsorption layers.

Complete carbonate substitution at A-sites (OH) of low-crystallinity hydroxyapatite with near stoichiometric composition (i.e. Ca/P ratio of 1.65) was achieved by heating in a dry carbon dioxide flow at 1173 K for 64 h. The carbonate content was analysed by thermogravimetry and infrared absorption spectrometry; the chemical composition was determined to be Ca9.9±0.1(PO4)6.00±0.1(CO3)0.9±0.1. The crystal structure and atomic configuration of the carbonate ion were determined by Rietveld refinement using X-ray powder diffraction data. This analysis revealed that the space group was monoclinic Pb with a = 0.9571(1), b = 1.9085(2), c = 0.68755(3) nm and γ = 119.847(7)°. The triangular planes of the carbonate ions were oriented parallel to the c- and a-axes, though there were two independent carbonate sites with occupancy factors of 0.56(1) and 0.34(1), where the triangles were oppositely rotated about the corresponding carbon atoms by 23° and −18°, respectively. The arrangement of the ions was disordered, which explains the lack of a thermal phase transition below 623 K.

We investigated electrical properties of epitaxial Mn doped bismuth ferrite BiFe0.97Mn0.03O3 (BFMO) thin films with different crystal orientations deposited on Si substrates with appropriate buffer layers. Epitaxial SrRuO3 (SRO) thin films with (001), (101), and (111) orientations were grown on CeO2/yttria-stabilized zirconia (YSZ)/Si(001) substrates and YSZ/Si(001), respectively, by the insertion of MgO and TiO2 atomic layers using pulsed-laser deposition (PLD). Using spin coating, we deposited BFMO thin films onto orientated SRO thin films. The BFMO orientation followed the SRO orientation. The Pr values of the BFMO were ordered as follows {111}>{110}>{100}, which is the same as that predicted by crystallographic considerations. The largest Pr value of the {111} orientation is 76 μC/cm2 at 100 kHz, 25°C.

A mechanism of adhesion between carbide molds and optical glass species with high refractive index in precision molding was elucidated on the basis of DV-Xα molecular orbital calculations. An interfacial cluster model comprising NbPNaO glass and glassy carbon (GC) was applied in order to examine the changes in the chemical bonds between atoms at the interface and the effect of the substitution of niobium with other transition metals (denoted with; MdI) at the interface. The bond overlap population (BOP) between oxygen atoms at the surface of the glass and carbon atoms at the surface of the GC increases when the surface of the glass approaches the GC, while that between MeIO correspondingly decreases. When introducing oxygen deficiency at the surface of the glass, the BOP of the MeIcarbon bonds against the MeIoxygen increased in the order of Nb

High refractive index aspheric glass lenses are often used in digital still cameras. However, in manufacturing, adhesion of softened glass to carbide mold causes various defects on the lens surface. We performed experimental transmission electron microscopy (TEM) observations and molecular dynamics/orbital calculations to investigate the glass–carbide adhesion mechanism. TEM revealed island-shaped glass adhesion on the surface of carbide (glassy carbon: GC). TEM–energy dispersion spectra (EDS) showed reduced atomic ratio of oxygen in adhered glass compared with bulk, indicating adhered glass could undergo reduction. From DV-Xα calculations focused on the oxygen atom on the surface of the glass; OI, as Nb–OI bonds at the glass surface approach GC, an overlap population between OI and C increases while that of the Nb–OI bonds decreases. This suggests that, in agreement with TEM–EDS results, OI of the Nb–OI bond forms no bridging bond such as Nb–OI–C at the glass–GC interface, while the C–OI bonding unit could be isolated at the GC surface, and supports our assumption that reduction of the glass induces adhesion to the GC mold.

A tube consisted of chitin/chitosan nanofibers is one of the candidates to support nerve regeneration. However, chitin/chitosan would cause inflammation when implanted in human body. This study indicates that chitosan nanofibers (degree of deacetylation; 78% and 93%) could be modified by alternate soaking in calcium and phosphate solutions, resulting in the improvement of their biocompatibility in terms of both in vitro cell culture experiment and in vivo animal test. Deacetylation of the chitosan nanofibers appeared to have little effect on in vitro and in vivo behaviors after 3 days. However, the alternate soaking process clearly improved in vitro and in vivo responses against the chitosan nanofibers. During the process, the surface morphology of the chitosan nanofiber was not changed, i.e. no hydroxyapatite was deposited due to the limited number of soaking. Thus, the surface chemical and physical states of the modified chitosan nanofiber such as surface charge, surface free-energy, and wettability was found to influence both the cell attachment and inflammation.

Hydroxyapatite (HAp) nanocrystals with different crystal sizes were deposited by the electrophoretic deposition method on the gold surface of a quartz crystal microbalance with a dissipation probe. The nanosensors formed this way were used to elucidate the adsorption mechanism of proteins with a similar pI value. The crystal sizes and the area of the a-plane affected only the adsorption amount of human serum albumin, but not that of bovine plasma fibrinogen. The viscoelastic property, Delta D/Delta f, of each absorbed layer on the nanosensors was almost constant. The protein adsorption mechanism can be explained as follows: the dissociated carboxyl groups (negative charge) of albumin were interacted with calcium ions and the hydrated amine groups (positive charge) at the alpha C domain of fibrinogen were with phosphate ions on the HAp surface.

The adsorption of multiple proteins derived from fetal bovine serum (FBS) in phosphate buffer saline (PBS) and alpha minimum essential (aMEM) was in situ analyzed with a quartz crystal microbalance with dissipation technique on gold, titanium and HAp sensors. The adsorption behaviors of FBS proteins were varied depending on the sensors. The DD/Df value of the HAp sensor were clearly different in PBS and aMEM, and others were not changed. The viscoelastic properties of the protein films adsorbed on the HAp sensor in PBS were flexible in comparison with those on the gold and titanium sensors. The D-f plots incidated that the proteins adsorbed on HAp in PBS would lead to competitive adsorption and conformational change and those in aMEM could form a monolayer. The adsorption behavior on the HAp in carbonate buffer saline was found to be similar to that in aMEM. These differential adsorption behaviors on the HAp surface were attributed to the pre-adsorptive ion, such PO43- or CO32- in the solvent.

Because cartilage has limited potential for self-repair, tissue engineering is expected to replace the present therapies for damaged cartilage, such as total knee arthroplasty. However, scaffolds suitable for cartilage tissue engineering have not been established. We synthesized a novel porous scaffold, a collagen sponge incorporating a hydroxyapatite/chondroitinsulfate composite (pCol-HAp/ChS), containing materials which resemble extracellular matrices in bone and cartilage tissues. In this report, the physical, mechanical and biological properties of the scaffold are compared with those of a collagen sponge (pCol) and pCol incorporating a hydroxyapatite composite (pCol-HAp). HAp/ChS had smaller crystals and a larger total surface area than HAp. SEM images of the three materials showed pCol-HAp/ChS to have the roughest surface. The mechanical properties suggest that pCol-HAp/ChS and pCol/HAp are similar, and superior to pCol. Seeding experiments showed a uniform distribution of mesenchymal stem cells (MSCs) in pCol-HAp/ChS and pCol/HAp. Histochemical staining after 2 weeks of culture revealed pCol-HAp/ChS to be the most chondrogenic. From these results, pCol-HAp/ChS is expected to be a candidate for a scaffold for cartilage tissue engineering in place of collagen sponge.

This study is concerned with the characterization of oxide layers formed on Ni-free stainless-steel and the immobilization of a silane coupling agent, i.e. � -aminopropyltriethoxysilane (APS). The Ni-free stainless-steel was oxidized at three different temperatures, 800 K, 1000 K and 1200 K in air, and then the APS molecules were immobilized on the surface at room temperature. The surface of the samples was characterized by X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM). The composition of surface oxides formed through the oxidizing treatment was identified to be two types of oxide, namely Fe2O3 and Cr2O3. The atomic ratio of Cr to Fe+Cr increased with an increase in the oxidizing temperature. The amounts of APS immobilized on each surface followed the sequence of 1200 K < 1000 K < 800 K of the oxidizing temperature. It was found that the surface oxide formed at 800 K is the best carrier of APS under these conditions. It is apparent that Fe2O3 is more easily fixed by APS than Cr2O3. [doi:10.2320/matertrans.ME200827]

Porous scaffolds, consisted of hydroxyapatite (HAp), chondroitinsulfate (ChS) and collagen, were prepared by freeze-drying technique. HAp/ChS composite particles were incorporated into a collagen matrix. Scanning electron microscope (SEM) observations showed that the porous scaffolds involved interconnected pores whose size was 80~200 µm in diameter. The HAp/ChS particles were homogeneously distributed in the collagen matrix. Surface area of the scaffolds was increased by the incorporation of the particles. Compression tests in phosphate buffer saline indicated that the porous scaffolds had elastic property and had larger compressive modulus than the pure collagen scaffold. The porous scaffolds obtained in this study could be useful for a cartilage tissue engineering.

Insulin delivery carriers using low crystalline porous zinc hydroxyapatite (ZnHAp) microparticles with different crystal sizes and novel formulation method of poly (lactic acid) (PLA) have been developed to achieve the sustained-release of insulin. The adsorption isotherm curves of insulin dissolved into acetic acid of pH4.5 onto ZnHAp nanocrystals show non-Langmuir type due to the dissolution of the ZnHAp microparticles; the adsorption amounts were increased with the increase of crystalline sizes. The PLA formulation, coating the outer layer of microparticles, showed the apparent reduction of initial burst for insulin. The amounts of initial release of insulin decreased with the increase of crystalline sizes of ZnHAp, which could be attributed to the different meso-porous structure depending on its crystal sizes.

Hydroxyapatite (HAp) sensor, available for quartz crystal microbalance with dissipation (QCM-D) technique, has been fabricated by an electrophoretic deposition method. The method of re-usability of the sensor after adsorption of fibrinogen and the biological apatite (BAp) growth on the sensor with and without the adsorption of feral bovine serum (FBS) from 1.5 simulated body fluid were investigated. The re-usability of the sensor, cleaning with the combination of ammonia and hydrogen peroxide mixture and UV/ozone treatment, achieved ten times reuses. BAp was grown on the HAp surface but not on the gold surface at 37.5 oC for 40 hours. The viscoelastic property (DD/Df value) of the BAp layer on the HAp sensor showed harder than that of the protein adsorption films from FBS. The amount of the BAp grown on the HAp sensor adsorbed FBS is lower than that on the HAp sensor. The adsorption of FBS proteins on the HAp surface strongly inhibited the BAp growth.

Lithium niobate (LiNbO3) thin films were deposited on Al2O3(001) substrates using metal-organic chemical vapor deposition (MOCVD), with Li(dpm) and Nb(C2H5)5 as precursors. By optimizing the conditions of thin film deposition, the c-axis oriented and epitaxially grown LiNbO3 thin films with stoichiometric composition were deposited on an Al2O3(001) substrate. The refractive index of the stoichiometric LiNbO3 thin film was 2.24 at = 632.8 nm, which is close to that of bulk crystal.

The effect of SrTiO 3 seed layer thickness on low-temperature crystallization and electrical properties Pb(Zr, Ti)O 3 (PZT) films by metalorganic chemical vapor deposition (MOCVD) were investigated. The thicknesses of SrTiO 3 seeds were varied with 1–18 nm by deposition time. The preferred (1 1 1) PZT films could be obtained at 304 °C on SrTiO 3 seeds prepared at 500 °C. The intensity of (1 1 1) PZT phase was increased with deposition time due to the enhancement of coverage of SrTiO 3 seeds on substrate. The AFM observation revealed that the growth of PZT films was initially started on SrTiO 3 seeds. The remanent polarization (2 P r ) and leakage current density were changed with seed layer thickness. It is considered that concentration of the electric field on SrTiO 3 seeds with capacitance changes were affected to electrical properties of PZT films. The 100 nm thick PZT films on 5 nm thick SrTiO 3 seeds showed 2 P r max (18 μC/cm 2 ) with 10 −6 A/cm 2 of leakage current density.

Real time adsorption behaviors of six proteins with different isoelectric points on hydroxyapatite (HAp) nanocrystal surfaces have been investigated by using HAp sensors for quartz crystal microbalance with dissipation technique (QCM-D). The dissipation (D)–frequency (f) plots clearly showed that the different types of protein adsorption behaviors; the D-f plots of acidic proteins lie on one straight line with a constant slope under all initial protein concentrations, while those of neutral and basic proteins lie on two straight lines with different slopes. The acidic proteins formed a monolayer, while the neutral and basic proteins could cause conformational changes with the adsorbed amount of proteins. The QCM-D technique with novel HAp nanocrystal sensor is useful for the liquid phase changes of proteins on the surface.