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The methylene blue (MB) adsorption states on the titania nanoparticles (NPs) prepared by two surfactant removal processes were investigated to demonstrate the singlet oxygen generation efficiency. The NPs with the BET surface areas of 250–350 m2/g exhibited the spherical particle sizes of 100–150 nm, indicating the nanoporous structures. The MB molecular states adsorbed on the NPs prepared by solvent extraction method (WT) were attributed to both the monomer and dimer states, whereas those on the NPs prepared by the baking at 250 °C (BT) were dominantly attributed to the monomer state, indicating the adsorbed states would be affected by the surface functional groups. The singlet oxygen generation efficiency from the MB adsorbed on the BT NPs were higher than that on the WT NPs, and those of the NPs were higher as compared with that the MB alone. Therefore, the generation efficiency would be controlled by the titania surface condition.

Immobilization of 2,2′-bipyridine-5,5′-dicarboxylic acid (Bpdc) into layered octacalcium phosphate was investigated in the hydrolysis process of α-tricalcium phosphate. 100 interlayer distance altered from 1.9 to 2.5–2.7 nm by the immobilization, suggesting the novel inorganic/organic nanohybrids. The nanohybrids exhibited the blue-shifted photoluminescence peaks with the higher internal quantum efficiency as compared with the case in the Bpdc alone.

Agave fibers were used to elaborate transparent and flexible cellulose hydrogel films used as a scaffold for tissue regeneration and tested by in vitro assays with NIH 3T3 fibroblast cells. Using a dimethylacetamide/lithium chloride (DMAc/LiCl) system made it possible to obtain cellulose solutions, and hydrogel films were prepared by phase inverse method without cross-linker. The concentration of LiCl in the DMAc solution was varied from 4 to 12 wt %. The resultant hydrogel films showed water contents in the range of 239–323% and enough film strength from 50 to 66 N/mm2, when the LiCl was changed from 4 to 12 wt % concentrations, respectively. The prepared agave cellulose films showed better cytocompatibility than the polystyrene dish used as control. Atomic force microscopy images showed that the hydrogel films with lower LiCl apparently contained ordered and aggregated fiber orientation. This comparison suggested that the segmental microstructure in the hydrogel films influenced fibroblast cells spreading.

Polyaniline–cellulose acetate hollow fibers prepared from cellulose acetate (CA) solution of aniline (ANI) were founded to show dual layers structure, when wet technique was applied for using syringe injection of the solution to acidic water for ANI polymerization. In this technique, the polymerization of ANI occurred simultaneously by the monomer injection in coagulated CA fibers. Then, the PANI–CA composite fibers were obtained. The formation of the PANI–CA composite fiber was dependent upon HCl concentration and initiator of ammonium persulfate. Especially, when the coagulation time was 1 min, the obtained PANI–CA fibers showed hollowed dual-layer structure having outer layer of PANI and inner layer of CA. Evidence was presented that the dual structure fiber had 40 μm outer layer and 60 μm inner porous layer in their thicknesses. Cyclic voltammograms of the PANI–CA fiber were indicated that the outer layer was composed of PANI layer showing electrochemical properties with electrical capacity of about 0.003 C.

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 effect of ultrasound (US) on the shear viscosity of water-soluble polymers, polyvinyl alcohol, polyethylene glycol and polyacrylic acid, was studied in aqueous solutions with US exposure of 23, 43, 96 and 141 kHz for an 8.5–9 W US. The US exposure significantly decreased the shear viscosity of the solutions in this order: 43>23>96>141 kHz. When US exposure was stopped, the shear viscosities of the aqueous polymer solutions reverted to their original values. US stimulation during the decrease in viscosity was supported by the ultrasonic power transmitted through the aqueous polymer solution. In addition, Fourier-transform infrared spectra obtained during US exposure showed that hydrogen bonds in the aqueous polymer solution could be broken, especially at 43 kHz. We concluded that US exposure influenced hydrogen-bond interactions between the OH groups of the polymer and water molecules in the aqueous medium. This finding was supported by US absorption of the aqueous polymer solution in the transmittance model, which shows the US absorptivity, ɛUS, for each polymer system. The effect of US on the shear viscosity of water-soluble polymer solutions was studied. The 43 kHz US significantly decreased the shear viscosity of the solutions. FT-IR spectra obtained during the US exposure showed that hydrogen bonds in the aqueous polymer solution could be broken. US absorption model was proposed to explain US absorption and the breakage in the hydrogen bonds. US effect influenced the condition of water solvation to the water-soluble polymers.

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, ...

Novel metal-like luster conductive films were prepared using straightforward chemical copolymerization of pyrrole (Py) and furfural (FFr). Critical parameters in the copolymerization such as monomer feed, reaction solvent, acid catalyst were studied to optimize their syntheses, film-forming properties, etc. These films showed a metal-like black luster and exhibited excellent mechanical properties with flexibility. The conjugate chemical bonds obtained from methine group were revealed in the copolymer film by Fourier transform infrared (FT-IR), ultraviolet–visible light (UV-vis), and 1H nuclear magnetic resonance (NMR) spectra. Differential scanning calorimetry (DSC) and cyclic voltammetry (CV) results implied that these copolymers showed better thermo and electrochemical stability. The density and smooth surface of the copolymer films contributed to the performance of metal-like luster, presenting the benefit of better surface reflection in the incident light.

The mechanochemical fabrication of the composites between carbon fibers (CFs) and nylon-6 (N6) was investigated using a milling process. By the milling, defected surfaces were generated on CFs to obtain the homogeneous length with preserving the cylindrical shape of CF. Fourier transform infrared spectra revealed that the band intensities due to C═O, C–N and O–H bondings increased with the milling. The band position of C–N was shifted to a higher wavenumber, while that of C═O did not change, implying that the main chain of N6 was dissociated at the C–N neighboring the C═O bonds by the force, and subsequently, new bonds between the N atoms of the activated N6 and the C atoms on CFs would be formed. Therefore, the efficient fabrication of the CF/N6 composite fibers with the interfacial bondings was achieved using the mechanochemical reaction.

Bamboo fibers were used as source to prepare cellulose hydrogel films for cell cultivation scaffold. The preparation of cellulose solutions was carried out by three different dissolving methods with NaOH-based and NaOH/urea aqueous solutions and DMAc/LiCl solution. Several hydrogel films were elaborated and their properties were compared to evaluate the effect of the dissolving method. It was found that tensile strength of the resultant hydrogel films increased from 21 to 66 N/mm2 when DMAc/LiCl was used instead of the NaOH/urea solution. The same tendency was observed in the obtained elongation values. Moreover, a remarkable difference in fibroblast cell cultivation was observed in higher cell density, when DMAc/LiCl method was used. The obtained results with DMAc/LiCl also were seen to be higher than the results for PS dish used as control. However, low cytocompatibility was observed when NaOH and NaOH/urea methods were used. The obtained results showed that hydrogel films elaborated with cellulose solution prepared with DMAc/LiCl method exhibited good cytocompatibility for the cell cultivation scaffold.

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.

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.

Hybrid nanocrystals of 8-hydroxyquinoline (8Hq) molecules and hydroxyapatite nanocrystals (HAp) were successfully prepared by a mechanochemical solid-state reaction. The hybrid nanocrystals exhibit a significant thermal stability and efficient photoluminescence peak at 500 nm, which were attributed to metal–ligand charge transfer at the interface between the oxygen atoms of 8Hq and the calcium ions of HAp, and the interfacial photofunctions were mechanochemically controlled. The interfacial bonding structures were also supported by a DV-Xα molecular orbital calculation.

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.

Biological apatite (BAp) growth from a simulated body fluid on various substrate surfaces (gold (Au), titanium (Ti), and hydroxyapatite (HAp)) with and without preadsorption of fetal bovine serum protein (FBS) at the initial nucleation stage was investigated using a quartz crystal microbalance with the dissipation (QCM-D) technique. The protein composition in the FBS adlayer and viscoelastic property was elucidated by the Voigt-based viscoelastic model and antibody-binding analysis, respectively. The bare HAp effectively induced the BAp growth to increase the mass to 25.9 ± 3.2 μg cm–2 in 40 h; however, a slight increased mass of less than 1 μg cm–2 was detected on the Au and Ti, indicating the superior biocompatibility of the HAp surface. The FBS adsorption on the bare Au and Ti rapidly reached a plateau as compared to that on the HAp, and the adsorbed amount of the FBS on the HAp was approximately 2 times greater than those on the Au and Ti. The FBS adlayer on HAp showed the higher saturated ΔD/Δf value...

The mineralized structure of aligned collagen fibrils in a tilapia fish scale was investigated using transmission electron microscopy (TEM) techniques after a thin sample was prepared using aqueous techniques. Electron diffraction and electron energy loss spectroscopy data indicated that a mineralized internal layer consisting of aligned collagen fibrils contains hydroxyapatite crystals. Bright-field imaging, dark-field imaging, and energy-filtered TEM showed that the hydroxyapatite was mainly distributed in the hole zones of the aligned collagen fibrils structure, while needle-like materials composed of calcium compounds including hydroxyapatite existed in the mineralized internal layer. Dark-field imaging and three-dimensional observation using electron tomography revealed that hydroxyapatite and needle-like materials were mainly found in the matrix between the collagen fibrils. It was observed that hydroxyapatite and needle-like materials were preferentially distributed on the surface of the hole zones in the aligned collagen fibrils structure and in the matrix between the collagen fibrils in the mineralized internal layer of the scale.

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.

The photoassisted fusion of a decanethiol-passivated Au-nanoparticle film on a glass substrate by exposure to vacuum-ultraviolet (vacuum-UV) light at 172 nm was investigated and compared to that by thermal fusion. On the basis of the thermal treatment at 200 °C, the X-ray diffraction patterns indicated that the Au-nanoparticle film with the particle diameter of 2.1 nm is completely converted to a crystalline Au film, and the film surface was coarsely granular, having a roughness of several tens of nanometers by field emission-scanning electron microscopy observation. After exposure to vacuum-UV light, the UV−vis absorption spectra revealed that the surface plasmon band at 535 nm showed a red shift with the increasing exposure time, and then the absorption band at 770 nm was clearly observed at 30 min. The diameter of the fused Au nanoparticles was larger than 20 nm on the basis of a transmission electron microscopy observation. These changes indicated that the Au nanoparticles were converted to the crysta...

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.

A supercapacitor composite electrode was effectively fabricated by using cyclic voltammetric deposition of poly(pyrrole-co-2-formylpyrrole)–multiwall carbon nanotube composite, P(Py-co-FPy)–MWCNT. ...

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.

Rattle-type hollow mesoporous silica spheres including an internal Fe 2 O 3 -containing particle were prepared using a carbon―iron template method. Elemental distribution of the silica spheres was analyzed using an energy-filter transmission electron microscopy, and the three-dimensional (3D) structure was visualized by a computer tomography with a scanning transmission electron microscopy (STEM). From the 3D structure reconstructed with a tilted series of high-angle annular dark field images, the diameter and shell thickness of the hollow mesoporous silica spheres were determined to be 381 ±14 and 61 ± 10 nm. It was also found that the internal Fe 2 O 3 -containing particle with the diameter of 104 ± 7 nm also exhibited a hollow structure with the shell thickness of 24 ± 6 nm.

Magnetic nanoparticle (MNP) composites with a magnetite (Fe(3)O(4)) core and a hydroxyapatite (HAp, Ca(10)(PO(4))(6)(OH)(2)) coating were prepared using a precipitation method and a subsequent hydrothermal treatment. The hydrothermal treatment diminished the lepidocrocite layer on the magnetite, enhanced the crystal growth of HAp and dissolved the MNPs. The divalent iron ions dissolved into solvent were not substituted for the HAp lattice. The three-dimensional (3D) nanostructure, the crystal morphology of HAp covered with the MNPs and the interfacial nanostructure of magnetite/HAp were analyzed using an energy-filter transmission electron microscopy (EF-TEM) and visualized by computer tomography in transmission electron microscopy (TEM). EF-TEM and 3D reconstruction images using a tilted series of high-angle annular dark-field images showed that the needlelike HAp nanocrystals covered with a magnetite core and the crystal growth of HAp attached to the magnetite surface was inhibited as a result of the lower density of the nucleation site of the lepidocrocite layer. The dissolution of iron ion from MNPs and the interfacial interaction of HAp and magnetite could cause the needlelike morphology of HAp nanocrystals.

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.

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.

Conjugated polymers containing anthracene backbone structures were synthesized through facile chemical oxidative polymerization and showed detection capacity toward several heavy metal ions for sen...

Composites between carbon fibers (CFs) and heterogeneous materials have been widely studied and their fabrication techniques have been developed. However, their hydrophobic surfaces make it difficult to disperse CFs into hydrophilic resins, which results in weak junctions with ceramics. To develop high-strength composite fibers, it is important to design interfacial chemical bonds. Thus, surface-modification techniques of CFs have recently become the main focus and their interfaces have been characterized by various analytical methods. In this Minireview, various techniques that modify the CF surface by coating with inorganic polymers (metal oxide compounds) are highlighted, and the applications of novel nanocomposite fibers are also described. Furthermore, interfacial bonds between CFs and polymer resins are reviewed and discussed in terms of CF-reinforced plastics and their future prospects.

Human induced pluripotent stem cells (hiPSCs) are a promising source of cells for medical applications. Recently, the development of polydimethylsiloxane (PDMS) microdevices to control the microenvironment of hiPSCs has been extensively studied. PDMS surfaces are often treated with low-pressure air plasma to facilitate protein adsorption and cell adhesion. However, undefined molecules present in the serum and extracellular matrix used to culture cells complicate the study of cell adhesion. Here, we studied the effects of vitronectin and γ-globulin on hiPSC adhesion to plasma-treated and untreated PDMS surfaces under defined culture conditions. We chose these proteins because they have opposite properties: vitronectin mediates hiPSC attachment to hydrophilic siliceous surfaces, whereas γ-globulin is adsorbed by hydrophobic surfaces and does not mediate cell adhesion. Immunostaining showed that, when applied separately, vitronectin and γ-globulin were adsorbed by both plasma-treated and untreated PDMS surfaces. In contrast, when PDMS surfaces were exposed to a mixture of the two proteins, vitronectin was preferentially adsorbed onto plasma-treated surfaces, whereas γ-globulin was adsorbed onto untreated surfaces. Human iPSCs adhered to the vitronectin-rich plasma-treated surfaces but not to the γ-globulin-rich untreated surfaces. On the basis of these results, we used perforated masks to prepare plasma-patterned PDMS substrates, which were then used to pattern hiPSCs. The patterned hiPSCs expressed undifferentiated-cell markers and did not escape from the patterned area for at least 7 days. The patterned PDMS could be stored for up to 6 days before hiPSCs were plated. We believe that our results will be useful for the development of hiPSC microdevices.

The goal of this article is to make a pattern of human induced pluripotent stem cells (hiPSCs) on a Polydimethylsiloxane (PDMS) surface. Here, we report that pattering of hiPSCs can be achieved by patterned plasma treatment followed by coating with a two protein mixture. The result is useful for future applications of micro devices in human cell culture.

When bioceramics are implanted into a body, proteins in the fluid adsorb and subsequently cells adhere on the surface. To detect the structural characteristics at the interface between the surfaces and cells, a quartz crystal microbalance with dissipation (QCM-D) technique is one of excellent in situ analytical methods. The QCM-D detecting the interfacial phenomena with the protein adsorption and cell adhesion has been recently researched, and hydroxyapatite sensor surfaces fabricated by an electrophoretic method have been also studied for understanding the interface. The interfacial viscoelastic properties (shear viscosity, elastic shear modulus and tan δ ) of the interface were estimated using a Voigt-based viscoelastic model from the measured frequency (Δ f ) and dissipation shift (Δ D ) curves. The different cell adhesion process, interfacial viscoelasticity, and morphology depending on the surfaces were successfully evaluated by the QCM-D technique. This chapter summarized the studies on the QCM-D technique that clarify the interfacial phenomena between bioceramics and cells.

This paper reviews the recent progress in the preparation of oxide-based and heteroatom-doped particles. Surfactant-templated oxide particles, e.g. silica and titania, are possible candidates for various potential applications such as adsorbents, photocatalysts, and optoelectronic and biological materials. We highlight nanoporous oxides of one element, such as silicon or titanium, and those containing multiple elements, which exhibit properties that are not achieved with individual components. Although the multicomponent nanoporous oxides possess a number of attractive functions, the origin of their properties is hard to determine due to compositional/structural complexity. Particles with a well-defined size and shape are keys for a quantitative and detailed discussion on the unique complex properties of the particles. From this viewpoint, we review the synthesis techniques of the oxide particles, which are functionalized with organic molecules or doped with heteroatoms, the physicochemical properties of the particles and the possibilities for their photofunctional applications as complex systems.

Terbium(III)-doped mesoporous silicas were synthesized, and the states of terbium ions in the silica frameworks were investigated. The mesopores were preserved upon doping at terbium ion molar concentrations relative to (Si+Tb) up to 15 mol %, indicating the interaction of terbium ions with Si–O bonds. Significant morphological changes of the particles were observed with increasing the doping concentration. The shapes of the photoluminescence spectra due to the transitions of 5D4 → 7F6 and 5D4 → 7F5 were indicative of the presence of terbium ions in the silica matrix, and the quantum efficiency (2.1–2.8%) and lifetime (1.6–1.9 ms) decreased with increasing the doping concentration up to 15 mol %. Therefore, the terbium ions are considered to be located inside the amorphous silica frameworks, where they electrostatically interact with the O atoms of silanol and siloxane groups.

The effect of ultrasound (US) stimulation on the shear viscosity of aqueous polyvinyl alcohol (PVA) solution was studied when the solution was exposed to US at 23, 43, 96, and 141 kHz. The US stimulus showed a marked decrease of the shear viscosity of the solution in the order of 43>96>23>141 kHz, respectively, under US power dissipation of 8.5, 8.9, 8.9, and 8.8 W. Subsequently, when US exposure was stopped, the shear viscosity of PVA reverted to its original value. The US stimulation was analyzed with the US power transmitted through the PVA aqueous media. Furthermore, FT-IR spectra measured at different durations of US exposure, suggest that hydrogen bonds in the PVA segments were broken by the US exposure. We conclude that structural changes of the hydrogen bonded crosslinks of PVA were induced to include water molecules for the re-forming of crosslinks of aqueous PVA.

When a biomaterial is implanted into the body, blood proteins adsorb on its surface and subsequently cells adhere via the protein adlayer. Thus, the understanding of protein adsorption and conformational change on the biomaterial surfaces is of great importance to control the biocompatibility such as antithrombotic properties and cell adhesion behaviors. In this study, we synthesized hydroxyapatite (HAp) and carbonate apatite (CAp) by a wet method. Then we successfully fabricated the HAp and CAp sensors for QCM-R by an electrophoretic deposition method. Adsorption behavior of proteins on the bone substitute material can be monitored by using these apatite sensors. Bovine serum albumin and fibrinogen were employed for the model proteins, and monitored the adsorption behavior on the HAp, CAp and reference gold (Au) sensors by the QCM-R technique. As a result, we revealed that fibrinogen and bovine serum albumin adsorbs on the gold surface by hydrophobic interaction, and adsorbs on the HAp and CAp surfaces mainly by electrostatic force. Besides, we revealed that fibrinogen adsorbs on the Au surface more rigid than on the HAp and CAp surfaces while bovine serum albumin adsorbs on the HAp and CAp surface more rigidly than on the Au surface.

The adhesion process of osteoblast-like cells on hydroxyapatite (HAp) and oxidized polystyrene (PSox) was investigated using a quartz crystal microbalance with dissipation (QCM-D), confocal laser scanning microscope (CLSM), and atomic force microscope (AFM) techniques in order to clarify the interfacial phenomena between the surfaces and cells. The interfacial viscoelastic properties (shear viscosity (η(ad)), elastic shear modulus (μ(ad)), and tan δ) of the preadsorbed protein layer and the interface layer between the surfaces and cells were estimated using a Voigt-based viscoelastic model from the measured frequency (Δf) and dissipation shift (ΔD) curves. In the ΔD-Δf plots, the cell adhesion process on HAp was classified as (1) a mass increase only, (2) increases in both mass and ΔD, and (3) slight decreases in mass and ΔD. On PSox, only ΔD increases were observed, indicating that the adhesion behavior depended on the surface properties. The interfacial μ(ad) value between the material surfaces and cells increased with the number of adherent cells, whereas η(ad) and tanδ decreased slightly, irrespective of the surface. Thus, the interfacial layer changed the elasticity to viscosity with an increase in the number. The tan δ values on HAp were higher than those on PSox and exceeded 1.0. Furthermore, the pseudopod-like structures of the cells on HAp had periodic stripe patterns stained with a type I collagen antibody, whereas those on PSox had cell-membrane-like structures unstained with type I collagen. These results indicate that the interfacial layers on PSox and HAp exhibit elasticity and viscosity, respectively, indicating that the rearrangements of the extracellular matrix and cytoskeleton changes cause different cell-surface interactions. Therefore, the different cell adhesion process, interfacial viscoelasticity, and morphology depending on the surfaces were successfully monitored in situ and evaluated by the QCM-D technique combined with other techniques.

Hepatocyte cell aggregation and adhesion to HAp nanocrystals covered with SU-8 polymer micropatterns by nano/microfabrication techniques is demonstrated. The surface roughness and wettability of the HAp nanocrystals are significantly different from those of the SU-8 polymer. QCM-D and microscopic observation clearly reveal that the cells realize the surface properties to form aggregation and preferentially adhere to the HAp nanocrystals at 2 h after seeding, indicating the importance of the microstructures as well as the interfacial phenomena at a nanometer scale.

The initial adhesion, spreading and cytoskeleton changes of fibroblast NIH3T3 cells onto hydroxyapatite (HAp) and oxidized poly(styrene) (PSox) sensors pre- adsorbed fetal bovine serum were analyzed by using a quartz crystal microbalance with dissipation technique and an atomic force microscopy (AFM). The frequency shift (Δf) and the dissipation shift (ΔD) curves on HAp nanocrystals showed the decrease in Δf with increasing ΔD for 80min and the subsequent increase in Δf with decreasing ΔD, while those on PSox showed the decrease in Δf for 120min with increasing ΔD for 50min and then with subsequent decreasing ΔD. The different adhesion behavior dependent on the surfaces was attributed to the cell-surface interactions; the cells on HAp had rough fibrous pseudopods and those on PSox had dense particulate pseudopods. The different structures indicated that the cytoskeleton changes and the rearrangement of the extracellular matrix at the interface caused the different adhesion behavior.

The initial adhesion, spreading and cytoskeleton changes of hepatocyte-like cells on hydroxyapatite (HAp) and oxidized poly(styrene) (PSox) sensors pre-adsorbed fetal bovine serum (FBS), collagen (Col) and fibronectin (FN) were analyzed by using a quartz crystal microbalance with dissipation technique and a confocal laser scanning microscope (CLSM). The ΔD-Δf plots of the cell adhesion behavior on HAp nanocrystals clearly depended on the pre- adsorbed proteins, while that on PSox showed almost same behavior irrespective of the proteins. The different adhesion behavior depended on the substrate surfaces was attributed to the cell-surface interactions. CLSM images showed that the morphology of the cultured cells depended on the surfaces and the cells on the HAp and PSox adsorbed Col or FN had sometimes pseudopods. The different cellular morphology indicated that the cytoskeleton changes and the rearrangement of the extracellular matrix at the interface caused the species of pre-adsorbed proteins.

Cross-linking degree of a poly(dimethylsiloxane) (PDMS) film was controlled, and the incorporation of hydrophobic decanethiol-passivated gold (Au) nanoparticles into the film was investigated. FT-IR spectra indicated that the hydrosilylation reaction between a vinyl group and a hydrosilyl group occurred with the cross-linking. The swelling degree of the film in toluene changed with a cross-linker concentration, indicating the control of the cross-linking degree of PDMS film. By EDX analysis, the amount of incorporated Au nanoparticles increased with decreasing a cross-linker concentration, indicating the enlarged free volume of the film. The Au nanoparticle-PDMS composite film containing a cross-linker at 6 wt% showed brown color attributed to plasmon resonance of Au nanoparticles, suggesting the Au nanoparticles in the film at monodispersion state. The UV-visible absorbance of the composite film decreased without spectralshift by swelling with toluene, and the changes were reversible. The aggregation among Au nanoparticles in the composite film after calcination also depended on the cross-linking degree. Thus, the control of cross-linking degree of PDMS film successfully leaded to a simple way of fabricating the Au nanoparticle-PDMS composite film at the mono-dispersion state.

Competitive adsorption of two-component solutions containing fibronectin (Fn) and albumin (Ab) on hydroxyapatite (HAp) nanocrystals was analyzed in situ using the quartz crystal microbalance with dissipation (QCM-D) technique. Adsorption of the one-component protein (Fn or Ab) and the two-component proteins adjusted to different molar ratios of Fn to Ab at a fixed Fn concentration was investigated. The frequency shift (Δf; Hz) and the dissipation energy shift (ΔD) were measured with the QCM-D technique, and the viscoelastic changes of adlayers were evaluated by the saturated ΔD/Δf value and the Voigt-based viscoelastic model. For the adsorption of the one-component protein, the Fn adlayer showed a larger mass and higher viscoelasticity than the Ab adlayer, indicating the higher affinity of Fn on HAp. For the adsorption of the two-component proteins, the viscoelastic properties of the adlayers became elastic with increase in Ab concentration, whereas the adsorption mass was similar to that of Fn in the one-component solution regardless of the Ab concentration. The specific binding mass of the Ab antibody to the adlayers increased with increase in Ab concentration, whereas that of the Fn antibody decreased. Therefore, Fn preferentially adsorbs on HAp and Ab subsequently interacts with the adlayers, indicating that the interfacial viscoelasticity of the adlayers was dominated by the interaction between Fn and Ab.

Elemental distribution of calcium, phosphorus, oxygen, and carbon in a single collagen fibril obtained from tilapia fish scales was identified with an electron energy-loss spectroscopy and an energy-filtered transmission electron microscopy, for the first time. The carbon intensity profile of the single collagen fibril showed the specific D-periodic pattern at 67 nm of type I collagen fibrils. The calcium L 2,3 -edge and oxygen K-edge peak positions were detected at 347/350 eV and 137 eV, respectively, and these positions were identical to those of hydroxyapatite. Calcium, phosphorus, and oxygen were present in the hole zones as the amorphous phase, while carbon was present in the overlap zone. Our results indicated that the hole zones preferentially attract calcium and phosphate ions and thus serve as possible nucleation sites for mineralization.