Mechanochemical Solid-State Immobilization of Photofunctional Dyes on Amorphous Silica Particles and Investigation of Their Interactive Mechanisms.

Amorphous silica particles (ASPs) have been reported to exhibit bioactive properties and are becoming the focus of attention as bioceramics. However, their interactions with proteins in living organisms remain to be understood and need to be investigated in order to achieve wider applications. Our research group found that chlorine (Cl)-containing ASPs are useful for protein immobilization. Photofunctional dyes (fluorescein (FS-), methylene blue (MB+)) that have the carboxy and amino groups as the main functional groups were immobilized on the Cl-containing ASPs via the mechanochemical method as the model molecule and their spectral properties were used to investigate and discuss the organic/inorganic interfacial bonding states. In FS-, the oxygen atoms of the carboxy groups in the molecule were immobilized by the hydrogen bonds with the silanol groups on the ASPs surfaces, indicating that there is an optimum Cl content for the immobilization as the monomer state. In the case of MB+, as the Cl concentration in the ASPs increases, the immobilization via the electrostatic interactions between the Cl in the ASPs and the terminal dimethylamino group, and the hydrogen bonding between the N atoms of the MB+ hetero ring and the particle silanol group were enhanced. These results mainly suggest that the protein adsorption system occurs through the hydrogen bonding between the carboxy groups of the protein and the silanol groups on the particles and via electrostatic interactions between the amino groups of the protein and the dissociated silanol groups and the contained Cl at the particles. Thus, the spectral characterization using dyes as probes is expected to predict the protein interactions with the amorphous silica particles.

Control of Biological Surface States on Chlorine-Doped Amorphous Silica Particles and Their Effective Absorptive Ability for Antibody Protein.

Amorphous silica particles (ASPs) have low biotoxicity and are used in foodstuffs; however, the adsorption states of proteins on their surfaces have not yet been clarified. If the adsorption states can be clarified and controlled, then a wide range of biological and medical applications can be expected. The conventional amorphous silica particles have the problem of protein adsorption due to the strong interaction with their dense silanol groups and denaturation. In this study, the surfaces of amorphous silica particles with a lower silanol group density were modified with a small amount of chlorine during the synthesis process to form a specific surface layer by adsorbing water molecules and ions in the biological fluid, thereby controlling the protein adsorption state. Specifically, the hydration state on the surface of the amorphous silica particles containing trace amounts of chlorine was evaluated, and the surface layer (especially the hydration state) for the adsorption of antibody proteins while maintaining their steric structures was evaluated and discussed. The results showed that the inclusion of trace amounts of chlorine increased the silanol groups and Si-Cl bonds in the topmost surface layer of the particles, thereby inducing the adsorption of ions and water molecules in the biological fluid. Then, it was found that a novel surface layer was formed by the effective adsorption of Na and phosphate ions, which would change the proportion of the components in the hydration layer. In particular, the proportion of the free water component increased by 21% with the doping of chlorine. Antibody proteins were effectively adsorbed on the particles doped with trace amounts of chlorine, and their steric adsorption states were evaluated. It was found that the proteins were clearly adsorbed and maintained the steric state of their secondary structure. In the immunoreactivity tests using streptavidin and biotin, biotin bound to the chlorine-doped particles showed efficient reactivity. In conclusion, this study is the first to discover the surface layer of the amorphous silica particles to maintain the steric structures of adsorbed proteins, which is expected to be used as a carrier particle for antibody test kits and immunochromatography.

Effects of interfacial interactions between metal and process control agents during ball milling on the microstructure of the milled Fe-based nanocrystalline alloy powder.

Fe-Si-B-P-Cu nanocrystalline alloy were treated with ball-mill using a lubricant as a process control agent (PCA). The resulting alloy powder is a strong candidate material for soft magnetic composites. Two ball milling methods (continuous and interval) were employed to control the interactions between the PCA and the alloy surface, and their effect on the microstructure of the prepared alloy particles was investigated. The alloy sheet was broken into small pieces and deformed plastically into flake-shaped particles regardless of the ball milling method implemented. Friction-force microscopy of the alloy immersed in the PCA revealed that the friction coefficient of the alloy surface exposed to air for a certain period was higher than that of the unexposed alloy surface (immediately after polishing). During ball milling, the ratio of the newly generated surface to the oxidized surfaces of the alloy subjected to interval milling was smaller than that of the alloy subjected to continuous milling. Therefore, the friction coefficient of the surface of the alloy subjected to interval milling was higher than that of the alloy subjected to continuous milling. Synchrotron radiation analysis revealed that the alloy subjected to interval milling exhibited enhanced surface friction, showing an obvious steepness and inflection in the diffraction intensity as a function of the tilt angle based on the Schulz reflection method. This indicates formation of crystallographic texture in α-Fe grains in an amorphous matrix. Hence, we demonstrated successfully that the ball milling process induced a crystallographic texture in the Fe-based nanocrystalline alloy due to plastic deformation due to the enhanced surface friction. The surface of the alloy was prepared based on the effect of the interfacial interactions between the alloy surface and the PCA.

Synthesis of nanostructured silica/hydroxyapatite hybrid particles containing amphiphilic triblock copolymer for effectively controlling hydration layer structures with cytocompatibility.

We synthesized nanostructured mesoporous silica (MS)/hydroxyapatite (HA) hybrid particles in the presence of amphiphilic poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO20PPO70PEO20) triblock copolymer (P123). The particles exhibited slit-shaped mesostructures and underwent hybridization reaction between the MS and HA phases containing P123. Furthermore, the aggregated form of the particles exhibited dispersion stability in water in the monodispersed state (average particle size: 145 nm and coefficient of variation: 4.3% in the case of the maximum added amount of P123). Then, the structures of the hydration layer and the adsorbed protein on the particles were investigated to understand the effect of the hydration layer structures on the protein secondary structures. The ratio of the bonding water (intermediate and nonfreezing water) to free water increased upon hybridization, and it decreased with increasing P123 concentration. Upon hybridization, the component ratio of the asymmetric O-H stretching vibration between free water molecules decreased, and that of the symmetric O-H stretching vibration of intermediate water molecules increased. With increasing P123 concentration, the asymmetric O-H stretching vibration between free water molecules increased and the symmetric O-H stretching vibration of intermediate water molecules decreased. It was found that the protein native state component ratios of α-helix and ß-sheet increased with increasing symmetric O-H stretching vibration between intermediate water molecules, and they decreased with decreasing asymmetric O-H stretching vibration between free water molecules. Moreover, the cytotoxicity against osteoblasts (MC3T3-E1) was evaluated and the hybrid particles exhibited a high cell density, indicating their bioactivity. On the hybrid particles interacting with P123, the cells were three-dimensionally assembled and uniaxially grown with the culture. Therefore, this is the first successful report of the synthesis of nanostructured MS/HA hybrid particles interacting with P123, and the controlled hydration layer structures on the particle surfaces were found to contribute to the protein secondary structures, promoting cytocompatibility.

Enhancement effect on antibacterial property of gray titania coating by plasma-sprayed hydroxyapatite-amino acid complexes during irradiation with visible light.

The aim of this study was to reveal the mechanism of enhancement of antibacterial properties of gray titania by plasma-sprayed hydroxyapatite (HAp)-amino acid fluorescent complexes under irradiation with visible light. Although visible-light-sensitive photocatalysts are applied safely to oral cavities, their efficacy is not high because of the low energy of irradiating light. This study proposed a composite coating containing HAp and gray titania. HAp itself functioned as bacteria catchers and gray titania released antibacterial radicals by visible-light irradiation. HAp-amino acid fluorescent complexes were formed on the surface of the composite coating in order to increase light intensity to gray titania by fluorescence, based on an idea bioinspired by deep-sea fluorescent coral reefs. A cytotoxicity assay on murine osteoblastlike cells revealed that biocompatibility of the HAp-amino acid fluorescent complexes was identical with the that of HAp. Antibacterial assays involving Escherichia coli showed that the three types of HAp-amino acid fluorescent complexes and irradiation with three types of light-emitting diodes (blue, green, and red) significantly decreased colony-forming units. Furthermore, kelvin probe force microscopy revealed that the HAp-amino acid fluorescent complexes preserved the surface potentials even after irradiation with visible light, whereas those of HAp were significantly decreased by the irradiation. Such a preservative effect of the HAp-amino acid fluorescent complexes maintained the bacterial-adhesion performance of HAp and consequently enhanced the antibacterial action of gray titania.

Effects of compression on orientation of ligands in fluorescent complexes between hydroxyapatite with amino acids and their optical properties.

This study aims to reveal the effects of pressure during cold isostatic pressing (CIP) on the microstructure and optical properties of fluorescent HAp complexes. Although the microsturucture-dependent properties of fluorescent HAp complexes have been reported to improve the antibacterial properties of photocatalyst coating layers, the mechanism behind the changes in the fluorescence properties of highly compressed HAp complexes has not yet been unveiled. CIP was successfully used to fabricate fluorescent HAp - amino acid complexes, and their fluorescence intensities increased with increasing fabrication pressure. Peak wavelength of fluorescence emitted by the HAp - amino acid complexes exhibited yellow to red shift. Although the thickness of the amino acid layer was saturated in higher pressure cases, the concentration of amino acids increased proportionally with pressure, which suggests changes in the packing structures of the ligands in the HAp- amino acid complexes. Polarized Raman spectroscopy measurements clearly detected ligands normally arranged to the HAp layer under high pressure fabrication conditions, which can provide the tightly packed ligand structure in the HAp- amino acid complexes. These tightly packed ligand structure in the HAp- amino acid complexes could emit stronger fluorescence owing to the increased density of complexations. This newly found pressure dependency in the optical properties of HAp-amino acid complexes is beneficial for developing biocompatible fluorescence materials or enhancement agents for antibacterial coating layers.

Formation of stacked luminescent complex of 8-hydroxyquinoline molecules on hydroxyapatite coating by using cold isostatic pressing.

Cold isostatic pressing successfully formed a chelate complex of 8-hydroxyquinoline (8 Hq) molecules on plasma-sprayed hydroxyapatite (HAp) coating by solid-state reaction. The complex emits a fluorescence peak at approximately 500 nm by UV irradiation. The red shift of the fluorescence was newly observed in the cases of highly compressed complex due to π - π stacking of aromatic ring in the molecular structure of 8 Hq. The immersed complex coating in Simulated Body Fluid (SBF) demonstrated amorphous apatite precipitation and kept its fluorescence property.

Effective Surface Functionalization of Carbon Fibers for Fiber/Polymer Composites with Tailor-Made Interfaces.

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.

Frontispiece: Effective Surface Functionalization of Carbon Fibers for Fiber/Polymer Composites with Tailor-Made Interfaces.

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.

Synthesis and luminescence properties of Eu(III)-doped nanoporous silica spheres.

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.