Structural metamorphosis and photophysical properties of thermostable nano- and microcrystalline lanthanide polymer with flexible coordination chains.

Luminescent lanthanide coordination polymer crystals (LCPCs) represent an area of growing interest in materials chemistry owing to their unique and tailorable functional properties. The LCPCs provide a high level of structural tunability, including size- and morphology-dependent properties; therefore, they are promising materials for next-generation phosphors in a wide range of applications such as light emitting diodes. Here, by controlling the morphology of thermostable europium coordination polymer crystals, [Eu(hfa)3(dpbp)]n, hfa: hexafluoroacetylacetonate and dpbp:4,4'-bis(diphenyl　phosphoryl) biphenyl), we realized a novel red phosphor with narrow linewidth emission (FWHM = 7.8 nm). The obtained luminescent LCPCs with unique structures were characterized by X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), dynamic light scattering (DLS) and thermogravimetric analysis. Among, them, size tunable crystalline polymer spheres were found to have high internal quantum efficiency (ex., IQE = 79%) and highly thermostability (>300°C), and to exhibit dispersibility in PMMA media. The obtained results on the structural tunability of these materials can be used for the development of synthesis techniques for nanoscale materials based on crystalline lanthanide-based coordination phosphors.

Effect of Vanadium Oxide on the Crystallization of CaO-Al2O3-SiO2 Glass.

This study investigated the effect of vanadium oxide on the crystallization of CaO-Al2O3-SiO2 (CAS) glass. Specifically, this study subjected CAS glass-ceramics (GCs) with precipitated hexagonal platy particles of metastable CaAl2Si2O8 (CAS GC-H), a layered crystal, that was prepared using metallic molybdenum (Mo) particles as nucleation agents. When the parent glass of CAS GC-H was crystallized with the addition of vanadium oxide in the 0.052-0.21 wt % range, the obtained platy particles of metastable CaAl2Si2O8 displayed an increase in the aspect ratio from 20 to 15 compared with conventional CAS GC-Hs. In addition, no crystallization occurred in the CAS glass with vanadium oxide in the 0.052-0.21 wt % range in the absence of metallic Mo particles. Meanwhile, a CAS glass containing 1.0 wt % vanadium oxide without the addition of metallic Mo particles showed the precipitation of metastable CaAl2Si2O8. Therefore, these results indicated that the aspect ratio of layered crystals in glass was controlled by the addition of a relatively small content of vanadium oxide, and a new nucleation agent for the precipitation of metastable CaAl2Si2O8 in CAS glass using a relatively high content of vanadium oxide was developed.

Photocatalytic Inactivation of Co-Culture of E. coli and S. epidermidis Using APTES-Modified TiO2.

The presented work shows the antibacterial activity of TiO2 photocatalysts modified by 3-aminopropyltriethoxysilane (APTES). The APTES-functionalized TiO2 samples were obtained by the solvothermal process followed by calcination. The antibacterial activity of APTES/TiO2 samples was evaluated with two species of bacteria, Escherichia coli and Staphylococcus epidermidis, under artificial solar light (ASL) irradiation. The used bacteria are model organisms characterized by negative zeta potential (approx. -44.2 mV for E. coli and -42.3 mV for S. epidermidis). For the first time, the antibacterial properties of APTES-functionalized TiO2 were evaluated against mono- and co-cultured bacteria. The high antibacterial properties characterized the obtained APTES-modified nanomaterials. The best antibacterial properties were presented in the TiO2-4 h-120 °C-300 mM-Ar-300 °C sample (modified with 300 mM of APTES and calcined at 300 °C). The improvement of the antibacterial properties was attributed to a positive value of zeta potential, high surface area, and porous volume.

Effect of carbon on the co-presence of metallic tungsten as a nucleation agent and Eu2+ in glass: crystallization of CaO-Al2O3-SiO2 glass probed with Eu2+ luminescence.

This study demonstrated simple redox control in glasses by improving the method used to added glass raw materials. Specifically, the effect of carbon on the co-presence of metallic tungsten (W) particles as nucleation agents and Eu2+ ions in CaO-Al2O3-SiO2 (CAS) glass was investigated via their crystallization to form CAS glass-ceramics (GCs). In this study, the glass specimens were prepared by mixing glass cullet containing metallic W particles and Eu2+ ions, respectively, with a glass batch containing carbon. Whereas the glass specimen was yellowish because of the presence of Eu2+ when carbon was not added during the remelting process, the glass specimen prepared with carbon was black because of the presence of metallic W particles. In addition, this specimen displayed the 470 nm emission band in its fluorescence spectrum recorded under 393 nm excitation, which was attributed to the presence of Eu2+. According to the fluorescence and transmission spectra, the glass specimen showed a darker coloration and more intense 470 nm emission band compared with the specimen prepared by the conventional melting method that included a remelting process. These results indicated that metallic W and Eu2+ were reduced with greater efficiency by the melting method that involved mixing the glass cullet and batch. In addition, the heat-treated glass specimen prepared by the aforementioned mixing method contained a greater amount of metastable CaAl2Si2O8 with increasing heat treatment time as revealed by X-ray diffraction analysis and scanning electron microscopy observation. The intensity of the 470 nm emission band decreased with increasing intensity of the band at 420 nm because of the incorporation of Eu2+ into the crystalline phase, and the increase in intensity of the 420 nm band was lineally proportional to the volume fraction of the crystallized glass specimens. The results therefore indicated that the co-presence of metallic W particles as nucleation agents and Eu2+ as a probe for tracking the crystallization process was achieved by the addition of carbon during the remelting process of mixed cullet containing W and Eu2+ through crystallization of the CAS glass. The results thus demonstrate the importance of improving the method used to added glass raw materials.

Microstructural Control of CaO-Al2O3-SiO2 Glass Ceramics by Oxidation and Mixing with Nucleation Agents.

Microstructural control of CaO-Al2O3-SiO2 (CAS) glass ceramics (GCs) was achieved by oxidation and mixing with nucleation agents. CAS GCs were precipitated with hexagonal platy particles of metastable CaAl2Si2O8 layered crystals (CAS GC-H), which are typically prepared under a reductive atmosphere that forms metallic Mo or W particles as nucleation agents. The average particle size of crystals decreased significantly from 50 to 11 µm when the CAS GC-H containing metallic W particles was prepared under an oxidative atmosphere. Compared to this CAS-GC-H, the crystal particle size increased from 8-20 to 10-30 µm when the CAS GC-H was prepared by mixing glass cullet containing metallic Mo and that containing metallic W particles. These results indicate that one microstructure of CAS GC-H is controlled on the micrometer scale from a parent glass with one composition by varying the experimental conditions related to the glass melting state.

Photoreduction of Copper Ions Using Silica-Surfactant Hybrid and Titanium (IV) Oxide under Sulfuric Acid Conditions.

Photoreduction of Cu2+ ions to Cu metal by titanium(IV) oxide (TiO2) was conducted in the presence of a silica-surfactant hybrid under sulfuric acid conditions. After irradiation, a dark-red color, reflections due to Cu metal in the X-ray diffraction pattern, and peaks due to Cu 2p1/2 and 2p3/2 in the X-ray photoelectron spectrum indicated the precipitation of Cu metal in the product. In addition, an increase in the Brunauer-Emmett-Teller specific surface area from 36 and 45 m2/g for the silica-surfactant and TiO2, respectively, to 591 m2/g for the product, and a decrease in the intensity of the C-H stretching band in the Fourier-transform infra-red spectra implied the removal of surfactant during the reaction. These characteristics were never observed when TiO2 was used solely. Therefore, this study indicated that the photoreduction of Cu2+ ions to Cu metal by TiO2 was facilitated under the sulfuric acid medium, where the surfactants extracted from silica-surfactant hybrids by protons in the acidic condition were successfully photo-oxidized by TiO2. Thus, this study presents a new application of the conversion of a silica-surfactant hybrid into mesoporous silicas.

Assessment of the Crystallization Process of CaO-Al2O3-SiO2 Glass Probed with Tb3+ Luminescence.

The ratio of the intensity of Tb3+ fluorescence at 543 nm because of an electric dipole transition (5D4-7F5) relative to that at 437 nm due to a magnetic dipole transition (5D3-7F4) was determined to be proportional to the amount of metastable CaAl2Si2O8 crystals precipitated in CaO-Al2O3-SiO2 glass. The present results indicate that Tb3+ luminescence can be used as a probe to evaluate the crystallization of glass.

Effect of kaolinite edge surfaces on formation of Tb3+-doped phosphor by solid-state reaction.

This study assessed the effect of kaolinite edge surfaces on solid-state reactions. Specifically, Tb3+-doped metastable CaAl2Si2O8 showing green phosphorescence was prepared via a solid-state reaction between expanded kaolinite, a methoxy-modified kaolinite, having Tb3+ ions adsorbed on its edge surfaces and CaCO3. This material cannot be obtained by the conventional grinding of kaolinite, CaCO3 and Tb2O3, indicating that the use of kaolinite edge surfaces is advantageous as a means of achieving certain solid-state reactions.

Regioselective Approach to Characterizing Increased Edge Availability in Layered Crystal Materials following Layer Expansion: Reaction of Kaolinite with Octadecyltrimethylammonium Salts.

In this paper, the regioselective reactions of kaolinite and methoxy-modified kaolinite (MeO-Kaol), methanol-expanded kaolinite, with octadecyltrimethylammonium salts are compared. This study mainly concerns the reactions of kaolinite or MeO-Kaol with octadecyltrimethylammonium chloride (C18TAC) in methanol and the subsequent exhaustive washing of the resultant products with ethanol. X-ray diffraction patterns of the products reveal no intercalation of C18TAC between pristine kaolinite layers. Additionally, intercalation and subsequent deintercalation of C18TAC proceed in the product using MeO-Kaol. In the Fourier-transform infrared spectra, the intensities of CH2 stretching bands of the product prepared using MeO-Kaol drastically increase compared to those using kaolinite. In addition, CH2 stretching bands of the product using kaolinite are hardly observed without enlarging the spectrum. The product using MeO-Kaol also displays mass loss in the range of 200-300 °C in the thermogravimetric curve and a nitrogen content with 0.15 mass% estimated using the CHN analysis. These results therefore demonstrate an increase in the available reactive edges in the layered crystal material following an expansion of the stacked layers.

Expansion of orderly stacked metakaolinite layers and order destruction using a kaolinite-tetraphenylphosphonium chloride intercalation compound.

The expansion of metakaolinite layers with stacking order and the order destruction were examined by the heat treatment of a kaolinite-tetraphenylphosphonium chloride intercalation compound (Kaol-TPhPCl) at 540 °C under a nitrogen atmosphere followed by the manual grinding of the product using a mortar and a pestle. Fourier-transform infrared spectroscopy and solid-state 27Al nuclear magnetic resonance spectroscopy with magic angle spinning revealed the kaolinite dehydroxylation. Moreover, the absence of kaolinite diffraction lines and the appearance of the 1.85 nm diffraction line in the X-ray diffraction pattern, together with the observation of the hexagonal plate-like morphology in the field-emission scanning electron microscopy, indicated the kaolinite amorphization with the orderly-stacked layers. These results, along with the disappearance of the 1.85 nm diffraction line upon the manual grinding of heat-treated Kaol-TPhPCl, clearly indicated the formation of expanded metakaolinite layers with stacking order and the subsequent order destruction by manual grinding.

Effects of kaolinite layer expansion and impurities on the solid-state reaction of kaolinite.

Expanded kaolinite without impurities was found to serve as a suitable raw material for the rapid formation of metastable CaAl2Si2O8 with the suppression of byproduct formation. This was accomplished based on the solid-state reaction of the kaolinite with calcium carbonate promoted by mechanical grinding.

Fabrication of a Silica-Silica Nanoparticle Monolayer Array Nanocomposite Film on an Anodic Aluminum Oxide Substrate and Its Optical and Tribological Properties.

The fabrication and properties of silica nanoparticle monolayer arrays (SNMAs) immobilized on silica films on nanoporous anodic aluminum oxide (AAO) substrates by polymerization of silicic acid and a two-step spin-coating technique are reported. Reflection spectra of the obtained silica-SNMA nanocomposite films on AAO substrates were almost the same as those of the original AAO substrate. The coefficient of friction at an applied load of 0.98 N under dry conditions for a film fabricated under optimal conditions was significantly decreased by 76% with respect to that without a silica-SNMA nanocomposite film on an AAO substrate. The results also showed a lower coefficient of friction than that for MoS2 nanoparticles (commonly used for self-lubricating films) deposited on an AAO substrate. We demonstrate that the silica-SNMA nanocomposite film with an optimal nanoroughness, thickness, and wear resistance can be used as a novel coating film for AAO substrates with both a high color degree of freedom and a low coefficient of friction at a high applied load (ca. 1 N).

Fabrication of Silica Nanoparticle Monolayer Arrays Using an Anodic Aluminum Oxide Template.

Non-close-packed (NCP) silica nanoparticle monolayer arrays (SNMA) on ordered porous anodic aluminum oxide (AAO) templates were fabricated for the first time by a novel two-step spin-coating technique. The obtained NCP-SNMA-AAO was composed of silica nanoparticles (average primary particle size of 440 nm) and well-organized nanopores on the AAO substrates. NCP-SNMA-AAO with a supporting ratio of 87% silica nanoparticles showed a hydrophilic surface (water contact angle of 51.0°), while the original AAO substrate shows a hydrophobic surface (water contact angle of 107.9°). The maximum coefficient of static friction was decreased by 29% (0.327 → 0.233). The coefficient of dynamic friction was also decreased by 20% (0.281 → 0.226). We found that controlling the silica supporting ratio using the two-step spin-coating technique is an effective approach for surface modification of an AAO substrate.

Simple and Convenient Method for the Isolation, Culture, and Re-collection of Cancer Cells from Blood by Using Glass-Bead Filters.

Circulating tumor cells (CTCs) are tumor cells that originate from primary cancer tissues, enter the bloodstream in the body, and metastasize to the other organs. Simple and convenient methods for their detection, capture, and recovery from the blood of cancer patients would be highly desirable. We report here on a simple and convenient methodology to trap, culture, and re-collect cancer cells, the sizes of which are greater than those of normal hematologic cells, by the use of glass-bead filters (GBFs). We prepared GBFs with a diameter of 24 mm and thicknesses of 0.4 mm and 1.2 mm, with well-defined pores, by sintering round-shaped glass beads (diameter: 63-106 µm). A small integrated glass-bead filter (iGBF) with a diameter of ca. 9.6 mm for the use in filtering a small volume of blood was also designed and prepared. Using GBF and iGBF, it was possible to efficiently capture mouse Lewis lung carcinoma cells expressing green fluorescent protein spiked in saline/blood by single and repeated (circulation) filtrations in in vitro experiments with very small amounts of red blood cells being captured. In addition, we successfully captured B16 CTCs from the blood of a B16 melanoma metastasis mouse model by iGBF. Cancer cells/CTCs captured on/in the GBF could be cultured and efficiently recovered from the filters. Filtration by GBF had negligible effect on the adherent and proliferative characteristics of cancer cells. Simple and convenient methods for the capture, culture, and re-collection of CTCs by GBF along with flexibility of GBF, which permits them to be molded into suitable architectures having the desired shape and size, should be useful for early and convenient diagnosis and treatment of cancer and related diseases.

Preparation of a titania/X-zeolite/porous glass composite photocatalyst using hydrothermal and drop coating processes.

Combinations of TiO2 photocatalysts and various adsorbents have been widely studied for the adsorption and photocatalytic decomposition of gaseous pollutants such as volatile organic compounds (VOCs). Herein, a TiO2-zeolite-porous glass composite was prepared using melt-quenching and partial sintering, hydrothermal treatment, and drop coating for preparation of the porous glass support and X-zeolite and their combination with TiO2, respectively. The obtained composite comprised anatase phase TiO2, X-zeolite, and the porous glass support, which were combined at the micro to nanometer scales. The composite had a relatively high specific surface area of approximately 25 m2/g and exhibited a good adsorption capacity for 2-propanol. These data indicated that utilization of this particular phase-separated glass as the support was appropriate for the formation of the bulk photocatalyst-adsorbent composite. Importantly, the photocatalytic decomposition of adsorbed 2-propanol proceeded under UV light irradiation. The 2-propanol was oxidized to acetone and then trapped by the X-zeolite rather than being released to the atmosphere. Consequently, it was demonstrated that the micrometer-scaled combination of TiO2 and zeolite in the bulk form is very useful for achieving both the removal of gaseous organic pollutants and decreasing the emission of harmful intermediates.

Particle size dependence of the surface-enhanced Raman scattering properties of densely arranged two-dimensional assemblies of Au(core)-Ag(shell) nanospheres.

We investigated the dependence of the surface-enhanced Raman scattering (SERS) activity of densely arranged two-dimensional assemblies of spherical Au(core)-Ag(shell) nanoparticles (Au/AgNSs) on the nanoparticle diameter. The size-controlled Au/AgNSs were synthesized using the Au nanosphere seed-mediated growth method without any bulky stabilizers. The diameters of the Au/AgNSs were 38, 53, and 90 nm and the ratio of the total diameter to the Au core diameter was adjusted to ca. 2.0. Extinction spectra of the colloidal solutions of these nanoparticles exhibited the prominent peak of the localized surface plasmon resonance (LSPR) of Ag and therefore the Au/AgNSs exhibited LSPR properties almost the same as Ag nanospheres. It was confirmed from SEM observation that the organic solvent-mediated liquid-liquid interface assembly technique easily generated densely arranged two-dimensional assemblies of the nanospheres. The extinction spectra of all the assemblies exhibited a prominent broad peak ranging from 500 nm to the near-infrared region, which is assigned to the longitudinal LSPR mode of the coupling nanospheres. The extinction intensity increased with increasing nanosphere diameter. The SERS activities of these assemblies were investigated using p-aminothiophenol as a probe molecule. The result revealed that the enhancement factor (EF) of the Raman signal dramatically increased upon increasing the particle diameter. The maximum EF obtained with a laser excitation wavelength of 785 nm was 1.90 × 10(6) for a nanosphere diameter of 90 nm. This renders the two-dimensional assemblies of the plasmonic Au/AgNSs promising for the development of highly sensitive SERS sensor platforms due to their strong electromagnetic effect.

Size- and shape-controlled conversion of tungstate-based inorganic-organic hybrid belts to WO3 nanoplates with high specific surface areas.

Two-dimensional monoclinic WO(3) nanoplates with high specific surface areas are synthesized through a novel conversion process using tungstate-based inorganic-organic hybrid micro/nanobelts as precursors. The process developed involves a topochemical transformation of tungstate-based inorganic-organic hybrid belts into WO(3) nanoplates via an intermediate product of H(2)WO(4) nanoplates, utilizing the similarity of the W-O octahedral layers in both H(2)WO(4) and WO(3). The as-obtained WO(3) nanoplates show a single-crystalline nanostructure with the smallest side along the [001] direction. The WO(3) nanoplates are 200-500 nm x 200-500 nm x 10-30 nm in size, and their specific surface areas are up to 180 m(2) g(-1). Photocatalytic measurements of visible-light-driven oxidation of water for O(2) generation in the presence of Ag(+) ions indicate that the activity of the as-obtained WO(3) nanoplates is one order of magnitude higher than that of commercially available WO(3) powders.

Effect of solid/solution ratio on apatite formation from CaSiO3 ceramics in simulated body fluid.

The effect of the solid/solution (S/S) ratio on apatite formation from CaSiO3 ceramics in simulated body fluid (SBF) was investigated. CaSiO3 ceramics with a Ca/Si ratio of 0.91 were prepared by sintering CaSiO3 powder coprecipitated from ethanol solutions of Ca(NO3)2. 4H2O and Si(OC2H5)4 using NH4OH as the precipitant. These ceramics were reacted with SBF at S/S ratios of 1.0, 2.5 and 8.3 mg/ml at 36.5 degrees C for various times. Formation of apatite was observed at all the S/S ratios after soaking for 1 day. The amount and microstructure of the apatite obtained at a S/S ratio of 8.3 mg/ml, however, differed largely from the product formed at the other two S/S ratios. The apatite formed at S/S = 8.3 mg/ml was of smaller particle size, formed in smaller amount and with less preferred orientation of the (001) of apatite crystals compared with those formed at S/S = 1.0 and 2.5 mg/ml. An increase of Ca and decrease of the P components occurred in the soaked SBF at S/S = 8.3 mg/ml, the changes being much more marked than with the other two S/S ratios. These differences in the concentration changes in SBF at different S/S ratios are attributed to the difference in the apatite formation from the CaSiO3 ceramics.

Porous properties of activated carbons from waste newspaper prepared by chemical and physical activation.

Activated carbons were prepared from old newspaper and paper prepared from simulated paper sludge by chemical activation using various alkali carbonates and hydroxides as activating reagents and also by physical activation using steam. In the chemical activation, the influence of oxidation, carbonization, and activation on the porous properties of the resulting activated carbons was investigated. The specific surface areas (S(BET)) of the activated carbons prepared by single-step activation (direct activation without oxidation and carbonization) were higher than those resulting from two-step activation (oxidation-activation and carbonization-activation) and three-step activation (oxidation-carbonization-activation) methods. The S(BET) values were strongly dependent on the activating reagents and the activating conditions, being >1000 m(2)/g using K(2)CO(3), Rb(2)CO(3), Cs(2)CO(3), and KOH as activating reagents but <1000 m(2)/g using Li(2)CO(3), Na(2)CO(3), and NaOH. These differences in S(BET) values are suggested to be related to the ionic radii of the alkalis used as activating reagents. The microstructures of the higher S(BET) samples show a complete loss of fiber shape but those of the lower S(BET) samples maintain the shape. In the physical activation, the porous properties of the activated carbons prepared by the single-step method were examined as a function of the production conditions such as activation temperature, activation time, steam concentration, and flow rate of the carrier gas. The maximum S(BET) and total pore volume (V(P)) were 1086 m(2)/g and 1.01 ml/g, obtained by activation at 850 degrees C for 2 h, flowing 20 mol% of steam in nitrogen gas at 0.5 l/min. A correlation was found between S(BET) and the yield of the product, the maximum S(BET) value corresponding to a product yield of about 10%. This result is suggested to result from competition between pore formation and surface erosion. Compared with chemically activated carbons using K(2)CO(3), the porous properties of the physically activated carbons have lower S(BET) and V(P) values because of the smaller size and lower volume of their micropores. On the other hand, they retain the original fiber shape and the paper sheet morphology after activation.

Adsorption properties of activated carbon from waste newspaper prepared by chemical and physical activation.

Adsorption properties of activated carbons prepared from waste newspaper by chemical and physical activation were investigated using water vapor, ammonia, methane, and methylene blue (MB) as adsorbents. The water vapor adsorption isotherms show type V behavior and the maximum vapor adsorption of the chemically and physically activated products is about 1050 and 450 ml/g, respectively. The higher water vapor adsorption of the chemically activated products is attributed to the higher specific surface area (S(BET)) and greater hydrophilic activity (arising from the surface oxygen-containing functional groups) than in the physically activated products. The adsorption of ammonia and methane was measured by temperature-programmed desorption (TPD). NH(3) adsorption is found to be higher in the chemically activated product than in the physically activated product while methane adsorption is slightly higher in the physically activated products even though these have lower S(BET) values. In the MB adsorption, the chemically activated products show higher adsorption (390 mg/g) than the physically activated product. These results are suggested to be related to the surface characteristics.