Formation mechanism for hexagonal-structured self-assemblies of nanocrystalline titania templated by cetyltrimethylammonium bromide

Hexagonal-structured self-assemblies of nanocrystalline (anatase) titania templated by cetyltrimethylammonium bromide (C(16)H(33)N(CH(3))(3)Br; CTAB) (Hex-ncTiO(2)/CTAB Nanoskeleton) were formed after mixing of aqueous solutions containing CTAB spherical micelles and titanium oxysulfate acid hydrate (TiOSO(4).xH(2)SO(4).xH(2)O) as a titania precursor in the absence of any other additives. Formation mechanism of the Hex-ncTiO(2)/CTAB Nanoskeleton was examined in terms of the reaction temperature, titania precursor/CTAB mixing ratio, surfactant type, electrostatic interaction, micelle formation and molecular component. We found that crystal growth of crystalline (anatase) titania (polymorphic crystallization) was promoted with higher temperature and lower titania precursor content in aqueous solutions. In addition, we revealed that the crystalline (anatase) titania was formed in polycation, poly(allylamine hydrochloride ([CH(2)CH(CH(2)NH(2))HCl](n); PAH), and formamide (HCONH(2)) solutions. On the other hand, no titania formation was observed in anionic systems such as sodium dodecyl sulfate (CH(3)(CH(2))(11)OSO(3)Na; SDS) and poly(sodium 4-styrenesulfonate ([C(8)H(7)SO(3)Na](n); PSSS). This indicates that hydrolysis reaction of the titania precursor is initiated by not only cations but also nitrogen atoms in molecules and polymers. Hexagonally structure was formed in only cationic surfactant micellar solutions but not in polycation solutions and formamide.     

Synthesis and catalytic properties of sulfonic acid-functionalized monodispersed mesoporous silica spheres

A new type of sulfonic acid-functionalized monodispersed mesoporous silica spheres (MMSS) were synthesized directly by co-condensation and subsequent oxidation. By changing the methanol ratio, sulfonic acid-functionalized MMSS with different particle diameters (390–830 nm) and the same mesopore sizes were successfully synthesized. TEM observations revealed that the mesopores were aligned radially from the center towards the outside of the spheres, even in the sulfonic acid-functionalized MMSS. The catalytic activities of the sulfonic acid-functionalized MMSS were studied in condensation reactions between 2-methylfuran and acetone, and it was found that their catalytic activities are highly dependent on the particle diameters. In addition, the catalytic activity of MMSS was much higher than that of other forms of mesoporous silica due to its radially-aligned mesopores.     

Amino acid sensing by impedance of porous monolith-type ion exchanger

A biological and chemical sensor with rapid response at the microlevel is required for health and environmental monitoring. To develop a high-performance sensor, we use a porous monolith-type ion exchanger having three-dimensional acceptors to sense chemical substances. This porous monolith-type ion exchanger has an open-cellular structure with 5-50-μm diameter pores. The concentration of amino acids in the solution can be detected by measuring the impedance of the monolith-type ion exchanger. The novel ion exchanger has a high-exchange rate and high-electrical conductivity compared with that of the conventional ion-exchange resins. It is found that the impedance of the porous ion exchanger varies widely, depending on the amino acids such as glycine, asparatic acid, lysine, and phenylalanine. The impedance of anion exchanger had the highest value for phenylalanine with a benzene ring. OH-ion conduction is suppressed possibly due to the phenylalanine molecules stabilized by the hydrophobic interaction with the anion exchanger. In addition, we succeeded in sensing amino acid ions with concentration as low as 10⁻⁷ mol. The porous ion exchanger has the potential of a high-performance device for biological and chemical sensing.     

Epoxidation catalysts derived from introduction of titanium centers onto the surface of mesoporous aluminophosphate: Comparisons with analogous catalysts based on mesoporous silica

Titanium/AlPO materials were prepared by grafting a titanium alkoxide (titanium isopropoxide) onto a mesoporous aluminophosphate. The structures of the surface-bound titanium species were investigated by UV–vis, FTIR, MAS NMR, and XANES/EXAFS spectroscopies. The titanium anchoring occurs by reaction between the alkoxide precursor and surface Al–OH and P–OH groups of the AlPO support. The titanium species exist in isolated tetrahedral coordination environments, and as oligomerized species. The catalysts prepared are selective and active for the liquid-phase epoxidation of cyclohexene in the presence of TBHP. The observed activities and selectivities were comparable with those obtained for similarly prepared titanium/SBA-15 samples of similar Ti content (but higher BET surface area).     

Comparison of DNA sequencing analysis with phenotyping test for identification of yeasts isolated from foods

The identification of 20 strains of yeasts isolated from foods by means of DNA sequence analysis with two kinds of universal primers for the rDNA region was examined, and the results were compared with those of the conventional phenotyping test using API 20C AUX. In the analysis of the 26S region, all 20 yeast strains tested were identified at the species level. In the ITS1 region, 16 strains were also classified at the species level. In addition, all results of DNA sequence analysis were consistent with those of the phenotyping test at the genus level. Furthermore, DNA sequence analysis was able to identify causative yeasts observed in two suspect foods, though phenotyping tests alone failed to identify them.     

Critical bubble radius for expansion in extrusion cooking

Strong wheat flour, weak wheat flour and rice flour were expanded by sudden reduction in pressure at the discharge port of an extruder. Their micropore-volume distributions were measured by nitrogen adsorption isotherms. The results were compared with the theoretical critical radius for expansion calculated from the balance of forces acting inside and outside a bubble. The micropore volume near the theoretical critical radius for expansion of an extrudate decreased remarkably after extrusion cooking, indicating that the theoretical critical radius for expansion almost coincided with the experimental one.     

Study of the nanostructure of Gum Metal using energy-filtered transmission electron microscopy

The nanostructure of Gum Metal, which has many anomalous mechanical properties, was investigated using transmission electron microscopy with energy filtering. A precise analysis of the weak diffuse electron scattering that was observed in the electron diffraction patterns of the Gum Metal specimen revealed that Gum Metal contains a substantial amount of the nanometer-sized ω phase. The morphology of the ω phase appeared to have a correlation with the faulting in the {2 1 1} planes, which are one of the characteristic lattice imperfections of the Gum Metal specimen. It is likely that the nanometer-sized ω phase may be a type of obstacle related to the restriction of the dislocation movement, which has been a significant problem in research on Gum Metal.     

Developments of new concept analytical instruments for failure analyses of sub-100 nm devices

We have developed analytical instruments based on new concepts for failure analyses of devices of 100 nm dimensions or less. They are a sputtered neutral mass spectrometer with focused ion beam for highly sensitive element analysis in microarea (10¹⁸ atoms/cm³ in 30 nm area), transmission electron microscope (TEM) with electron energy loss spectrometer for chemical bond analysis in less than 2 nm area, Nanoprober for electrical characteristics inspection in actual circuits, computed tomography-TEM for three-dimensional observation of crystalline defect with 1 nm spatial resolution, atmospheric pressure ionization mass spectrometer for trace impurities ppq (parts per quadrillion) analysis in gases, and glow discharge optical emission spectrometer for rapid and precise composition analysis. Using these instruments, it was found that the formation of SiO₂ or TiO_x film by water from titanic acid (TiO_x·H₂O) is the cause of the high resistivity in a contact (CVD-W/CVD-TiN/Ti/Si) and vaporization of silicon dioxide by phosphorus trifluoride (PF₃) is the cause of voids in interlayer dielectric film borophosphosilicate glass.