Easy formation process of anatase-TiO2 coating layer strongly bonded to titanium metal surface

Because of the formation of a surface passive film (rutile TiO₂) on its surface layer, titanium metal shows adequate corrosion resistance. As the surface layer (passive film) of titanium metal is very stable, any functionalization of the titanium metal has been generally performed using relatively complicated methods. This is because any direct oxidation of titanium metal only leads to the formation of rutile TiO₂ over the entire temperature range. Chemical reactions using titanium chemicals can easily produce anatase TiO₂ at temperatures of ≤600°C. Using precursors is one of the ways of producing an anatase TiO₂ coating on titanium metal. However, in previous studies, anatase TiO₂ layers easily peeled off when they were used in flowing water. Herein, we describe a simple process for obtaining an anatase TiO₂ coating layer strongly bonded to the titanium metal surface. In our process, titanium metal was pretreated with a reducing agent to create a surface TiH₂ layer, whose condensation reaction easily proceeds with a precursor (composed of oxalic acid and tetra-butoxy titanium). Subsequently, the treated titanium metal was calcinated at 550°C in air to achieve strong bonding between the anatase TiO₂ coating layer and titanium metal surface. The treated titanium metal exhibited excellent photocatalytic activity.     

Catalytic C-h/olefin coupling

The cleavage and addition of ortho C-H bonds in various aromatic compounds such as ketones, esters, imines, imidates, nitrile, and aldehydes to olefins and acetlylenes can be achieved catalytically with the aid of ruthenium catalysts. The reaction is generally highly efficient and useful in synthetic methods. The coordination to the metal center by a heteroatom in directing groups such as carbonyl and imino groups is the key. The reductive elimination to form a C-C bond is the rate-determining step.     

Mirror Constant for Tyranno® Silicon-Titanium-Carbon-Oxygen Fibers Measured in Situ in a Three-Dimensional Woven Silicon Carbide/Silicon Carbide Composite

The strength, S , of ceramic and glass fibers often can be estimated from fractographic investigation using the fracture mirror radius, r _m, and the relationship S = A _m/( r _m)^1/2, where A _mis the "mirror constant." The present work estimates the value of A _mfor Tyranno^® Si-Ti-C-O fibers in situ in a three-dimensional woven SiC/SiC-based composite to be 2.50 ± 0.09 MPa·m^1/2. This value is within the range of 2–2.51 MPa·m^1/2 previously obtained for nominally similar Nicalon^® Si-C-O fibers.     

ARCOR,a new photolithography technique with antireflective coating on resist

The multiple interference effect is one of the major causes of the fluctuation in critical dimension control (CD) and in mark detection for alignment. Suppressing this effect is critical for future photolithography. We propose a new photolithography technique called anti reflective coating on resist (ARCOR), which improves linewidth accuracy and overlay accuracy by suppressing multiple interference. ARCOR consists of relatively simple processes: A clear antireflective film is spun onto the resist prior to the mark detecting for alignment and exposure. The film is subsequently removed and the resist developed in the conventional way. ARCOR differs from ARC, which suppresses the reflection at the resist/substrate interface. ARCOR suppresses the reflection at the air/resist interface. ARCOR allows mark detection and exposure without light intensity-loss and multiple interference. The experiments mainly examine polysiloxane and perfluoroalkylpolyether as ARCOR materials. It is shown that linewidth accuracy can be improved from 0.3 to 0.03 μm. The signal-to-noise ratio of the alignment signal is drastically improved, and the overlay error is about half that of the conventional method. ARCOR is also effective for directly measuring the reflectivity at the resist/substrate interface, which is a key parameter of the multiple interference effect and the halation. Using ARCOR and a thin resist film, the measured ratio of reflected light to incident light indicates the reflectivity at the resist/substrate interface. Because, the probe light does not reflect off the resist surface and the intensity-loss at the resist surface is suppressed. With perfluoroalkylpolyether film, the measurement error is ～ 1.5%.     

Thermal Response and Oxidation of Tyranno™-Fiber-Reinforced Si-Ti-C-O Matrix Composites for a Thermal Protection System in High-Enthalpy Dissociated Air

The thermal response and oxidation of Tyranno™ Lox-M fiber-reinforced Si-Ti-C-O matrix composites in high-enthalpy dissociated air was investigated in an arc jet facility (an arc wind tunnel). The maximum surface temperature reached 1310–1670°C. Catalytic recombination of oxygen and nitrogen on the composite surface under dissociated air was not significant. Surface recession was insignificant below 1600°C surface temperatures and above 5 kPa of oxygen partial pressure at the stagnation point. Passive-to-active oxidation transition of the composite agreed with Balat's theory for monolithic silicon carbide. A glass sealant prevented active oxidation of the composite for short-time exposures.     

Advantage of Sodium Polyoxyethylene Lauryl Ether Carboxylate as a Mild Cleansing Agent

Five anionic surfactants widely used in commercial skin cleansers were studied: sodium polyoxyethylene lauryl ether carboxylate (EC), sodium polyoxyethylene alkyl ether sulfate (ES), sodium dodecyl sulfate, potassium laurate, and N-cocoyl-l-glutamic acid monosodium salt. The amount of surfactant from aqueous solution adsorbed into the stratum corneum (SC), the degree of SC swelling, the change of the secondary structure of SC proteins (denaturation). The surface tension of surfactant–zein mixed solutions, and the solubilization behavior of zein were measured. Results showed that EC had the lowest adsorption into SC, the lowest SC swelling, and lowest denaturation of SC proteins. Low interactions between surfactants and SC proteins were also observed for EC/ES mixture solutions as well as. Mixing EC with ES good foaming performance. The EC/ES mixture, at about 1:1 ratio, is an excellent surfactant system for skin cleanser applications having cleansing characteristics and mildness to the skin.     

Synthesis and Sintering of Cerium(II) Monosulfide

Cerium monosulfide (CeS) powder was synthesized by the reduction of Ce₂S₃ powder with metallic Ce, which was obtained from ceria (CeO₂) powder using carbon disulfide (CS₂) gas. To obtain the maximum amount of CeS from a mixture of Ce₂S₃ and Ce, an excess amount of metallic Ce, a stoichiometric composition, was necessary in the synthesis at 1273 K for 10.8 ks. The preliminary sintering experiments also were performed using a synthetic CeS powder containing a small amount of Ce, Ce₂O₂S, and β-Ce₂S₃ as impurities. It was found that the oxygen content in the sintered compact decreases gradually as the sintering temperature increases, because of the removal of the impurities due to the evaporation of the volatile CeO. Single-phase CeS was formed by sintering at 2173 K. To evaluate the activation energy for densification of single-phase CeS, a CeS powder was prepared by milling an initial sintered compact and was used as an ingredient for hot-press experiments. Densification data during hot-press sintering were analyzed using a kinetic equation, showing that boundary diffusion is a rate-limiting process. The results suggest that this boundary diffusion model can explain well the densification data, with an apparent activation energy of 479 kJ·mol^-1.     

A Multiple‐Labeling Strategy for Nonribosomal Peptide Synthetases Using Active‐Site‐Directed Proteomic Probes for Adenylation Domains

Genetic approaches have greatly contributed to our understanding of nonribosomal peptide biosynthetic machinery; however, proteomic investigations are limited. Here, we developed a highly sensitive detection strategy for multidomain nonribosomal peptide synthetases (NRPSs) by using a multiple‐labeling technique with active‐site‐directed probes for adenylation domains. When applied to gramicidin S‐producing and ‐nonproducing strains of Aneurinibacillus migulanus (DSM 5759 and DSM 2895, respectively), the multiple technique sensitively detected an active multidomain NRPS (GrsB) in lysates obtained from the organisms. This functional proteomics method revealed an unknown inactive precursor (or other inactive form) of GrsB in the nonproducing strain. This method provides a new option for the direct detection, functional analysis, and high‐resolution identification of low‐abundance active NRPS enzymes in native proteomic environments.     

Oxidative Stress and Its Significant Roles in Neurodegenerative Diseases and Cancer

Reactive oxygen and nitrogen species have been implicated in diverse pathophysiological conditions, including inflammation, neurodegenerative diseases and cancer. Accumulating evidence indicates that oxidative damage to biomolecules including lipids, proteins and DNA, contributes to these diseases. Previous studies suggest roles of lipid peroxidation and oxysterols in the development of neurodegenerative diseases and inflammation-related cancer. Our recent studies identifying and characterizing carbonylated proteins reveal oxidative damage to heat shock proteins in neurodegenerative disease models and inflammation-related cancer, suggesting dysfunction in their antioxidative properties. In neurodegenerative diseases, DNA damage may not only play a role in the induction of apoptosis, but also may inhibit cellular division via telomere shortening. Immunohistochemical analyses showed co-localization of oxidative/nitrative DNA lesions and stemness markers in the cells of inflammation-related cancers. Here, we review oxidative stress and its significant roles in neurodegenerative diseases and cancer.     

Hydrostatic Pressure Influences HIF-2 Alpha Expression in Chondrocytes

Hypoxia-inducible factor (HIF)-2α is considered to play a major role in the progression of osteoarthritis. Recently, it was reported that pressure amplitude influences HIF-2α expression in murine endothelial cells. We examined whether hydrostatic pressure is involved in expression of HIF-2α in articular chondrocytes. Chondrocytes were cultured and stimulated by inflammation or hydrostatic pressure of 0, 5, 10, or 50 MPa. After stimulation, heat shock protein (HSP) 70, HIF-2α, nuclear factor kappa B (NF-κB), matrix metalloproteinase (MMP)-13, MMP-3, and vascular endothelial growth factor (VEGF) gene expression were evaluated. The levels of all gene expression were increased by inflammatory stress. When chondrocytes were exposed to a hydrostatic pressure of 5 MPa, HIF-2α, MMP-13, and MMP-3 gene expression increased significantly although those of HSP70 and NF-κB were not significantly different from the control group. In contrast, HIF-2α gene expression did not increase under a hydrostatic pressure of 50 MPa although HSP70 and NF-κB expression increased significantly compared to control. We considered that hydrostatic pressure of 5 MPa could regulate HIF-2α independent of NF-κB, because the level of HIF-2α gene expression increased significantly without upregulation of NF-κB expression at 5 MPa. Hydrostatic pressure may influence cartilage degeneration, inducing MMP-13 and MMP-3 expression through HIF-2α.