Catalytic Aerobic Photo‐oxidation of a Methyl Group on a Heterocycle to Produce an Aldehyde via Homolytic C?I Bond Cleavage caused by Irradiation with Visible Light

A new catalytic method was developed for photo‐oxidizing the methyl group on aromatic heterocycles such as benzothiazole, benzoxazole, and quinoline to produce the corresponding aldehyde. This is the first report of the metal‐free catalytic synthesis of benzothiazole‐2‐carboxaldehydes using molecular oxygen as the terminal oxidant.

     

Site‐Selective Iron(III) Chloride‐Catalyzed Arylation of 4‐Aryl‐4‐methoxy‐2,5‐cyclohexadienones for the Synthesis of Polyarylated Phenols

The iron(III) chloride‐catalyzed Friedel–Crafts arylation of 4‐aryl‐4‐methoxy‐2,5‐cyclohexadienones, which were easily prepared by the phenyliodine(III) diacetate (PIDA)‐mediated oxidation of 4‐arylphenols in methanol, proceeded site‐selectively to form meta‐terphenyl (2,4‐diarylphenol) derivatives in good yields. The subsequent PIDA‐mediated oxidation and iron(III) chloride‐catalyzed Friedel–Crafts arylation of the resulting products gave the corresponding 2,4,6‐triarylphenol derivatives. The present method provides useful highly substituted polyarylated compounds.

     

Depassivation-repassivation behavior of a pure iron surface investigated by micro-indentation

Depassivation-repassivation behavior on a pure iron surface in borate buffer solution was examined under potentiostatic control by a micro-indentation test. Current peaks emerge during both downward and upward drives of the indenter due to depassivation which is caused by plastic deformation of the substrate but not elastic deformation and repassivation. The total electric charge of the current peaks is proportional to the maximum load. The total electric charge also increases with increase in intermission time of the indentation, indicating that the passive film is ruptured even during stress relaxation. It is estimated from the electric charge balance that 82% and 18% of the film rupture occurs during the downward drive and intermission, respectively, and that no rupture occurs during the upward drive. Furthermore, the film-ruptured area is estimated to be 80% of the plastic deformed surface area. The partial retainment of the passive film on iron suggests that the ductility of the passive film is higher than that of the substrate.     

Structural Investigation of the Binding of 5‐Substituted Swainsonine Analogues to Golgi α‐Mannosidase II

Golgi α‐mannosidase II (GMII) is a key enzyme in the N‐glycosylation pathway and is a potential target for cancer chemotherapy. The natural product swainsonine is a potent inhibitor of GMII. In this paper we characterize the binding of 5α‐substituted swainsonine analogues to the soluble catalytic domain of Drosophila GMII by X‐ray crystallography. These inhibitors enjoy an advantage over previously reported GMII inhibitors in that they did not significantly decrease the inhibitory potential of the swainsonine head‐group. The phenyl groups of these analogues occupy a portion of the binding site not previously seen to be populated with either substrate analogues or other inhibitors and they form novel hydrophobic interactions. They displace a well‐organized water cluster, but the presence of a C(10) carbonyl allows the reestablishment of important hydrogen bonds. Already approximately tenfold more active against the Golgi enzyme than the lysosomal enzyme, these inhibitors offer the potential of being extended into the N‐acetylglucosamine binding site of GMII for the creation of even more potent and selective GMII inhibitors.     

Functional analysis of genes encoding putative oxidoreductases in Aspergillus oryzae, which are similar to fungal fructosyl-amino acid oxidase

We found 11 genes (FAO1-11) encoding putative oxidoreductases in the Aspergillus oryzae genome, which are similar to fungal fructosyl-amino acid oxidases. The cDNAs corresponding to the genes were cloned and expressed in Escherichia coli. rFao2 had fructosyl-amino acid oxidase activity, whereas rFao1 did not show any enzyme activity, even though the deduced amino acid sequence of Fao1 is identical to that of one of the fructosyl-amino acid oxidase isozymes from Aspergillus oryzae. rFao7 and rFao8 showed oxidase activity toward sarcosine, L-pipecolate, and L-proline. rFao10 was active toward only sarcosine, of the substrates tested. The functions of the other proteins were also predicted from a phylogenetic analysis.     

Estimation of concentrations of antifungal agents allowed as food additives in foods and their daily intake based on official inspection results in Japan in fiscal year 1998

The mean concentrations and daily intake of four antifungal agents were estimated based on the results of an analysis of 7,005 samples of food obtained in official inspections by Japanese local governments in fiscal year 1998. The mean concentration of diphenyl was 0.0004% of the allowable limit, and those of imazalil, o-phenylphenol, and thiabendazole were 14.0%, 3.5%, and 5.7%, respectively. The daily intakes of these antifungal agents per person, estimated from their concentrations and the daily consumption of the foods, were 0.000326, 1.89, 11.5, and 23.3 micrograms, respectively, and assuming a body weight of 50 kg, the amounts of these antifungal agents consumed were 0.000013%, 0.15%, 0.12%, and 0.47% of the acceptable daily intake, respectively. These values are similar to the values obtained on the basis of the results of the official inspection in fiscal years 1994 and 1996, except that the amount of diphenyl is much lower (1/100).     

Detection of CpG Methylation in G-Quadruplex Forming Sequences Using G-Quadruplex Ligands

Genomic DNA methylation is involved in many diseases and is expected to be a specific biomarker for even the pre-symptomatic diagnosis of many diseases. Thus, a rapid and inexpensive detection method is required for disease diagnosis. We have previously reported that cytosine methylation in G-quadruplex (G4)-forming oligonucleotides develops different G4 topologies. In this study, we developed a method for detecting CpG methylation in G4-forming oligonucleotides based on the structural differences between methylated and unmethylated G4 DNAs. The differences in G4 topologies due to CpG methylation can be discriminated by G4 ligands. We performed a binding assay between methylated or unmethylated G4 DNAs and G4 ligands. The binding abilities of fluorescent G4 ligands to BCL-2, HRAS1, HRAS2, VEGF G4-forming sequences were examined by fluorescence-based microtiter plate assay. The differences in fluorescence intensities between methylated and unmethylated G4 DNAs were statistically significant. In addition to fluorescence detection, the binding of G4 ligand to DNA was detected by chemiluminescence. A significant difference was also detected in chemiluminescence intensity between methylated and unmethylated DNA. This is the first study on the detection of CpG methylation in G4 structures, focusing on structural changes using G4 ligands.     

Gas analysis of the CVD process for high yield growth of carbon nanotubes over metal-supported catalysts

Changes in the gas composition during the methane chemical vapor deposition growth of single- and double-walled carbon nanotubes over metal-supported MgO catalysts were investigated in an attempt to increase the nanotube yield. Monitoring the gas composition by gas chromatography as a function of the reaction time provides information on the activity and lifetime of the catalyst. The degree of methane decomposition, i.e., the C-H bond dissociation, was closely related to the nanotube yield, and the Fe-Mo binary catalyst exhibited a high activity. The effects of water vapor on the catalytic nanotube growth were also studied by introducing water vapor in the inlet gas. An appropriate amount of water prolonged the lifetime of the catalyst and increased the nanotube yield by 35%.     

Structural Distortion and Compositional Gradients Adjacent to Epitaxial LiMn2O4 Thin Film Interfaces

Thin film electrode materials are key components in the development of high rate, high capacity solid‐state Li‐ion batteries. Detailed knowledge of the epitaxial film/substrate(current‐collector) interface structures, which provides insights into epitaxial growth mechanisms and the effects of microstructure on electrochemical properties, is essential for efficient materials and device design. Here we report the epitaxial growth mechanism of a typical cathodic LiMn₂O₄ thin film by exploring the detailed structural and compositional variations in the vicinity of a film/substrate interface using state‐of‐the‐art scanning transmission electron microscopy. Direct observation of atom columns shows the epitaxial film forms an atomically flat and coherent heterointerface with the substrate, but that the crystal lattice is tetragonally distorted with a measurable compositional gradient from the interface to the crystal bulk. The growth mechanism is interpreted in terms of a combination of chemical and physicomechanical effects, namely a complex interplay between the internal Jahn‐Teller distortions induced by oxygen non‐stoichiometry and the lattice misfit strain.     

High-pressure studies on Tc and crystal structure of iron chalcogenide superconductors

The superconducting transition temperature, T_c, in iron-based solids can be enhanced by applied pressure: T_c increases from 8 to 37 K for the 11-type FeSe when the pressure is raised from 0 to 4 GPa. High-pressure studies can elucidate the mechanism of superconductivity in such novel materials. In this paper, we present a high-pressure study of Fe(Se_1−xTe_x) and Fe(Se_1−xS_x). In the case of Fe(Se_1−xTe_x), the maximum T_c under high pressure did not exceed the T_c of FeSe, which can be attributed to the structural transition to the monoclinic phase. For Fe(Se_1−xS_x) (0 < x < 0.3), T_c exhibited a significant increase with pressure; however, the maximum T_c under high pressure did not exceed the T_c of FeSe. This may be due to the disorder induced by substituting S for Se, which is similar to the pressure effect on T_c for the 1111-type superconductor Ca(Fe_1−xCo_x)AsF. The T_c of Fe(Se_1−xS_x) showed a complex behavior below 1 GPa, first decreasing and then increasing with increasing pressure. From high-pressure x-ray diffraction measurements, the T_c (P) curve was correlated with the local structural parameter.