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A 98-year-old woman with aspiration pneumonia caused by vomiting was admitted to our hospital. Abdominal computed tomography and ultrasonography showed common bile duct dilation and occlusion of the gastrointestinal tract due to a large tumor in the duodenum. Aspiration pneumonia and hepatic failure led to the patient's death. Pathological autopsy showed an 11 × 6 × 2.5-cm polypoid tumor originating from the descending part of the duodenum and involving the common bile duct. Histological examination of the tumor showed mainly spindle cells but also some adenocarcinoma cells. Tumor cells, including spindle cells, were strongly positive for cytokeratin 7; therefore, sarcomatoid carcinoma originating from the duodenum was diagnosed. To the best of our knowledge, only 5 cases of sarcomatoid carcinoma originating from the duodenum have been reported, and they often show polypoid growth. The possibility of sarcomatoid carcinoma should be considered if such findings are noted.

Since the first 3b/cell (X3) NAND flash memory paper in ISSCC 2008 [1], market demand for applications using high-density low-cost flash memory such as tablets, smart phones, and SSDs, has increased rapidly. Various electronic devices already use X3 NAND. The use of all BL (ABL) architecture, advanced circuitry, and enhanced algorithms enables this work to achieve 18MB/s performance, allowing penetration of markets where 2b/cell (D2) NAND has been used. As NAND memory scales aggressively towards 10nm, achieving the same level of performance with X3 chips is increasingly difficult. This paper addresses challenges with improvements made over previous NAND generations to achieve high performance while maintaining a low fail-bit count (FBC) and cost savings from an improved architecture and tightly packed peripheral circuits. Air gap [2,3] technology further improves write throughput by reducing neighbor interference and WL RC. A toggle mode 400Mb/s I/O interface reduces system overhead and enhances overall performance.

α-Synuclein is the main component of Lewy bodies, the intraneuronal inclusion bodies characteristic of Parkinson’s disease. Although α-synuclein accumulation is caused by inhibition of proteasome and autophagy-lysosome, the degradation of α-synuclein inclusions is still unknown. Formation of Lewy body-like inclusions can be replicated in cultured cells by introducing α-synuclein fibrils generated in vitro. We used this cell culture model to investigate the autophagy of α-synuclein inclusions and impaired mitochondria. The intracellular α-synuclein inclusions immediately underwent phosphorylation and ubiquitination. Simultaneously they were encircled by an adaptor protein p62/SQSTM1 and directed to the autophagy-lysosome pathway in HEK293 cell line. Most phospho-α-synuclein-positive inclusions were degraded in 24 h, however, lysosomal dysfunction with bafilomycin A1 significantly affected their clearance. Moreover, inhibition of autophagy by Atg-5 siRNA treatment reduced the incorporation of α-synuclein inclusions into LC3-positive autophagosomes. Knockdown experiments demonstrated the requirement of p62 for α-synuclein autophagy. These results demonstrate that α-synuclein inclusions are preferred targets for p62-dependent autophagy. Next, we investigated the autophagic clearance of impaired mitochondria in α-synuclein inclusion-containing cells. Impaired mitochondria were almost completely eliminated after mitochondrial uncoupling even in the presence of α-synuclein inclusions, suggesting that mitochondrial clearance is not prevented by α-synuclein inclusions in HEK293 cells.

Ru{sub 3}(CO){sub 12}/1,10-phenanthroline catalyzes the carbonylation of allylic alkyl carbonates to give esters. The authors studied this reaction with various substrates at different CO pressures.

Aluminium nitride (AlN) thin films have been synthesized by evaporation of aluminium and simultaneous irradiation with nitrogen ions (ion-vapour deposition method). The substrate temperature has been kept at room temperature or 473 K and the kinetic energy of the incident nitrogen ion beam has been varied from 0.5 to 2.0 keV. The microstructure of the synthesized films has been examined by X-ray diffraction (XRD) and transmission electron microscopy (TEM). In the XRD patterns of films synthesized at both room temperature and 473 K the diffraction line indicating the AlN (100) plane can be discerned and the broad peak composed of two lines indicating the AlN(002) and AlN(101) planes is also observed. TEM observations reveal that the films synthesized at 473 K show a more highly crystallized structure rather than the films synthesized at room temperature. The intensity of the AlN(002) and AlN(101) planes is found to increase with decreasing nitrogen ion energy at the substrate temperature of 473 K. The present results suggest that the synthesis ofc-axis-oriented AlN films is feasible by controlling the substrate temperature and the incident ion energy.

Atomic force microscope images of fracture surfaces of soda-lime glass, barium-borosilicate glass, and fused silica, fractured in low vacuum and subsequently exposed to humid air are reported. The observations reveal that: (1) soda-lime glass fracture surfaces exposed to air develop swellings 50–70 nm high after three days, while vacuum-stored samples show protrusions 10 nm high; with continued exposure to humid air, these swellings disappear and cone-like structures are formed; (2) barium-borosilicate fracture surfaces exposed to air develop relatively small numbers of crystalline protrusions typically 65 nm high after 3 days, while no similar features are observed on vacuum-stored material; and (3) fused silica fracture surfaces exposed to humid air for 3 days show no significant surface features compared with vacuum-stored material. The nm-scale structures observed on air-exposed fractured surfaces of soda-lime silica and barium-borosilicate are attributed to interactions between alkali and/or alkaline-earth cations in the material and water from the air.

Amorphous carbon nitride (a-CN x ) deposited by reactive sputtering shows deformation, photoconductive behavior, and thermal radiation by visible light irradiation. In this study, we investigated these photoresponse behaviors of a-CN x . To obtain films with different bonding structures, the films were deposited at various temperatures from 473 to 873 K. A reduction in N/C ratio led to a decrease in C–N bonding fraction and an increase in graphite component. The optical band gaps decreased with increasing temperature. Under white light illumination, the surface temperature of a-CN x increased with the narrowing of the band gap owing to the conversion of photon energy primarily into thermal energy. On the photoconductivity and deformation, a nonlinear relationship to the band gap energy was observed. In addition, both these photoresponses showed opposite trends in relation to the deposition temperature. The photoinduced deformation was suppressed by increasing the graphite component and decreasing the C–N bonding fraction.

Amorphous carbon nitride (a-CN x ) films show photoinduced deformation under visible light illumination. To investigate the effect of nitrogen on this deformation, we compared the deformation of a-CN x films with that of nitrogen-free amorphous carbon films. The films were deposited on a rectangular ultrathin Si substrate to obtain the amount of deformation estimated from the bending curvature of the substrate. The amount of photoinduced deformation was increased by nitrogen incorporation. In the case of a nitrogen concentration (N/C) of 0.3, the deformation was under the detection limit of our apparatus. By detailed analysis of chemical bonding states, the amount of deformation was found to increase with increasing N/C ratio and N–sp3C/N–sp2C ratio, which increased with increasing nitrogen content. Furthermore, from the results of Fourier transform infrared spectroscopy, it is found that the photoinduced deformation occurred through the formation of triple bonds as the termination structures related to nitrogen and chain bonds.

The maternal effect is one of the important factors in mammalian growth in conjunction with the genetic effect. The present study investigated the prenatal maternal effect of a dam on the intrauterine craniofacial growth of a mouse fetus using embryo transfer and cephalometry. DDD/Qdj strain mouse embryos were transferred to four strains of recipient female mice (DDD/Qdj, C3H/Qdj, C57BL/Qdj, and DBA/1J Sea). Just after parturition cephalometric observation of the newborn offspring, which developed in the uteri of the four strains of dams, was performed and then the craniofacial size of the newborn offspring was calculated on the lateral cephalogram. Statistical analyses were performed to examine the correlation between the dam's weight and the craniofacial size of the newborn offspring, to test the significance of the effect of the dam's strain on the craniofacial size of the newborn offspring, and to evaluate the interstrain difference of the intrauterine craniofacial growth of the mouse fetuses.It was disclosed that there were a direct relation between the dam's weight and the craniofacial size of the newborn offspring, a significant effect of the dam's strain on the craniofacial size of the newborn offspring, and a significant interstrain difference in the craniofacial size of the newborn offspring after eliminating the effects of litter size and gestation period on the craniofacial size of the newborn offspring (DDD/QdjC3H/Qdj = C57BL/QdjDBA/1J Sea).Thus, it could be concluded that the four strains of dams affected differently the intrauterine craniofacial growth of the DDD/Qdj strain fetuses through each uterine condition, indicating that the dam's weight played an important role as one of the prenatal maternal effects on the intrauterine craniofacial growth of mouse fetuses.

Various transition-metal complexes including Group 7 and 8–10 metal carbonyls are highly active catalyst precursors for the photochemical carbonylation of alkyl iodides having β-hydrogens on saturated sp 3 -carbons at room temperature under 1 atm of carbon monoxide. Primary, secondary and tertiary alkyl iodides are smoothly carbonylated by this catalyst system without β-hydride elimination (dehydrohalogenation) to give the corresponding esters or amides in high yields. In employment of Mn 2 (CO) 10 as a catalyst, electrochemical carbonylation of alkyl iodides also occurred via generation of an anionic manganese carbonyl intermediate. Actually, anionic manganese carbonyl complexes (pentacarbonylmanganates) showed high catalytic activity for thermal carbonylation of alkyl iodides at room temperature under 1 atm of carbon monoxide without photo-irradiation and electrolysis. Mechanistic studies were performed with kinetics and ESR and it was suggested that the present photo-, electro- and thermal carbonylation would involve a non-chain radical mechanism.

The dichlorobis(triphenylphosphine)palladium (PdCl 2 (PPh 3 ) 1 )-tin(II) chloride (SnCl 2 ) system shows high catalytic activity for the reductive N-heterocyclization of various 2-nitrostyrene and N-(2-nitrobenzylidene)amine derivatives when employed at 100 o C for 16 h under 20 kg cm -2 of initial carbon monoxide pressure, to give the corresponding indole and 2H-indazole derivatives in good yield. For example, 2-phenylindole was obtained in 75% yield from the reductive N-heterocyclization of 2-nitrostilbene

The mechanism of CO 2 gasification of carbon catalyzed with alkaline earth catalyst (Ca, Sr, Ba) was investigated with pulsed reaction and temperature programmed desorption techniques using labeled CO 2 . Several reaction paths similar to those of alkali metals were observed in both the oxidation of the catalyst and the reduction of the catalyst. Dispersed alkaline earth metal oxide and metal oxide cluster or alkaline earth metal cluster containing a large amount of oxygen were the main surface species. The catalysts oxidation by CO 2 and reduction with carbon proceed on these sites but characteristic features of these sites were quite different between Ca and Ba or Sr

Co2(CO)8-catalyzed ring-opening carbonylation of oxiranes and oxetane smoothly proceeds with high regioselectivity under 1 atm of carbon monoxide at room temperature to give the corresponding β- and γ-siloxy amides in high yields, respectively. [(R3Si)2NR1R2]+[Co(CO)4]− is thought to be an active catalyst species and directs the high regioselectivity of the carbonylation.

The effect of the structural change of metallic glasses on fracture is studied by observing the fracture surfaces of as-cast and annealed Fe78B13Si9 metallic glasses on the nanometer scale using atomic force microscopy (AFM). X-ray diffraction (XRD) was applied in studying the structural change. Metallic glass ribbons were fractured by the tensile test machine at room temperature. In the as-cast specimens, the fracture surface displays a characteristic vein pattern macroscopically. AFM observations of the fracture surface of the as-cast specimen show nanometer-scale steps and grooves, suggesting that the fracture has occurred associated with plastic deformation. However, in the fracture surfaces of the specimens annealed at and above 723 K, AFM observations reveal many pyramid-like features, although the fracture surface is featureless macroscopically. The pyramid-like features appear to be crystallites produced during heating, because the XRD indicates a crystalline structure. Since the pyramid-like features are not observed in the original annealed surface, they are found to be formed by fracture. This suggests that the fracture of the specimens annealed above 723 K has occurred along the crystallite facets, i.e. a kind of cleavage fracture.

We report scanning tunneling microscope images of gold-coated fracture surfaces of soda lime glass and fused silica in the mirror region. The scans show a variety of nanometer scale features that are attributed to fracture phenomena at this scale. We find considerable similarity to the structures observed in regions of extensive crack branching (e.g., “mist”). The density of these features increases as one progresses away from the crack origin toward the mirror-mist boundary. Comparisons are made between soda lime glass and fused silica, revealing differences in the local deformation behavior of these two materials. Self-similarity of the observed structures is probed by measurements of the fractal dimension, Df, of the surfaces created in soda lime glass near the mirror-mist boundary, where we observe 2.17 > Df > 2.40.

Iron, cobalt, and ruthenium carbonyls show novel catalytic activities. The Fe(CO)5/S system is an excellent catalyst precursor for coal liquefaction using carbon monoxide/water, syngas/water, and carbon monoxide/alcohol as hydrogen sources. The carbonyl trinuclear ferrate/KOH/support system exhibits high catalytic activity with high selectivity for lower olefins in Fischer-Tropsch synthesis. Using Co2(CO)8/N-silylamine, a variety of cyclic ethers are smoothly carbonylated to give the corresponding siloxy amides. The Ru-catalyzed C-H bond activation of a variety of formyl groups is widely applicable for hydroamidation, hydroesterification, and hydroacylation of olefins using formamides, formates, and aldehydes, respectively. The Ru3(CO)12/carbon monoxide system is effective for deoxygenative transformation of oximes and nitroarenes. Ketoximes, amidoximes, and aldoximes are converted into ketimines, amidines, and aldimines, respectively. N-(2-Nitrobenzoyl)amide is converted into a quinazolinone derivative via a nitrene intermediate.

A 71-year-old Japanese male with myelodysplastic syndrome progressing to overt leukaemia and hepatocellular carcinoma developed dyspnea and urticaria immediately after infusion of platelet concentrate (PC). He exhibited an identical reaction following blood transfusion. Serum haptoglobin was undetectable. The patient was determined to be homozygous for Hp(del) by polymerase chain reaction (PCR). Antibody to haptoglobin was detected by enzyme-linked immunosorbent assay (ELISA) and Western blot analysis. No antibodies against human leucocyte antigen (HLA) or platelet-specific antigens were detected. Washed PC and washed red blood cells were effective in preventing the transfusion-related anaphylactoid reactions.

Thin films of microcrystalline CH3NH3PbX3 (X = halogen) as well as their mixed-halide crystals were fabricated by the spin-coating technique, and their optical properties were investigated. X-ray diffraction investigation revealed that CH3NH3PbBr3 − x Cl x (x = 0–3) were successfully formed on glass substrate self-assembly and oriented with the a-axis. Owing to due to their large exciton binding energy, these materials showed clear exciton absorption and free-exciton emission in the visible region at room temperature. Replacing Br with CI made it possible to control the band structure of these materials. As a result, the peak position of the exciton band shifted continuously towards blue region with increasing the CI content in the films.

A cemental tear is a pathologic condition in which a complete or incomplete separation of the cementum occurs along the root surface and is usually accompanied by a deep periodontal pocket. Past articles report that the incidence of cemental tears has usually been limited to 1 tooth per individual. We encountered a clinical case with cemental tears involving 14 teeth in 1 individual. Multiple cemental tears in 1 individual have not been previously described in the dental literature. We present the clinical and pathologic features of this rare case and suggest that the probable cause of multiple cemental tears is structural weakness of the cementum.

Proteolytic systems and the aggresome pathway contribute to preventing accumulation of cytotoxic aggregation-prone proteins. Although polyubiquitylation is usually required for degradation or aggresome formation, several substrates are processed independently of ubiquitin through a poorly understood mechanism. Here, we found that p62/SQSTM1, a multifunctional adaptor protein, was involved in the selective autophagic clearance of a non-ubiquitylated substrate, namely an aggregation-prone isoform of STAT5A (STAT5A_ΔE18). By using a cell line that stably expressed STAT5A_ΔE18, we investigated the properties of its aggregation and degradation. We found that STAT5A_ΔE18 formed non-ubiquitylated aggresomes and/or aggregates by impairment of proteasome functioning or autophagy. Transport of these aggregates to the perinuclear region was inhibited by trichostatin A or tubacin, inhibitors of histone deacetylase (HDAC), indicating that the non-ubiquitylated aggregates of STAT5A_ΔE18 were sequestered into aggresomes in an HDAC6-dependent manner. Moreover, p62 was bound to STAT5A_ΔE18 through its PB1 domain, and the oligomerization of p62 was required for this interaction. In p62-knockdown experiments, we found that p62 was required for autophagic clearance of STAT5A_ΔE18 but not for its aggregate formation, suggesting that the binding of p62 to non-ubiquitylated substrates might trigger their autophagic clearance.

Epigenetic mechanisms are essential for normal development and maintenance of tissue-specific gene expression patterns in mammals. Disruption of epigenetic processes can lead to altered gene function and malignant cellular transformation. Global changes in the epigenetic landscape are a hallmark of cancer. Methylation of cytosine bases in DNA provides a layer of epigenetic control in many eukaryotes that has important implications for normal biology and disease. DNA methylation is a crucial epigenetic modification of the genome that is involved in regulating many cellular processes. These include embryonic development, transcription, chromatin structure, X-chromosome inactivation, genomic imprinting, and chromosome stability. Consistent with these important roles, a growing number of human diseases including cancer have been found to be associated with aberrant DNA methylation. Recent advancements in the rapidly evolving field of cancer epigenetics have described extensive reprogramming of every component of the epigenetic machinery in cancer, such as DNA demethylation. Hypomethylation of the genome largely affects the intergenic and intronic regions of the DNA, particularly repeat sequences and transposable elements, and it is believed to result in chromosomal instability and increased mutation events. Therefore, we propose that R/G-chromosome band boundaries, which correspond with the early/late-switch regions of replication timing and a transition in relative GC content, correspond to "unstable" genomic regions in which concentrated occurrences of repetitive sequences and transposable elements including LINE and Alu elements are hypomethylated during tumorigenesis. In this review, we discuss the current understanding of alterations in DNA methylation composing the epigenetic landscape that occurs in cancer compared with normal cells, the roles of these changes in cancer initiation and progression, and the potential use of this knowledge in designing more effective treatment strategies.

NAND flash memories are now indispensable for our modern lives. The application range of the storage memory devices began with digital still cameras and has been extended to USB memories, memory cards, MP3 players, cell phones including smart phones, netbooks, and so on. This is because higher storage capacity and lower cost are realized through means of technology scaling every year. Emerging markets, such as solid-state drives (SSDs) and data-storage servers, require lower bit cost, higher program and read throughputs, and lower power consumption

Relaxin-3 is a neuropeptide belonging to the relaxin/insulin superfamily. Studies using rodents have revealed that relaxin-3 is predominantly expressed in neurons in the nucleus incertus (NI) of the pons, the axons of which project to forebrain regions including the hypothalamus. There is evidence that relaxin-3 is involved in several functions, including food intake and stress responses. In the present study, we generated relaxin-3 gene knockout (KO) mice and examined them using a range of behavioral tests of sensory/motor functions and emotion-related behaviors. The results revealed that relaxin-3 KO mice exhibited normal growth and appearance, and were generally indistinguishable from wild genotype littermates. There was no difference in bodyweight among genotypes until at least 28 weeks after birth. In addition, there were no significant differences between wild-type and KO mice in locomotor activity, social interaction, hot plate test performance, fear conditioning, depression-like behavior, and Y-maze test performance. However, in the elevated plus maze test, KO mice exhibited a robust increase in the tendency to enter open arms, although they exhibited normal performance in a light/dark transition test and showed no difference from wild-type mice in the time spent in central area in the open field test. On the other hand, a significant increase in the acoustic startle response was observed in KO mice. These results indicate that relaxin-3 is slightly involved in the anxiety-related behavior.

Hydrogenated amorphous carbon (a-C:H) films on a silicon substrate have been prepared from toluene vapour by an r.f. plasma chemical vapour deposition method. The effect of oxygen on the composition and the surface morphology in the a-C:H films has been studied by adding a small amount of oxygen during deposition. Raman spectroscopy showed that the ratio of the amount of sp 3 -bonded carbon to that of non-sp 3 -bonded carbon is increased by the oxygen addition. By IR absorption measurements, it was found that absorption by the stretching of sp 3 -bonded carbon and hydrogen atoms is increased with increasing amount of oxygen added. These results suggest that non-sp 3 -bonded carbon is removed by oxygen during deposition. By visible light absorption measurements, it was found that the optical energy gap decreased with increasing amount of oxygen added. Volume resistivity measurements show that the resistivity has decreased with increasing amount of oxygen added. These changes in the optical energy gap and the volume resistivity can be explained by the assumption that hydrogen in the films is removed by oxygen. Observations of the surface by atomic force microscopy revealed that the centre-line average roughness of the films was reduced to approximately one-ninth by oxygen additions. These results show that oxygen addition during deposition plays an important role in removing non-sp 3 -bonded carbon and creating a smoother surface.

Diamond particles have been synthesized on an abraded silicon substrate from a gas mixture of methane and hydrogen by hot filament chemical vapour deposition. The nucleation and growth process of the diamond particles have been studied by varying the deposition time. The intermediate layer between the diamond particle clusters and the substrate was observed by scanning electron microscopy of the films deposited for 60 and 120 min. By micro-IR absorption measurements, absorptions were detected between 2800 cm−1 and 3000 cm−1 for the intermediate layer, while for the diamond particle clusters little absorption was observed in the same region. Raman spectra from the intermediate layer displayed the broad peak lying between 1300 cm−1 and 1600 cm−1, indicating amorphous carbon. The intermediate layer was found to be a hydrogenated amorphous carbon (a-C:H) film. Atomic force microscopy (AFM) studies have been performed on the surfaces of films deposited for 30, 60 and 120 min. AFM observations revealed that the surface of the intermediate a-C:H layer in the films deposited for 60 min was covered with numerous protrusions and in the films deposited for 120 min these protrusions were developed to layered triangular pyramids. Several aggregates of triangular pyramids were found in the a-C:H layer, suggesting a precursor to the diamond particles. However, the surfaces of the films deposited for only 30 min were not covered with the protrusions, but were covered with particle-like features. It is proposed that a-C:H films are initially formed on the substrate and that diamond nuclei are created in the a-C:H films and grow to be diamond particles.

We report scanning tunneling microscope observations of fracture surfaces formed during catastrophic crack growth in three metallic glasses: Ni56Cr18Si22B4, Co69Fe4Ni1Mo2B12Si12, and Fe78B13Si9. Macroscopically, the first two glasses fail along a slip band formed during loading and display a characteristic, μm-scale pattern of vein-like ridges; in contrast, Fe78B13Si9 displays little slip prior to fracture, and its fracture surface shows a μm-scale chevron pattern of steps. STM observations of fracture surfaces of all three materials show nm-scale grooves. The grooves in Co69Fe4Ni1Mo2B12Si12 are especially prominent and display stepped edges which we attribute to the intersection of shear bands with the surface. STM observations of the vein-like features on Ni56Cr18Si22B4 also show stepped edges. We attribute the vein features to the interaction of adjacent crack fingers in which the material between adjacent fingers fails in plane stress. The origin of the grooves is uncertain, but may be due to other shear instabilities along crack fingers.

Ruthenium complex-catalyzed N-heterocyclization of 2-aminopyridines with vicinal-diols offers a novel synthetic method for various imidazo[1,2-a]pyridines. For example, the reaction of 2-amino-4-methylpyridine with 1,2-cyclohexanediol in the presence of a catalytic amount of RuCl2(PPh3)3 under reflux in diglyme for 24 h afforded 2-methyl-6,7,8,9-tetrahydropyrido[1,2-a]benzimidazole in 74% yield.

Activities of n-type solid metal oxide semiconductors for aerobic photo-oxidation of simple C1-C3 alkanes were examined at temperatures from ambient to ca. 550 K. Whereas the reaction with methane produced a small amount of methanal (4.7 μmol h−1) together with carbon dioxide, and selectivity for methanal was low (ca. 10% ), photo-oxidation of ethane with 0.25 g of zinc oxide at 493 K produced 84 μmol h−1 of ethanal with a high selectivity of ca. 75%. The reaction with propane under similar conditions gave 57 μmol h−1 of propanal and 56 μmol h−1 of acetone with a combined selectivity of over 75 % on carbon base. For these reactions UV irradiation was indispensable, and catalytic performances of zinc oxides depended greatly on their properties and preparation. The yields of the products were very small at ambient temperature, and increased with increasing temperature up to 500–550 K. The titanium oxide catalysts produced aldehydes and ketones from light alkanes, but in lower selectivities than the Zinc oxide catalysts.

Allylic carbonates except for allyl methyl carbonate reacted with carbonucleophiles such as ethyl acetoacetate in the presence of a catalytic amount of Ru(cod)(cot) [cod = cycloocta-1,5-diene, cot = cycloocta-1,3,5-triene] in N -methylpiperidine at 80°C to give the corresponding monoallylated carbonucleophiles in high yields with high regioselectivity. The regioselectivity was quite different from that in the palladium-catalyzed reactions. The allylation of carbonucleophiles using allyl methyl carbonate selectively gave the diallylated carbonucleophiles in high yields.

In order to elucidate a mechanism for exoelectron emission from metallic glasses during heat treatment, metallic glasses Fe40Ni38Mo4B18, which have a 140 K lower crystallization temperature than the metallic glasses Fe78B13Si9 reported previously, were heated up to 723 K with a constant heating rate of 0.5 K/s under ultrahigh vacuum condition. Although specimens were not excited by ionizing radiations, mechanical treatment, or chemical processes prior to measurements, exoelectrons have been detected for the first heating cycle. However, in the subsequent heating cycles, the counting rate does not exceed the background level. These results agree well with our previous report about metallic glasses Fe78B13Si9, but it is recently found that from the present glasses exoelectrons are emitted from the lower temperature region, and the total number of emitted exoelectrons is larger than that from the previous glasses. An atomic force microscopy (AFM) study reveals many crystallites formed on the surface of the heated specimen, and the spatial density of crystallites on the surface is much higher than that of previous glasses. Both results of exoelectron measurements and AFM observations show that the number of emitted exoelectrons increases with increasing the number of crystallites on the surface. This result implies that exoelectrons are emitted associated with the crystallites formation process on the surface.

Ru 3 (CO) 12 showed a high catalytic activity for the selective deoxygenation of aromatic and N -heteroaromatic amidoximes to the corresponding amidines at 80°C for 5 h under carbon monoxide pressure (5 kg cm −2 ). For example, the deoxygenation of benzamidoxime afforded benzamidine in 82% yield. Furthermore, the present deoxygenation reaction of amidoximes catalyzed by Ru 3 (CO) 12 was applied to the one-pot synthesis of pyrimidine derivatives. When the deoxygenation of amidoximes was carried out in the presence of 1,3-dicarbonyl compounds such as acetylacetone, acetylacetophenone, and ethyl acetoacetate, the corresponding pyrimidine derivatives, which were the condensation products of the generated amidines with 1,3-dicarbonyl compounds, were obtained in up to 93% yield.

Iron/sulfur-catalyzed liquefaction of Yallourn coal using alcohol-carbon monoxide has been investigated. Pentacarbonyliron (Fe(CO)5)/sulfur was found to be an excellent catalyst precursor. In the Fe(CO)5/sulfur catalyzed liquefaction (375 °C-120 min) of Yallourn coal, high conversion (99.5%) was achieved in the presence of ethanol and CO.

Pentacarbonyliron with sulfur was found to be an excellent catalyst precursor for liquefaction of Yallourn coal using syngas-water as a hydrogen source. Both the high coal conversion and well-balan...

In the presence of a catalytic amount of RuCl2(PPh3)3, various alkyl N-arylcarbamates are obtained in 23–82% yields by dehydrogenative reaction of N-aryl substituted formamides with alcohols. The present reaction offers an alternative method for phosgene- and carbon monoxide-free synthesis of carbamates.

The photoinduced oxidation of methane or ethane over zinc oxide based catalysts under UV irradiation at 500–550 K gives formaldehyde with high selectivity or acetaldehyde, respectively.

The selective photo-oxidation of ethane with oxygen is achieved usingMo/O 3 SiO 2 catalyst above 463 K. At 493 K, acetaldehyde is formed in the yield of 60 μmol/h along with 22 μmol/h of formaldehyde combined with the selectivity for aldehydes over 90%.

Rutherium complexes such as RU(COD)(COT) [COD = cyclooctadiene, COT = cyclooctatriene], catalyze the dehydrohalogenative coupling of vinyl halides with olefins to give the corresponding substituted dienes. Even the sp 2 -carbon-chloride bond of β-chlorostyrene is activated by ruthenium catalysts.

Indole derivatives were readily prepared from the reductive N-heterocyclization of o-nitrostyrene derivatives in the presence of a catalytic amount of PdCl2(PPh3)2–SnCl2 under carbon monoxide pressure (20 kg/cm2) at 100 °C for 16 h. With o-nitrostilbene, 2-phenylindole was obtained in 75% yield.

Allylamines react with acrylic compounds in the presence of Ru(cod)(cot) catalyst to give cyclobutane-β-amino acid derivatives in high yield (up to 85%); cod = cycloocta-1,5-diene, cot = cycloocta-1,3,5-triene.

Ru(cod)(cot) catalyzes highly selective codimerization of 1,3-dienes with acrylic compounds and first linear coupling reaction of allylic carbonates with the acrylic amide to give 3,5-dienoic acid derivatives; cod = cycloocta-1,5-diene, cot = cycloocta-1,3,5-triene.

Allylic carbonates except for allyl methyl carbonate reacted with carbonucleophiles such as ethyl acetoacetate in the presence of a catalytic amount of Ru(cod)(cot) [cod = cycloocta-1,5-diene, cot = cycloocta-1,3,5-triene] in N -methylpiperidine at 80°C to give the corresponding monoallylated carbonucleophiles in high yields with high regioselectivity. The regioselectivity was quite different from that in the palladium-catalyzed reactions. The allylation of carbonucleophiles using allyl methyl carbonate selectively gave the diallylated carbonucleophiles in high yields.

Ruthenium complex-catalyzed N-heterocyclization of 2-aminopyridines with vicinal-diols offers a novel synthetic method for various imidazo[1,2-a]pyridines. For example, the reaction of 2-amino-4-methylpyridine with 1,2-cyclohexanediol in the presence of a catalytic amount of RuCl2(PPh3)3 under reflux in diglyme for 24 h afforded 2-methyl-6,7,8,9-tetrahydropyrido[1,2-a]benzimidazole in 74% yield.

Co2(CO)8-catalyzed ring-opening carbonylation of oxiranes and oxetane smoothly proceeds with high regioselectivity under 1 atm of carbon monoxide at room temperature to give the corresponding β- and γ-siloxy amides in high yields, respectively. [(R3Si)2NR1R2]+[Co(CO)4]− is thought to be an active catalyst species and directs the high regioselectivity of the carbonylation.

The dichlorobis(triphenylphosphine)palladium (PdCl 2 (PPh 3 ) 1 )-tin(II) chloride (SnCl 2 ) system shows high catalytic activity for the reductive N-heterocyclization of various 2-nitrostyrene and N-(2-nitrobenzylidene)amine derivatives when employed at 100 o C for 16 h under 20 kg cm -2 of initial carbon monoxide pressure, to give the corresponding indole and 2H-indazole derivatives in good yield. For example, 2-phenylindole was obtained in 75% yield from the reductive N-heterocyclization of 2-nitrostilbene

A combination of the palladium complex PdCl2(PPh3)2 with MoCl5 shows a high catalytic activity for the intermolecular reductive N-heterocyclization of 2-nitrobenzaldehyde or 2-nitrophenyl ketones with formamide to give the corresponding quinazoline derivatives in moderate yields. For example, in the reaction of 2-nitrobenzaldehyde with formamide, quinazoline was obtained in 46% yield. We assume that the present reaction proceeds via an active nitrene intermediate which would be generated by selective deoxygenation of nitro group by carbon monoxide.

Ru{sub 3}(CO){sub 12}/1,10-phenanthroline catalyzes the carbonylation of allylic alkyl carbonates to give esters. The authors studied this reaction with various substrates at different CO pressures.