Synthesis of the Bi-2222 Compounds of Bi–Sr–Ln(Zr)–Cu–O (Ln = Sm,Eu, Gd,and Dy)

Bi-based superconducting compounds with the 2222 structure has been already synthesized in the Bi₂Sr₂- (Ln_1−x Ce _x )₂Cu₂O_10+y (Ln = Sm, Eu, and Gd) systems. One of the characteristics of these compounds is the existence of the fluorite-like (Ln_1−x Ce _x )₂O₂ block between two CuO₅ pyramids in the crystal structure. The tetravalent ions of Ce⁴⁺ are reported to be necessary to stabilize the 2222 structure. Recently, we have discovered that the Bi-2222 phase could be composed in the Bi₂Sr₂(Ln_2−x Zr _x )Cu₂O _z (Ln = Sm, Eu, Gd, and Dy) systems, where Zr⁴⁺ is used as a new tetravalent ion stabilizing the 2222 structure in stead of Ce⁴⁺. In the new system, nearly single 2222 phase samples have been obtained at the nominal composition of x=0.5 (Ln = Sm, Eu, and Gd) and in the range of 0.1≤x≤0.3 (Ln = Dy). Among them, the sample with Ln = Gd has the smallest resistivity at 273 K. But it is a semiconductor, and the conduction process at low temperatures is assumed to be followed by a two-dimensional VRH. The experimental results for the Gd samples with a partial substitution of Pb for Bi in the Bi₂Sr₂(Gd_2−x Zr _x )Cu₂O _z system are also reported.     

Electron beam nanoprocessing of a carbon nanotube film using a variable pressure scanning electron microscope

We demonstrate a novel method of processing carbon nanotubes using a variable pressure scanning electron microscope. Lines were processed in a nanotube film by electron beam irradiation in oxygen gas and nitrogen gas. The processing mechanism can be explained in terms of gas ion sputtering and chemical reaction. In this experiment, the narrowest line width of 120 nm was achieved in a nitrogen atmosphere.     

Multivariate evaluation of prognostic determinants for renal cell carcinomas which are metastatic at initial diagnosis

To clarify the relative importance of clinicopathological factors potentially affecting the survival of individuals initially diagnosed as having metastatic renal cell carcinoma (RCC), univariate and multivariate analyses using Cox's proportional hazards model were performed for 111 RCC patients who were admitted to four hospitals in Nagoya, Japan, between 1978 and 1993. Survival time was calculated from the date of diagnosis to the date of death or the end of May, 1995. Nineteen factors (17 clinically applicable before treatment and 2 histological in nature) were included for assessment. Univariate analysis revealed that 10 of the total 19 factors were significantly associated with patient survival. Multivariate analysis found 7 factors to be statistically significant determinants. Survival was further evaluated by categorizing the patients into three groups according to the number of the 7 factors. These groups showed clearly different survivals (log-rank test, p < 0.0001), confirming the importance of the 7 factors as definite determinants. They should therefore prove to be of advantage for classifying metastatic RCC patients when designing clinical prospective studies of immunotherapy and chemotherapy.     

Effect of Compressive Stress in Tumor Microenvironment on Malignant Tumor Spheroid Invasion Process

In this study, we proposed an in vitro tumor model to simulate the mechanical microenvironment and investigate the effect of compressive stress on the invasion process of malignant tumors. It has been pointed out that the biomechanical environment, as well as the biochemical environment, could affect the transformation of cancer cell migration, invasion, and metastasis. We hypothesized that the solid stress caused by the exclusion of surrounding tissue could transform tumor cells from noninvasive to invasive phenotypes. Colorectal cell spheroids were embedded and cultured in agarose gels of varying concentrations to simulate the earliest stages of tumor formation and invasion. The spheroids embedded in gels at higher concentrations showed peculiar growth after 72 h of culture, and the external compressive loading imposed on them caused peculiar growth even in the gels at lower concentrations. In conclusion, the mechanical microenvironment caused the transformation of tumor cell phenotypes, promoting the growth and invasion of tumor cell spheroids.     

Radiation-induced polymerization of ethylene in a pilot plant. I. Bulk process

Radiation-induced bulk polymerization of ethylene was carried out with use of a pilot plant with a 10 liter reactor at pressures of 225–400 kg/cm², temperatures of 30–95°C, ethylene feed rates of 5–28 kg/hr, and dose rate of 3.8 × 10⁵ rad/hr. Characteristics of the process are mild polymerization conditions and capability of producing medium density polyethylene in powder form. The spacetime yield and molecular weight of polymer were in the range of 3.5 to 13.1 g/liter hr and 2.2 × 10⁴ to 14 × 10⁴, respectively. The space-time yield increased with mean residence time and 2.4 powders of pressure, and decreased with temperature. Molecular weight changed similarly with the reaction conditions. These results were consistent with those of the bench plant experiment and the scale effect was small. Polymer deposit to the reactor wall limited a period of continuous operation of the plant. The amount of deposited polymer was increased with the square of reaction time. The rate of polymer deposit was proportional to polymer concentration and to the cube of pressure. The polymer deposit cannot be solved in the bulk process.     

The MHD effect and its relaxation process on electric current in the electrolysis of ferricyanide reduction and ferrocyanide oxidation

The electrolytic reduction of ferricyanide and the electrolytic oxidation of ferrocyanide have been carried out with exposing the magnetic field of 1000 or 1800 gauss. The current clearly increased after the magnetic exposure. The maximum current was obtained when the magnetic flux directed in parallel with the surface of electrode. These are speculated in terms of magnetohydrodynamic mechanism. The current decrease caused by relaxation process was observed after the removal of magnetic flux. The relaxation time obtained was temperature-dependent. Therefore the values of apparent transition energy, E_trans, were determined from the Arrhenius' plots of relaxation time against temperature. The magnitude of E_trans was dependent on the concentration of ferricyanide or ferrocyanide, and the viscosity and the conductivity of electrolyte solution. The activation energy of viscosity of electrolyte solution was compared with E_trans. As a conclusion, it was suggested that E_trans may be influenced by the velocity of magnetohydrodynamic flow, which was controlled by the diffusion current in electrolysis and the viscosity of electrolyte solution.     

An application of Monte Carlo method to simulate disorders in polymer crystals

The Monte Carlo method is applied to polymer crystals of idealized linear chain molecules of 30 carbon atoms, and the unharmonic, large-amplitude, oscillations and the subsequent conformational disorders of the chains are investigated. A crystalline field that confines the chain is treated by the molecular field approximation, and assumed to be cylindrical in this work. A production type simulation is adopted taking into account rigorous statistical weights for each sample conformation. Both the rotational isomeric model and the continuous rotation model of chain conformation are considered. By averaging over 10⁴–8 × 10⁴ chains, mean-square end-to-end distance, fractions of gauche and trans states and a detailed distribution of internal rotation angle are obtained. The effects of temperature and pressure on the conformation of the chain in the crystals are also simulated.     

Oxidative coupling of methane over LaCoO3−δ-based mixed oxides

The catalytic activity of LaCoO_3–-based mixed oxides for the oxidative coupling of methane has been tested by TPR and cyclic reaction. Characterization has been done by XRD, TGA and Mössbauer spectrometry. It is likely that the perovskite-crystal structure containing hypervalent metal ions has an important role and that unique structural oxygen species in the perovskite contribute to the partial oxidation of methane.     

Decomposition of Carbon Dioxide to Carbon with Active Wustite at 300°C

Active wustite (FeδO, with a δ value of 0.98) was prepared by keeping normal wustite (δ value of 0.94) in a N₂ atmosphere at 300°C for 10 min. This reaction is given by (4δ₂–3)Fe_δ1O→(4δ₁–3)Fe_δ2O + (δ₂–δ₁)Fe₃O₄ where δ₁= 0.94 and δ₂= 0.98. The equation indicates that the normal wustite undergoes eutectoid decomposition into active wustite and stoichiometric magnetite (Fe₃O₄). Carbon dioxide (1.013 × 10⁵ Pa) was almost completely (100%) decomposed into carbon (zero valence) by the active wustite at the low temperature of 300°C, which was associated with the transformation of the active wustite into the stoichiometric magnetite. The internal pressure of the reaction cell eventually became a vacuum.     

Asymmetric organocatalysis of structurally well-defined chiral quaternary ammonium fluorides

Unique organocatalysis of both naturally occurring cinchona alkaloid-derived and purely synthetic chiral quaternary ammonium fluorides in synthetically useful stereoselective bond-forming reactions is overviewed. The development of this chemistry was initiated by the in situ generation of generally hygroscopic ammonium fluorides from the corresponding easy-to-handle ammonium salts in the presence of excess metal fluorides and their direct use for subsequent enantioselective reactions. On the other hand, chiral ammonium fluorides have been prepared by using ion-exchange resins and successfully applied as catalyst to various asymmetric bond formation reactions under homogeneous conditions. In addition, utilization of chiral quaternary ammonium bifluorides as organocatalysts in asymmetric synthesis is described, featuring their characteristic reactivity and selectivity.