Molybdenum‐Catalyzed Stereospecific Deoxygenation of Epoxides to Alkenes

Mild and simple catalytic systems consisting of molybdenum(VI) dichloride dioxide [MoO₂Cl₂] as a catalyst and a phosphine as reductant have been developed for the stereospecific deoxygenation of epoxides to alkenes. The reactions using 1,2‐bis(diphenylphosphino)ethane (dppe) and triphenylphosphine (PPh₃) proceed with retention and inversion of stereochemistry, respectively. The mild reaction tolerates the presence of various functional groups and affords stereodefined substituted olefins in good yields.

     

An overheating‐tolerant space vector modulation algorithm for multilevel inverters

As promising and suitable candidates for high‐power applications, multilevel inverters have become one of the most promising solutions in various applications. However, power switching devices are highly subjected to thermal overheating, which leads to shortened lifetime and reduced reliability. Thermal overheating may result from the degradation of power switching devices due to continuous overloading and power cycling. In addition, degradation and faults in the cooling system of power switching devices may cause thermal stresses as well. A new overheating‐tolerant space vector modulation algorithm is proposed in this paper to alleviate thermal stresses from overheated power switching device. The proposed algorithm relies on using the redundancy property between switching states in multilevel inverters to continuously evaluate a cost function of the junction temperature of the overheated device for all possible switching sequence sets and then selects the optimal switching sequence. In addition, the proposed algorithm preserves the DC‐link capacitor voltage without reduction in the output current of the inverter. The proposed algorithm is general, which can be applied to n‐level inverters. Both simulation and experimental results reveal the efficient performance of the proposed algorithm using a three‐level T‐type inverter as a case study. Accordingly, the lifetime and reliability of the inverter are enhanced considerably using the proposed algorithm. © 2016 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Navigation behavior based on self-organized spatial representation in hierarchical recurrent neural network

ABSTRACT

A cognitive map is an internal model of the external world and contains the spatial representation of the surrounding environment. The existence of the cognitive map was first identified in rats; rats can navigate to their desired destination using cognitive maps while dealing with environmental uncertainty. We performed a mobile robot navigation experiment where obstacles were randomly placed using hierarchical recurrent neural network (HRNN) with multiple timescales. The HRNN was trained to navigate the mobile robot to the destination indicated by a snapshot image. After the training, the HRNN was able to successfully avoid the obstacles and navigate to the destination from any location in the environment. Analysis of the internal states of the HRNN showed that the module with fast timescale handles obstacle avoidance and the one with slow timescale has spatial representation corresponding to the spatial position of the destination. Moreover, in the experiment wherein the novel path appeared, the trained HRNN performed shortcut behavior. The shortcut behavior shows that the HRNN performed navigation using the self-organized spatial representation in the slow recurrent neural network. This indicates that training of goal-oriented navigation, i.e. the navigation motivated by a snapshot image of the destination results in the self-organization of cognitive map-like representation.     

Deoxidation of Ti Melt by Newly Developed Two-Step Plasma Arc Melting Process Using Hydrogen

Metallurgical and Materials Transactions B - A two-step plasma arc melting process, comprising a first step under Ar-30 pct H2 gas flow and the second step under Ar gas flow, has been...     

Selective nonanal molecular recognition with SnO2 nanosheets for lung cancer sensor

SnO₂ nanosheets were developed to detect nonanal gas in the order of ppb which was a marker of lung cancer. The nanosheets showed higher resistance change in nonanal gas than that in carbon monoxide (CO), nitrogen dioxide (NO₂), acetone (CH₃COCH₃), hydrogen (H₂), ethanol (C₂H₆O), ammonia (NH₃), hydrogen sulfide (H₂S), formaldehyde (HCHO), acetaldehyde (CH₃CHO), or butanal (C₄H₈O). Crystal surfaces of the nanosheets would be effective for adsorption of nonanal molecules. Furthermore, it was shown that resistance changed with an increase in carbon number in aldehyde. The nanosheets had molecular selectivity for a series of aldehyde molecules. Molecular recognition of the nanosheets gave us a great advantage to detect nonanal gas which was produced by lung cancer.     

Production of hyaluronic‐acid‐based cell‐enclosing microparticles and microcapsules via enzymatic reaction using a microfluidic system

This article describes the preparation of cell‐enclosing hyaluronic acid (HA) microparticles with solid core and microcapsules with liquid core through cell‐friendly horseradish peroxidase (HRP)‐catalyzed hydrogelation. The spherical vehicles were made from HA derivative possessing phenolic hydroxyl moieties (HA‐Ph) cross‐linkable through the enzymatic reaction by extruding cell‐suspending HA‐Ph aqueous solution containing HRP from a needle of 180 μm in inner diameter into the ambient coaxial flow of liquid paraffin containing H₂O₂ in a microtubule of 600 μm in diameter. By altering the flow rate of liquid paraffin, the diameters of gelatin and HA‐Ph microparticles were varied in the range of 120–220 μm and 100–300 μm, respectively. The viability of the enclosed human hepatoma HepG2 cells in the HA‐Ph microparticles of 180 μm in diameter was 94.2 ± 2.3%. The growth of the enclosed HepG2 cells was enhanced by decreasing the HRP concentration. The microcapsules of 200 μm in diameter were obtained by extruding HA‐Ph aqueous solution containing thermally liquefiable cell‐enclosing gelatin microparticles of 150 μm in diameter using the same microfluidic system. The enclosed cells grew and filled the cavity within 10 days. Spherical tissues covered with a heterogeneous cell layer were obtained by degrading the microcapsule membrane using hyaluronidase after covering the surface with a heterogeneous cell layer. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43107.     

Impact of Serum Chemerin Levels on Liver Functional Reserves and Platelet Counts in Patients with Hepatocellular Carcinoma

Obesity-related metabolic abnormalities, including adipokine imbalance and chronic inflammation, are involved in liver carcinogenesis. Chemerin, a novel adipokine, plays a critical role in adipogenesis, energy metabolism, and inflammation. We evaluated the impact of serum chemerin levels on liver functional reserves in hepatocellular carcinoma (HCC) patients and on the recurrence and prognosis of HCC. This study included 44 patients with any stage of HCC who underwent curative treatment at Gifu Municipal Hospital (Gifu, Japan) between 2006 and 2007. Recurrence-free survival and overall survival were estimated using the Kaplan-Meier method. Serum albumin levels (Pearson’s correlation coefficient; r = 0.3110, p = 0.0399), platelet counts (r = 0.4159, p = 0.0050), and prothrombin times (r = 0.3775, p = 0.0115) were significantly correlated with serum chemerin levels in patients with HCC, and they were inversely correlated with Child-Pugh scores (r = −0.3732, p = 0.0126), serum alanine aminotransferase levels (r = −0.3864, p = 0.0105), and total bilirubin levels (r = −0.4023, p = 0.0068). Among these variables, a multiple comparison test identified that platelet counts and total bilirubin levels were associated with serum chemerin levels (p < 0.0083). No significant correlation was found between serum chemerin levels and recurrence-free survival (p = 0.3691) or overall survival (p = 0.7916). In HCC patients, serum chemerin concentrations were correlated with liver functional reserves and platelet counts, but not with recurrence or prognosis.     

Colorless polyimides with low coefficient of thermal expansion derived from alkyl‐substituted cyclobutanetetracarboxylic dianhydrides

Alkyl‐substituted cyclobutanetetracarboxylic dianhydrides (CBDAs) were synthesized by photo‐dimerization of alkyl‐substituted maleic anhydrides to obtain novel colorless polyimides (PIs). Dimethyl‐substituted CBDA (DM‐CBDA) showed much higher polymerizability with various diamines than conventional cycloaliphatic tetracarboxylic dianhydrides and led to high molecular weights of PI precursors. Polyaddition of non‐substituted CBDA and trans‐1,4‐cyclohexanediamine (t‐CHDA) was completely inhibited by salt formation in the initial reaction stage. The use of DM‐CBDA allowed the formation of a homogeneous/viscous PI precursor solution by overcoming the salt formation problem. The prominent substituent effect probably reflects how the methyl substituents of DM‐CBDA contributed to increasing the salt solubility. Some of the thermally imidized DM‐CBDA‐based systems simultaneously possessed non‐coloration, low coefficient of thermal expansion (CTE), very high T_g exceeding 300 °C and very low dielectric constant. Copolymerization was very effective for improving the solubility of DM‐CBDA‐based PIs. The copolyimide cast films prepared via chemical imidization displayed a further decreased CTE without sacrificing other target properties, suggesting that the present materials can be useful as plastic substrates in display devices. The mechanism of self‐chain orientation behavior during solution casting is also discussed. A potential application of the copolyimide systems as optical compensation film materials in liquid crystal displays is proposed. © 2013 Society of Chemical Industry .     

Prediction of residual stress distributions due to surface machining and welding and crack growth simulation under residual stress distribution

In nuclear power plants, stress corrosion cracking (SCC) has been observed near the weld zone of the core shroud and primary loop recirculation (PLR) pipes made of low-carbon austenitic stainless steel Type 316L. The joining process of pipes usually includes surface machining and welding. Both processes induce residual stresses, and residual stresses are thus important factors in the occurrence and propagation of SCC. In this study, the finite element method (FEM) was used to estimate residual stress distributions generated by butt welding and surface machining. The thermoelastic-plastic analysis was performed for the welding simulation, and the thermo-mechanical coupled analysis based on the Johnson-Cook material model was performed for the surface machining simulation. In addition, a crack growth analysis based on the stress intensity factor (SIF) calculation was performed using the calculated residual stress distributions that are generated by welding and surface machining. The surface machining analysis showed that tensile residual stress due to surface machining only exists approximately 0.2 mm from the machined surface, and the surface residual stress increases with cutting speed. The crack growth analysis showed that the crack depth is affected by both surface machining and welding, and the crack length is more affected by surface machining than by welding.     

Normal Spectral Emissivity Measurement of Molten Cu–Co Alloy Using an Electromagnetic Levitator Superimposed with a Static Magnetic Field

The normal spectral emissivity of molten Cu–Co alloy with different compositions was measured in the wavelength range of 780 nm to 920 nm and in the temperature range of 1430 K to 1770 K including the undercooled condition by an electromagnetic levitator superimposed with a static magnetic field. The emissivity was determined as the ratio of the radiance from a levitated molten Cu–Co droplet measured by a spectrometer to the radiance from a blackbody calculated by Planck’s law at a given temperature, where a static magnetic field of 2.5 T to 4.5 T was applied to the levitated droplet to suppress the surface oscillation and translational motion of the sample. We found little temperature dependence of the normal spectral emissivity of molten Cu–Co alloy. Concerning the composition dependence, the emissivity decreased markedly above 80 at%Cu and reached that of pure Cu, although its dependence was low between 20 at%Cu and 80 at%Cu. In addition, this composition dependence of the emissivity of molten Cu–Co alloy can be explained well by the Drude free-electron model.