Evaluation for sintering of electrocatalysts and its effect on voltage drops in high-temperature proton exchange membrane fuel cells (HT-PEMFC)

Durability performance such as sintering and voltage drops of HT-PEMFC was theoretically evaluated under non-humid conditions at 150 °C, 170 °C and 190 °C. The quantum chemical molecular dynamics showed that the affinity of the platinum (Pt) electrocatalysts with carbon support decreased with increasing temperature. The degree of agglomeration of electrocatalysts over time simulated by three-dimensional kinetic Monte Carlo method was compared and quantitatively agreed with experimentally measured Transmission Electron Microscopy (TEM) results. Agglomeration of electrocatalysts due to the sintering caused losses of electrochemically active surface area, and found to be occurred more severe as temperature increased. Decreased rate of the proton conductivity due to the evaporation of phosphoric acid affected voltage drops as temperature increased. A theoretical breakdown of the voltage drops indicated that the voltage drops that occurred during the first several hundreds of hours and those occurring for the latter stage were due to different effects.     

A numerical simulation of pulverized coal combustion employing a tabulated-devolatilization-process model (TDP model)

A new coal devolatilization model employing a tabulated-devolatilization-process model (TDP model) is developed, and its validity is investigated by performing a numerical simulation of a pulverized coal combustion field formed by an industrial low-NO_x burner in a 100 kg-coal/h test furnace. The predicted characteristics of the pulverized coal combustion field obtained from the simulation employing the TDP model are compared with those employing the conventional devolatilization model, those employing the two competing reaction rate model, and the experiments. The results show that drastic differences in the gas flow patterns and coal particle behavior appear between simulations. In particular, the recirculation flow behavior is strongly affected by the difference in the coal devolatilization model because of the difference in the volatile matter evolution rate. The TDP model captures the observed behavior of the coal particles in the experiment better than the other models. Although it is considered that by adjusting the devolatilization parameters the prediction similar to the TDP model is also possible by the other models, appropriate devolatilization parameters are automatically set to particles depending on the particle heating rate without trial–error method by employing the TDP model.     

Triazolecarbaldehyde Reagents for One-Step N-Terminal Protein Modification

Site-specific modification of peptides and proteins is a key aspect of protein engineering. We developed a method for modification of the N terminus of proteins using 1H-1,2,3-triazole-4-carbaldehyde (TA4C) derivatives, which can be prepared in one step. The N-terminal specific labeling of bioactive peptides and proteins with the TA4C derivatives proceeds under mild reaction conditions in excellent conversion (angiotensin I: 92 %, ribonuclease A: 90 %). This method enables site-specific conjugation of various functional molecules such as fluorophores, biotin, and polyethylene glycol attached to the triazole ring to the N terminus. Furthermore, a functional molecule modified with a primary amine moiety can be directly converted into a TA4C derivative through a Dimroth rearrangement reaction with 1-(4-nitrophenyl)-1H-1,2,3-triazole-4-carbaldehyde. This method can be used to obtain N-terminal-modified proteins via only two steps: 1) convenient preparation of a TA4C derivative with a functional group and 2) modification of the N terminus of the protein with the TA4C derivative.     

Kinetics of property change associated with atmospheric humidity changes in alumina powder granules with PVA binder

A microcompression testing machine was used on single Al₂O₃ powder granules to study their stress–strain behavior as a function of relative humidity. The test granules were prepared by spray-drying slurries containing 3 mass% poly(vinyl alcohol) and Al₂O₃ powder. The stress–strain curves and granule strength were determined at regular time intervals, after step changes in atmospheric humidity. When stress was applied, deformation increased rapidly with the stress. This stress corresponded to the fracture strength of the granule. In a dry atmosphere, the granules deformed linearly with increasing stress, and a rapid change in strain was noted above a certain critical value of increased stress. In a wet atmosphere, the granules deformed continuously at lower stress. The mechanical properties of the granules changed rapidly with time when the atmospheric relative humidity was changed. Within 3 min of exposure to a new atmosphere, the mechanical properties of the granules reached equilibrium values. The change in properties with humidity was controlled by moisture diffusion in the granules and was reversible.     

Impedance of vapor feed direct methanol fuel cells—polarization dependence of elementary processes at the anode

Membrane electrode assemblies of direct methanol fuel cells (DMFCs) with different catalyst and ionomer loading were prepared. Anode performance and impedance spectra were measured to clarify the characteristics of vapor feed DMFCs (VF-DMFCs). The impedance spectra were deconvolved into three semi-circles with different time constants, each showing a different dependence on the anodic polarization. The middle-frequency range arc decreased as the anodic polarization increased, indicating that this process represents the oxidation reaction of methanol. The high-frequency range arc showed little dependence on the anodic polarization, but increased with the thickness of the electrode, indicating that this process might be related to proton conduction through the electrode. The low-frequency range arc was observed only when the methanol concentration was low, in contrast to liquid feed DMFCs (LF-DMFCs), for which the removal of the product gas presents a large resistance. A simpler design can therefore be used for a VF-DMFC, giving it an advantage over an LF-DMFC. A decreasing ionomer to catalyst ratio (I/C) caused the interfacial conductivity (σ_E) to increase, but it intensively decreased when I/C was below 0.25. Thus, the connection of the catalysts is important for the anode’s performance.     

Promotion Effect of Hydrogen on Grain Refinement in Pure Fe by High-Pressure Torsion-Straining

Metallurgical and Materials Transactions A - We revealed that hydrogen (H) in pure Fe promotes grain refinement during plastic deformation, which is caused by the increase in dislocation density by...     

Inhibition of Calcineurin and Glycogen Synthase Kinase-3β by Ricinoleic Acid Derived from Castor Oil

Ricinoleic acid (RA) is the main fatty acid component of castor oil and was found to inhibit Ca²⁺-signal transduction pathway-mediated cell cycle regulation in a yeast-based drug screening assay. RA is expected to have antidiabetic, antiallergy, and/or anticancer properties but its target molecule is unknown. To identify a novel pharmacological effect of RA, we investigated its target molecule in the Ca²⁺-signal transduction pathway. RA inhibition of calcineurin (CN) was examined in a yeast-based CN inhibitor screening assay using the rsp5^A401E mutant and in a phosphatase assay using recombinant human CN. RA showed growth-restoration activity at 5 μg/spot in the CN inhibitor screening assay with the rsp5^A401E yeast strain. Furthermore, it directly inhibited CN without immunophilins at K_i = 33.7 μM in a substrate-competitive manner. The effects of RA on CN in mammalian cells were further evaluated by measuring β-hexosaminidase (β-HEX) release in RBL-2H3 cells. RA at 50 μM suppressed the release of β-HEX from RBL-2H3 cells. Moreover, this compound was found to inhibit glycogen synthase kinase-3β (GSK-3β), as determined by a kinase assay using recombinant human GSK-3β. RA inhibited GSK-3β at K_i = 1.43 μM in a peptide substrate-competitive manner. The inhibition of GSK-3β by this molecule was further assessed in mammalian cells by measuring the inhibition of glucose production in H4IIE rat hepatoma cells. RA at 25 μM suppressed glucose production in these cells. These findings indicate that RA and/or castor oil could be a useful functional fatty acid to treat allergy or type 2 diabetes.     

Grain Growth During Hot Isostatic Pressing of Presintered Alumina

Grain growth during hot isostatic pressing is examined at 1373 to 1673 K at 5 to 200 MPa for 0.5 to 4 h on alumina presintered at 1723 to 1873 K. A linear relation is found between logarithms of grain size and porosity. To account for this result, the development of similar microstructures is suggested regardless of the histories of the starting powder and process. Temperature dependences of grain growth and densification must also be equal during hot isostatic pressing. Both grain growth and densification were controlled by the grain-boundary diffusion of the aluminum ions.     

Production of 8,11-cis-eicosadienoic acid by a Δ5 and Δ12 desaturase-defective mutant derived from the arachidonic acid-producing fungus Mortierella alpina 1S-4

The Δ5 and Δ12 desaturase (DS)-blocked mutants of an arachidonic acid-producing fungus, Mortierella alpina 1S-4, were obtained. These mutants accumulated 8,11-cis-eicosadienoic acid (20:2n-9). One of the mutants, M226-9, in which Δ5 and Δ12 DS are perfectly blocked, produced 1.68 mg of 20:2n-9 per mL of culture medium (101 mg/g dry mycelia) and no 5,8,11-cis-eicosatrienoic acid (20:3n-9) when grown in a medium containing 4% glucose and 1% yeast extract at 28°C for 2 d and then at 12°C for 12 d. The mycelial lipid comprised 77.4% triacylglycerol (TG) and 9.8% phosphatidylcholine (PC), among others. TG contained 69.0% of the total 20:2n-9, whose percentage in total TG fatty acids was 15.9%. The highest percentage (44.4%) of 20:2n-9 was found in PC. The addition of olive oil to the culture medium enhanced the production of 20:2n-9.