Generation of Brønsted Acid Over Alumina-Supported Niobia Calcined at High Temperatures

Nb₂O₅/Al₂O₃ catalysts calcined at high temperatures exhibited the Brønsted acid property. A monolayer of niobic acid-like compound, which has distorted octahedral symmetry, was stabilized over 16 wt% Nb₂O₅/Al₂O₃ catalyst calcined at 1,173 K. The two-dimensional Nb–O–Nb network of stabilized niobic acid-like compound probably accounts for the generation of Brønsted acid.     

A Mutant D‐Fructose‐6‐Phosphate Aldolase (Ala129Ser) with Improved Affinity towards Dihydroxyacetone for the Synthesis of Polyhydroxylated Compounds

A mutant of D ‐fructose‐6‐phosphate aldolase (FSA) of Escherichia coli, FSA A129S, with improved catalytic efficiency towards dihydroxyacetone (DHA), the donor substrate in aldol addition reactions, was explored for synthetic applications. The k_cat/K_M value for DHA was 17‐fold higher with FSA A129S than that with FSA wild type (FSA wt). On the other hand, for hydroxyacetone as donor substrate FSA A129S was found to be 3.5‐fold less efficient than FSA wt. Furthermore, FSA A129S also accepted glycolaldehyde (GA) as donor substrate with 3.3‐fold lower affinity than FSA wt. This differential selectivity of both FSA wt and FSA A129S for GA makes them complementary biocatalysts allowing a control over donor and acceptor roles, which is particularly useful in carboligation multi‐step cascade synthesis of polyhydroxylated complex compounds. Production of the mutant protein was also improved for its convenient use in synthesis. Several carbohydrates and nitrocyclitols were efficiently prepared, demonstrating the versatile potential of FSA A129S as biocatalyst in organic synthesis.     

间歇过程的故障分析和互锁控制器综合的集成

Integration amongst various decision-making processes, such as planning, design, and operation is necessary to dynamic and flexible batch production. To achieve a batch production integration, utilization of common models used for various decision-making processes is an effective approach. From this point of view, a batch system common model as described by a Petri net is proposed. In this article, a fault diagnosis technique for batch processes is presented using information about fault propagation and the possibilities of integration of fault analysis and controller synthesis are discussed on the basis of the Petri net based common models.     

Controllable electrode activities of nano-carbon films while maintaining surface flatness by electrochemical pretreatment

A carbon film consisting nanocrystallites with mixed sp² and sp³ bonds formed by using the electron cyclotron resonance (ECR) sputtering method was studied with respect to the changes in characteristics caused by electrochemical pretreatment (ECP). Unlike glassy carbon, our sputtered nanocrystalline carbon film deposited at an acceleration voltage of 75 V (ECR-75 nano-carbon film) largely retained its surface flatness after the ECP. This robust surface could be caused by an increase of 42% in the sp³ carbon realized by increasing the acceleration voltage during sputtering. The electrode activity of ECR-75 nano-carbon film was improved for surface sensitive species including Fe^3+/2+ unlike the boron doped diamond (BDD) electrode. This is because a sufficient quantity of surface sp² bonds remained and because the introduction of surface oxygen-containing groups is more efficient than with the BDD electrode. With pretreated ECR-75 nano-carbon film, the peak potential of glutathione was reduced solely due to the increase in the surface hydrophilicity with a sufficient quantity of surface sp² bonds, thus achieving the lowest detection limit (0.4 μM) ever obtained with carbon electrodes. We also achieved the stable measurement of 30 μM of serotonin (20 times) without the electrode surface fouling found with other electrodes.     

Recent advance in catalysis for solving energy and environmental problems

Recent advances in catalysis for solving the energy and environmental problems are summarized. For these purposes, rapid conversion and selective reaction even under conditions deviating extremely from reaction stoichiometry must be indispensable requisites. In order to realize these requisites, changes in the state of catalyst surface during the reaction were studied, and the catalyst structures on which the optimum reaction performance occurs were determined. An ultra-rapid reforming of methane to syngas with a space–time yield (STY) of 25 000 mol/l h was achieved by using a Rh-modified Ni–Ce₂O₃–Pt catalyst in which the Rh played the role of portholes for hydrogen spillover and prevents coke deposition on the catalyst surface. As a result, a stable state of the catalyst and the high reaction rate were exhibited. A new catalyst composed of Cu–Zn–Cr–Al–Ga oxides modified with supported Pd exerted a high activity with a high STY of methanol, 6700 g/l h. The catalyst components, Pd and Ga, controlled the reduction state of the catalyst surface by their role on normal and inverse spillover of hydrogen, respectively. The methanol thus produced was then totally converted selectively on a metallosilicate catalyst containing Ga or Fe into an aromatics-lean gasoline using an STY of 1860 g/l h. Finally, non-linear reaction mechanism is used to explain the elimination of NO on metallosilicate catalysts under O₂-excess conditions.     

New catalytic technologies in Japan

Recent trends in R&D of catalytic technology in Japan (cleaner and more efficient production, environmental catalysts, and recycling processes) are overviewed and examples of recent achievements are listed. Examples are then described as zeolite-catalyzed organic reactions recently commercialized and expected to be commercialized: hydration of cyclohexene, synthesis of pyridine derivatives and gas-phase Beckmann rearrangement of cyclohexanone oxime. Finally, as an example of environmental catalysts, the NO_x storage–reduction type three-way automobile catalyst, is introduced.     

Measurement of Young’s Modulus and Poisson’s Ratio of Thermal Barrier Coating Based on Bending of Three-Layered Plate

Thermal barrier coatings (TBCs) are used to protect the hot sections of gas turbine engines and airplane engines. A TBC system comprises a substrate, bond coat, and TBC topcoat. The development of an accurate method for determining the Young’s modulus and Poisson’s ratio of TBC using a multilayered specimen is of importance. In this study, we applied the bending theory of a laminated plate to a three-layered material and proposed models to determine the Young’s modulus and Poisson’s ratio of the TBC layer using the bending strain of the TBC system specimen. Three methods were developed by utilizing (i) the coating biaxial strain, (ii) substrate biaxial strain, or (iii) coating and substrate biaxial strains. Subsequently, we determined appropriate dimensions of the specimen and span by using three-dimensional finite element analysis, and numerically verified the usefulness of the three proposed methods. However, the Young’s modulus and Poisson’s ratio determined using the multilayered specimen with a substrate are sensitive to experimental errors. Therefore, we evaluated the sensitivity of the three proposed methods to experimental error, and we determined the most insensitive method among them. Finally, we experimentally demonstrated the usefulness of this method.     

Experimental study on relationship between heat parameter and angular distortion

It is well known that weld residual stress and distortion should be controlled appropriately for structural integrity. Recently, it has become much more necessary to control weld distortion to highly improve manufacturing efficiency. Various studies on control of weld distortion had been conducted based on clarification of influential dominant factors for that. The influential dominant factors had been studied from a viewpoint of temperature distribution in plate thickness section. Without considering moving the weld heat source, the temperature distribution is controlled by weld heat input (Q_net) per weld length. Angular distortion, which is controlled by temperature distribution along the direction of plate thickness (h), is controlled by heat input parameter (Q_net/h²). However, it has recently become known that the conventional results cannot be applied to all welding processes because such processes are becoming more diversified. It is significant for more accurate control of angular distortion to investigate once again the relationship between the heat input parameter and angular distortion. In this study, a series of experiments on the relationship between heat input parameter and angular distortion are carried out. The effects of welding current and welding speed are investigated individually in both TIG and MAG welding. The difference between these welding methods is also investigated. Based on the result, the effects of them are discussed in relation to temperature distribution during welding. It is considered that angular distortion is affected by temperature distribution not only in plate thickness section but also along welding direction. So, angular distortion is not always controlled by only the conventional heat input parameter because the heat input parameter is proposed as the influential dominant factor for temperature distribution in plate thickness section. It is concluded that generation characteristics of inherent strain should be considered in relation to three-dimensional temperature distributions during welding for more accurate control of angular distortion.     

Crystallographic analysis for acicular ferrite formation in low carbon steel weld metals

Inclusions contributing to acicular ferrite nucleation were investigated from a crystallographic point of view in low carbon low alloy steelweld metals. The samples from electro slag welding (ESW) and submerged arc welding (SAW) deposits with various cooling rates were prepared in this study. In those samples, intragranular acicular ferrite formation was observed from inclusions. The inclusions contributing to acicular ferrite formation were of multi-phase type consisting of amorphous phase, spinel type and MnS. They were surrounded by a Ti-enriched layer. It was confirmed by selected area diffraction patterns and energy-dispersive X-ray spectrometer analyses that the Ti-enriched layer was TiO. The acicular ferrite had a Baker–Nutting orientation relationship with the TiO layer on the inclusion surface. The misfit was 3.0% at the interface between the acicular ferrite and TiO. Therefore, it is considered that TiO on the inclusion surface contributes to the heterogeneous nucleation of acicular ferrite by small lattice misfit. However, themorphologies of ferrite growth which nucleated from inclusions were different in both samples. Whereas the growth of ferrites nucleated from TiO was enough in ESW, the size of nucleated ferrite in SAW was a few hundred millimetres in size. In the early stage of nucleation from TiO, ferrite had small deviation from Kurdjumov–Sachs orientation relationship (K–S relationship) in both ESW and SAW. However, there was a difference in the growth stage of ferrite. The ferrite orientations were gradually changed to fit to the K–S relationship in ESW. On the other hand, the nucleated ferrite in SAW stopped growing and the newly nucleated ferrite which had K–S relationship prior to austenite was formed adjacently because of large super cooling due to small heat input.     

Supramolecular Nanofibers from Collagen-Mimetic Peptides Bearing Various Aromatic Groups at N-Termini via Hierarchical Self-Assembly

Self-assembly of artificial peptides has been widely studied for constructing nanostructured materials, with numerous potential applications in the nanobiotechnology field. Herein, we report the synthesis and hierarchical self-assembly of collagen-mimetic peptides (CMPs) bearing various aromatic groups at the N-termini, including 2-naphthyl, 1-naphtyl, anthracenyl, and pyrenyl groups, into nanofibers. The CMPs (R-(GPO)_n: n > 4) formed a triple helix structure in water at 4 °C, as confirmed via CD analyses, and their conformations were more stable with increasing hydrophobicity of the terminal aromatic group and peptide chain length. The resulting pre-organized triple helical CMPs showed diverse self-assembly into highly ordered nanofibers, reflecting their slight differences in hydrophobic/hydrophilic balance and configuration of aromatic templates. TEM analysis demonstrated that 2Np-CMP_n (n = 6 and 7) and Py-CMP₆ provided well-developed natural collagen-like nanofibers and An-CMP_n (n = 5–7) self-assembled into rod-like micelle fibers. On the other hand, 2Np-CMP₅ and 1Np-CMP₆ were unable to form nanofibers under the same conditions. Furthermore, the Py-CMP₆ nanofiber was found to encapsulate a guest hydrophobic molecule, Nile red, and exhibited unique emission behavior based on the specific nanostructure. In addition to the ability of CMPs to bind small molecules, their controlled self-assembly enables their versatile utilization in drug delivery and wavelength-conversion nanomaterials.