Electron-Doping Mottronics in Strongly Correlated Perovskite

The discovery of hydrogen-induced electron localization and highly insulating states in d-band electron correlated perovskites has opened a new paradigm for exploring novel electronic phases of condensed matters and applications in emerging field-controlled electronic devices (e.g., Mottronics). Although a significant understanding of doping-tuned transport properties of single crystalline correlated materials exists, it has remained unclear how doping-controlled transport properties behave in the presence of planar defects. The discovery of an unexpected high-concentration doping effect in defective regions is reported for correlated nickelates. It enables electronic conductance by tuning the Fermi-level in Mott–Hubbard band and shaping the lower Hubbard band state into a partially filled configuration. Interface engineering and grain boundary designs are performed for H_xSmNiO₃/SrRuO₃ heterostructures, and a Mottronic device is achieved. The interfacial aggregation of hydrogen is controlled and quantified to establish its correlation with the electrical transport properties. The chemical bonding between the incorporated hydrogen with defective SmNiO₃ is further analyzed by the positron annihilation spectroscopy. The present work unveils new materials physics in correlated materials and suggests novel doping strategies for developing Mottronic and iontronic devices via hydrogen-doping-controlled orbital occupancy in perovskite heterostructures.     

An Active Carbon Catalyst Prevents Coke Formation from Asphaltenes during the Hydrocracking of Vacuum Residue

Active carbons were prepared by the steam activation of a brown coal char. The active carbon with mesopores showed greater adsorption selectivity for asphaltenes. The active carbon was effective at suppressing coke formation, even with the high hydrocracking conversion of vacuum residue. The analysis of the change in the composition of saturates, aromatics, resins, and asphaltenes in the cracked residue with conversion demonstrated the ability of active carbon to restrict the transformation of asphaltenes to coke. The active carbon that was richer in mesopores was presumably more effective at providing adsorption sites for the hydrocarbon free-radicals generated initially during thermal cracking to prevent them from coupling and polycondensing.     

Synthesis of ettringite from portlandite suspensions at various Ca/Al ratios

Synthesis of ettringite, Ca₆Al₂(OH)₁₂(SO₄)₃·26H₂O has been attempted in suspensions of portlandite, Ca(OH)₂ under CO₂-free condition, agitating by a magnetic stirrer for constant 3 h at room temperature. Al-sulfate hydrate, Al₂(SO₄)₃·(14–18)H₂O solution (0.01 M) was used for Al₂O₃ and SO₃ sources and appropriate amount of portlandite was mixed with the solution together with sucrose for boosting portlandite dissolution. The Ca/Al atomic ratio in suspensions was varied from 1.0 to 5.0 at intervals of 0.5. Run products were collected by filtration and washing and air-dried and evaluated by XRD, XRF, and RF-SEM. No ettringite formed at Ca/Al = 1.0, but ettringite began to form at Ca/Al = 1.5 and over. Measurement of pH of supernatants indicated pH 9.86 as a critical point of ettringite formation, and this mineral was always identified in a pH region above this point. Minute crystallites of ettringite were obtained up to 2 μm. The Yield of ettringite was suspended around 95 wt% as dry-base even in stoichiometric mixing due to the presence of portlandite remaining undissolved as relicts. As a consequence, no marked difference of the yield was found among Ca/Al 2.0 to 3.5 runs. The remaining portlandite was apt to decompose into crystalline calcite during the air-dry process. However, formation of amorphous calcite was estimated in some runs during this decomposition process. The text was submitted by the authors in English.     

Kinetic Study on the Hydrocracking Reaction of Vacuum Residue Using a Lumping Model

Based on the experimental hydrocracking of vacuum residue, a kinetic study using a lumping model was carried out to gain insight into the characteristics of catalytic reactions. The lumped species were the saturates, aromatics, resins, and asphaltenes (SARA) constituents in the residue (798 K⁺) fraction and gas, naphtha, kerosene, gas oil, vacuum gas oil, and coke in the products. The pyrite reaction favoring hydrocracking to lighter products was more temperature-dependent than that using a mixture of pyrite and active carbon. The kinetic study showed that the addition of active carbon to pyrite limited the transformation of resins to asphaltenes.     

Measurement of rotation of individual spherical particles in cohesive granulates

To explore dynamical processes in granular matter, we use a combination of 3D imaging and mechanical testing. We analyze structural changes using confocal microscopy while applying a compression load simultaneously. Fluorescently labeled polydisperse silica particles were hydrophobized with long alkyl chains and dispersed in an index-matching liquid. The particles show a weak attraction. Photobleaching the central plane of individual particles generates an optical anisotropy without changing particle interaction. In a series of 3D images, we follow trajectories and rotation of single particles. We focus on particle translation and rotation in dependency of the local volume fraction. During compression, restructuring happens predominantly in regions of low packing density. We show that rotation plays an important role and is hence a key parameter for explaining dynamical processes in granular systems.     

Nanowire of hexagonal gallium oxynitride: Direct observation of its stacking disorder and its long nanowire growth

The crystal structure of gallium oxynitride nanowire was investigated by using scanning transmission electron microscopy. Gallium oxynitride nanowire was directly observed to have a biphasic wurtzite and zinc-blende structure. There was a stacking disorder of several atomic layers between the two phases. The new biphasic nanowire formed due to the presence of Ni in starting material because its nitride has a zinc-blende structure whereas gallium oxynitride has the wurtzite structure. Crystal growth of gallium oxynitride nanowires was studied using seed crystals. Seed crystals and amorphous gallium oxide precursors were annealed under different ammonia flow rates to grow gallium oxynitride nanowires. The nanowires grew to length of 150 μm but they did not grow laterally when the ammonia flow rate was 50 mL/min.     

Reconnaissance report on geotechnical damage caused by a localized torrential downpour with emergency warning level in Kyushu,Japan

Kumamoto and Kogoshima prefectures are located in the southern Kyushu district of western Japan. In July 2020, a warm, humid air front triggered the delayed rains of the rainy season, resulting in torrential rains in many parts of Japan, especially in Kyushu. In particular, heavy downpours occurred in the southern Kyushu district on July 4th, causing severe damage to much of the infrastructure. Details could not be analyzed as usual because some branch office of local government were also damaged by floods. The spatial distribution of precipitation in the Kuma River basin, in the southern part of Kumamoto, was characterized by the uniformity of 400–500 mm on July 3rd and 4th. Finally, emergency warnings of torrential rain were issued for the southern Kumamoto and the northern Kagoshima Prefectures by Japan Meteorological Agency (JMA) at 4:50 a.m., July 4th, 2020. Then, the active rain front gradually shifted towards northern Kyushu. Again, torrential rain fell on northern Kyushu in the afternoon due to a stagnant rainy season front, and the JMA issued an emergency warning for a localized torrential downpour for parts of Fukuoka, Saga and Nagasaki prefectures at 4:30 pm. Gradually, the damage status involving geodisasters such as several types of slope failures, road subsidence, damage of the river levee was reported by local governments in each area where there had been emergency warnings.Based on the brief report of the pre-investigation team from the Kyushu branch of the Japan Geotechnical Society (JGS) in the first week after the disaster on July 4th, the geo-research teams investigated the following: 1) landslides; 2) damaged roads; 3) damaged river levees, and 4) any geotechnical infrastructures which were partially damaged and may be even more severely damaged by the next torrential rain. This reconnaissance report introduces the geological features in Kyushu, the analysis of precipitation distribution and geotechnical damages on the slope failures, road failures and river embankments based on reports obtained from July 4th to August 31st, 2020.     

Near-infrared fluorescence probes for enzymes based on binding affinity modulation of squarylium dye scaffold

We present a novel design strategy for near-infrared (NIR) fluorescence probes utilizing dye-protein interaction as a trigger for fluorescence enhancement. The design principle involves modification of a polymethine dye with cleavable functional groups that reduce the dye's protein-binding affinity. When these functional groups are removed by specific interaction with the target enzymes, the dye's protein affinity is restored, protein binding occurs, and the dye's fluorescence is strongly enhanced. To validate this strategy, we first designed and synthesized an alkaline phosphatase (ALP) sensor by introducing phosphate into the squarylium dye scaffold; this sensor was able to detect ALP-labeled secondary antibodies in Western blotting analysis. Second, we synthesized a probe for β-galactosidase (widely used as a reporter of gene expression) by means of β-galactosyl substitution of the squarylium scaffold; this sensor was able to visualize β-galactosidase activity both in vitro and in vivo. Our strategy should be applicable to obtain NIR fluorescence probes for a wide range of target enzymes.     

Bottom-up synthesis of carbon materials with high pyridinic-nitrogen content from dibenzacridine isomers with zigzag and armchair edges

Journal of Materials Science - Nitrogen-doped carbon materials, especially pyridinic nitrogen, have attracted attention because of the high performance for various applications such as electrodes...