Measuring grain rotation at the nanoscale

In this paper, we introduced a method to measure grain rotation of nanomaterials under external stress using a high pressure diamond anvil cell and the Laue microdiffraction technique at a synchrotron facility. We used tungsten carbide marker crystals to investigate grain rotation activities of 3 and 500?nm nickel media. Our results show that the grain rotation of 3 and 500?nm nickel nanocrystals increase with pressure and finally rotation of 500?nm nickel tends to stop at a lower pressure/stress level than 3?nm nickel. 3?nm nickel nanocrystals show a higher rotation magnitude than 500?nm nickel nanocrystals. Our measurements show an effective method to study the grain rotation of nanomaterials especially in ultrafine nanocrystals.     

An asymptotic approximation for EPMC in linear discriminant analysis based on two-step monotone missing samples

In this paper, we consider the expected probabilities of misclassification (EPMC) in the linear discriminant function (LDF) based on two-step monotone missing samples and derive an asymptotic approximation for the EPMC with an explicit form for the considered LDF. For this purpose, we also provide some results of the expectations for the inverted Wishart matrices in this paper. Finally, we conduct the Monte Carlo simulation for evaluating our result.     

Metal insulator transition characteristics of macro-size single domain VO2 crystals

The metal insulator transition (MIT) characteristics of macro-size single-domain VO₂ crystal were investigated. At the MIT, the VO₂ crystal exhibited a rectangular shape hysteresis curve, a large change in resistance between the insulating and the metallic phases, in the order of ～10⁵, and a small transition width (i.e. temperature difference before and after MIT) as small as 10^?3°C. These MIT characteristics of the VO₂ crystals are discussed in terms of phase boundary motion and the possibility of controlling the speed of the phase boundary, with change in size of crystal, is suggested.     

Observation of insulating–insulating monoclinic structural transition in macro‐sized VO2 single crystals [Phys. Status Solidi RRL 5, No. 3, R107–R109 (2011)]

In our article, we reported the observation of monoclinic M2 to M1 structural phase transition in VO₂ single crystal near the temperature of ～49 °C. However, the re‐examination of Laue patterns reveals that previously defined monoclinic M1 and M2 phases can be interpreted as monoclinic M2 and triclinic T phases instead. Careful experimental geometry calibration and further refinement of the lattice parameter ratios and angles show that monoclinic M2 and triclinic T phases fit better with the experimental data. On the other hand, our previous misidentification of the insulating phases does NOT affect the conclusions of our article. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Development of Rapid and Facile Solid-Phase Synthesis of PROTACs via a Variety of Binding Styles

Optimizing linker design is important for ensuring efficient degradation activity of proteolysis-targeting chimeras (PROTACs). Therefore, developing a straightforward synthetic approach that combines the protein-of-interest ligand (POI ligand) and the ligand for E3 ubiquitin ligase (E3 ligand) in various binding styles through a linker is essential for rapid PROTAC syntheses. Herein, a solid-phase approach for convenient PROTAC synthesis is presented. We designed azide intermediates with different linker lengths to which the E3 ligand, pomalidomide, is attached and performed facile PROTACs synthesis by forming triazole, amide, and urea bonds from the intermediates.     

Conformational transition of copolymer of maleic acid and styrene in aqueous solution. III

Kinetic studies of the pH-induced conformational transition of the hydrophobic copolyelectrolyte of maleic acid and styrene in aqueous NaCl at ionic strength 0.09 were performed by an optical method at 25.0°C with a rapid reaction analyzer of high resolving power. A pH jump applied to a solution, in which the molecule is in the compact form, gives a kinetic trace from which, by appling the general kinetic theory of cooperative transitions, two mean relaxation times are determined. Plots of these relaxation times against the degree of ionization of the primary carboxyl groups of the maleic acid units agree well with theoretical predictions from the linear Ising model, where the molecule in the compact form is described as a random coil with hydrophobic “pockets.” The initiation parameter for a pocket obtained from the kinetic data is 0.036. On the other hand, the parameter calculated from the previous pH-titration results by applying Zimm–Rice theory is 0.015 at the ionic strength 0.09 and 25.0°C. Such values are compared with those determined from pH-titration data on other hydrophobic polyelectrolytes.     

Synthesis of thiophene derivatives via palladium-catalyzed coupling reactions

Thiophene derivatives with multiple substitutions are prepared from vinylidene bromide, which is synthesized by the reaction of thiophene-2-carboxaldehyde with carbon tetrabromide in the presence of PPh₃, as a core molecule through several coupling reactions such as Suzuki-Miyaura coupling and palladium-catalyzed CH arylation. The reactions with a wide variety of organic halides lead to a series of substituted thiophene derivatives in moderate to good yields.     

Observation of insulating–insulating monoclinic structural transition in macro‐sized VO2 single crystals

VO₂ single crystals with unprecedented quality, exhibiting a first‐order metal–insulator transition (MIT) at 67.8 °C and an insulator –insulator transition (IIT) at ～49 °C, are grown using a self‐flux evaporation method. Using synchrotron‐based X‐ray microdiffraction analysis, it is shown that the IIT is related to a structural phase transition (SPT) from the monoclinic M2 phase to the M1 phase upon heating while the MIT occurs together with a SPT of M1 to the rutile R phase. All previous reports have shown that VO₂ exists in the M1 phase at room temperature in contrast to the M2 phase observed in this work. We suggest that internal strain inside single crystal VO₂ may generate the previously unobserved IIT and the unusual room temperature structure. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Comparison of radioactive and stable cesium uptake in aquatic macrophytes affected by the Fukushima Dai-ichi Nuclear Power Plant accident

Concentrations of ^134+137Cs and ¹³³Cs in aquatic macrophytes, water, and sediment were measured in samples collected from Fukushima Prefecture, Japan. The concentrations of ¹³⁷Cs in submerged and floating-leaved plants were higher than the values for emergent plants according to their main Cs uptake mode. The geometric mean water-to-plant concentration ratio for ¹³⁷Cs and ¹³³Cs was comparable observed in submerged and floating-leaved plants, while the geometric mean sediment-to-plant concentration ratio for ¹³⁷Cs in emergent plants was higher than that of ¹³³Cs, which suggest that the mobility of Fukushima accident-derived ¹³⁷Cs is not in steady state 4–5 years after the accident.