Nickel‐Catalyzed Suzuki–Miyaura Coupling of a Tertiary Iodocyclopropane with Wide Boronic Acid Substrate Scope: Coupling Reaction Outcome Depends on Radical Species Stability

We describe a nickel‐catalyzed Suzuki–Miyaura arylation of a tertiary iodocyclopropane with arylboronic acids; this is an efficient and convergent strategy for providing various enantioenriched arylcyclopropanes with a quaternary stereogenic center. This is the first metal‐catalyzed coupling between a tertiary alkyl electrophile and a wide range of aromatics, including heteroaromatics. We found that the outcome of the Ni‐catalyzed coupling with halides as electrophiles was dependent on the stability of the radical species formed during the reaction. The use of tert‐butyl alcohol (t‐BuOH) as the reaction solvent was very effective, because of its stability under the radical‐generating reaction conditions.

     

Dual-Function Semaphorin 4D Released by Platelets: Suppression of Osteoblastogenesis and Promotion of Osteoclastogenesis

Effects of the antiosteoblastogenesis factor Semaphorin 4D (Sema4D), expressed by thrombin-activated platelets (TPs), on osteoblastogenesis, as well as osteoclastogenesis, were investigated in vitro. Intact platelets released both Sema4D and IGF-1. However, in response to stimulation with thrombin, platelets upregulated the release of Sema4D, but not IGF-1. Anti-Sema4D-neutralizing monoclonal antibody (mAb) upregulated TP-mediated osteoblastogenesis in MC3T3-E1 osteoblast precursors. MC3T3-E1 cells exposed to TPs induced phosphorylation of Akt and ERK further upregulated by the addition of anti-sema4D-mAb, suggesting the suppressive effects of TP-expressing Sema4D on osteoblastogenesis. On the other hand, TPs promoted RANKL-mediated osteoclastogenesis in the primary culture of bone-marrow-derived mononuclear cells (BMMCs). Among the known three receptors of Sema4D, including Plexin B1, Plexin B2 and CD72, little Plexin B2 was detected, and no Plexin B1 was detected, but a high level of CD72 mRNA was detected in RANKL-stimulated BMMCs by qPCR. Both anti-Sema4D-mAb and anti-CD72-mAb suppressed RANKL-induced osteoclast formation and bone resorptive activity, suggesting that Sema4D released by TPs promotes osteoclastogenesis via ligation to a CD72 receptor. This study demonstrated that Sema4D released by TPs suppresses osteogenic activity and promotes osteoclastogenesis, suggesting the novel property of platelets in bone-remodeling processes.     

Novel High‐Temperature Antiferroelectric‐Based Dielectric NaNbO3–NaTaO3 Solid Solutions Processed in Low Oxygen Partial Pressures

The (1?x)NaNbO₃–(x)NaTaO₃ solid solution was investigated for x ≤ 0.4 in terms of new high‐temperature and high‐permittivity dielectric system that is suitable for base metal inner electrode capacitor applications. The addition of Ta significantly enhanced the resistivity of the dielectric, resulting in superior resistivity than the dielectrics‐formulated BaTiO₃ systems that dominate the multilayer ceramic capacitor dielectric devices. The voltage dependence of the permittivity was also superior to BaTiO₃‐based materials, providing higher capacitance at higher temperatures. A transmission electron microscopy study illustrated that the grains had so‐called core‐shell structure. According to the electron diffraction analysis, the core region had an inhomogeneous structure between antiferroelectric and ferroelectric phases, and shell region had an incommensurate ferroelectric‐like structure. The core and shell region had Nb‐ and Ta‐rich composition, respectively, and their interface was compositionally sharp, implying that shell region was formed via a liquid phase during the sintering process with an incongruent Ta dissolution reprecipitation. We anticipate that these or similar materials based on the alkali‐niobate perovskites can be further enhanced to provide capacitor solutions from 150°C to 250°C, which is an important range for a number of new AC–DC invertor and engine control units.     

不锈钢在扭转/拉伸复合载荷下近门槛值的疲劳裂纹扩展行为

研究了带环状预裂纹的奥氏体不锈钢圆棒试样在循环扭转／拉伸复合载荷下,门槛值附近的疲劳裂纹扩展行为,分析了复合加载时不同载荷比对裂纹扩展的影响,对裂纹扩展的初始阶段进行了详细研究,用应力强度因子表征了裂纹扩展开始的门槛值．提出了椭圆方程表达的疲劳裂纹扩展开始的门槛值模型,该方程可在裂纹尖端位移准则的基础上导出．疲劳裂纹扩展停止的门槛值条件也可用椭圆方程表达．     

Direct and Indirect Exciton Dynamics in Few‐Layered ReS2 Revealed by Photoluminescence and Pump‐Probe Spectroscopy

Atomically thin‐layered ReS₂ with a distorted 1T structure has attracted attention because of its intriguing optical and electronic properties. Here, the direct and indirect exciton dynamics of a three‐layered ReS₂ is investigated by polarization‐resolved transient photoluminescence (PL) and ultrafast pump‐probe spectroscopy. The various time scales of the decay signals of the time‐resolved PL (<10 ps), with monitoring of the populations of electron–hole pairs (exciton), and the transient differential reflectance (≈1 and 100 ps), with monitoring of the populations of electrons and/or holes in the excited states, are observed. These results reveal the characteristic exciton dynamics: rapid relaxation of direct excitons (electron–hole pairs) and slow relaxation of the momentum‐mismatched indirect excitons accompanied by a one‐phonon emission process. These findings provide important information regarding the indirect bandgap nature of few‐layered ReS₂ and its characteristic exciton dynamics, boosting the understanding of the novel electronic and optical properties of atomically thin‐layered ReS₂.     

Germanium recovery using polyphenol microspheres prepared by horseradish peroxidase reaction

BACKGROUND: The formation of polyphenol microspheres by the polymerization of 3‐methylcatechol was performed in a methanol/phosphate buffer solution using horseradish peroxidase (HRP), without the use of a surfactant or a water/oil interface, to be used for germanium recovery. RESULTS: The polyphenol microspheres were of diameter 1 mm. The functional group density of phenol group in the polymer was approximately 15 mol kg^?1 determined by the Folin‐Denis method. In batchwise experiments, the amount of germanium adsorbed was 0.23 mol kg^?1. CONCLUSION: Because germanium is a rare metal, a system for its recovery is required. Using the proposed system, continuous recovery of germanium can be achieved using multilayered microspheres. Copyright © 2011 Society of Chemical Industry     

Development of a new X-ray source using backscattered X-ray with the use of a cold cathode

The development of an intense X-ray source using backscattered X-ray produced using an advanced electrode configuration is described. The electrodes were composed of field emitters deposited on a wire mounted on a perforated plate as the cathode and a copper plate as the anode. Electrons from these emitters collided with the copper plate and X-ray was generated at collision points. The backscattered X-ray in the direction normal to the electron trajectory through a hole in the anode escaped from the vacuum chamber through a beryllium window. Continuous and characteristic X-rays were detected at an applied voltage lower than that of a conventional X-ray source from 3.0 to 9.4 kV, respectively. Moreover, the X-ray dosage measured with a survey meter reached 0.95 mSv/h at 5.0 kV of applied voltage. The transmission images of three types of material used as an X-ray source for the X-ray imaging system indicate three advantages; low power consumption, focal point controllable by adjusting applied voltage, and photographable motion picture of X-ray transmission.     

Novel circular-beam equalizing techniques that use graded-index fiber optics for a high-power laser diode

We demonstrate a novel method of equalizing a laser diode (LD) beam into a circular beam. This method uses the twist effect of graded index (GI) fiber optics. An asymmetric LD beam with beam qualities of M2 = 500 in the slow axis and M2 = 4 in the fast axis is converted successfully into a symmetric circular beam with a beam quality of M2 = 175. The circular-output beam with 92% coupling efficiency from the fiber input to the fiber output is obtained with a 5-m-long GI1200 (1200 means a core diameter of 1200 microm) fiber for a 2-W LD array. We extend the experiments to a higher-power source with higher asymmetric beam qualities of M2 = 3000 and M2 = 4. By slightly bending the GI10000 (10000 means a core diameter of 10,000 microm) fiber, we have succeeded in generating a symmetric beam with a improved beam quality of M2 = 2000. The average beam quality is preserved when the asymmetric ratio is not high, and the beam quality degradation ratio is investigated up to asymmetric ratios of 750.     

Structural evolution in Fe ion implanted Si upon thermal annealing

We have performed high-dose Fe ion implantation into Si and characterized ion-beam-induced microstructures as well as annealing-induced ones using transmission electron microscopy (TEM) and grazing-incidence X-ray diffraction (GIXRD). Single crystals of Si(1 0 0) substrate were irradiated at 623 K with 120 keV Fe⁺ ions to a fluence of 4 × 10¹⁷ cm⁻². The irradiated samples were then annealed in a vacuum furnace at temperatures ranging from 773 K to 1073 K. Cross-sectional TEM observations and GIXRD measurements revealed that a layered structure is formed in the as-implanted specimen with ε-FeSi, β-FeSi₂ and damaged Si, as component layers. A continuous β-FeSi₂ layer was formed on the topmost layer of the Si substrate after thermal annealing.