Synthesis and Self‐Assembly of Cyclic 2,7‐Anthrylene Ethynylene 1,3‐Phenylene Ethynylene Trimer with a Planar Conformation

Cyclic arylene ethynylene hexamer 1 , composed of alternating 2,7‐anthrylene ethynylene units and meta‐phenylene ethynylene units, was synthesized. It shows C₃ symmetry and possesses a flat and rigid conformation with a large equilateral triangle‐like cavity. Macrocycle 1 self‐associates through π–π stacking interactions between the anthracene‐containing macrocyclic aromatic cores with indefinite‐association constant K_E=6980 m ^?1 in CDCl₃ at 303 K. Macrocycle 1 also self‐assembles into π‐stacked nanofibers in the drop‐cast film.     

Evolution of long-period stacking order (LPSO) in Mg97Zn1Gd2 cast alloys viewed by HAADF-STEM multi-scale electron tomography

We have studied three-dimensional (3D) structures and growth processes of 14H-type long-period stacking order (LPSO) formed in Mg₉₇Zn₁Gd₂ cast alloys by single tilt-axis electron tomography (ET) using high-angle annular dark-field scanning transmission electron microscopy. Evolution of the solute-enriched stacking faults (SFs) and the 14H LPSO by ageing were visualised in 3D with a high spatial resolution in multi-scale fields of views from a few nanometres to ~10 μm. Lateral growth of the solute-enriched SFs and the LPSO in the (0?0?0?1)_Mg plane is notable compared to the out-of-plane growth in the [0?0?0?1]_Mg direction. The 14H LPSO grows at the cost of decomposition of the (Mg, Zn)₃Gd-type precipitates, and accompany a change of in-plane edge angles from 30 to 60°. We have updated the Time–Temperature–Transformation diagram for precipitation in Mg₉₇Zn₁Gd₂ alloys: starting temperatures of both solute-enriched SFs and LPSO formation shifted to a shorter time side than those in the previous diagram.     

Dynamic recording of a digital hologram with single exposure by a wave-splitting phase-shifting method

The wave-splitting phase-shifting digital holography using a pixelated microretarder array is proposed. By using four intensity images recorded by the pixelated microretarder array, Stokes parameters of the incident wave can be calculated. The fully complex amplitude distribution of the object wave can be obtained by using Stokes parameters, if the polarization states of the object and reference waves are linear and orthogonal. Two sets of experimental results are provided to verify the feasibility of the proposed method. One is the result for a movie recording using a CW laser and the other is the result for instant recording using a single pulsed laser.     

Abnormal Li diffusion in β-LiGa by the formation of defect complex

The diffusion coefficients of Li in the NaTl-type Li intermetallic compound of β-LiGa have been measured by using a short-lived radioactive diffusion tracer. As the tracer, the α-emitting radioisotope of ⁸Li delivered as the energetic and pulsed beam from Tokai Radioactive Ion Accelerator Complex (TRIAC) was implanted into the β-LiGa compounds with the composition in the range of about 43 to 54 at.% Li. By analyzing the time-dependent yields of the α-particles measured according to the repetition cycle of the beam, the tracer diffusion coefficients were extracted over the wide range of Li composition. Abnormal composition-dependence of Li diffusion coefficients in β-LiGa was observed; the stoichiometric β-LiGa showed the highest diffusivity of Li. By referring to the composition-dependent diffusivity of Li in the iso-structural β-LiAl and β-LiIn, we could identify the abnormal diffusion of Li in very Li-poor composition of β-LiGa. The anomaly has been discussed qualitatively in terms of the formation of defect complex and the interaction between the constitutional defects.     

Mechanistic action of ferric oxide in the hydrosilylation of 1,6-divinyl(perfluorohexane) with trichlorosilane

In the hydrosilylation of 1,6-divinyl(perfluorohexane) (FDV) with trichlorosilane (TCS) in the presence of catalytic chloroplatinic acid (Pt-Cat) under an air atmosphere (0.99 MPa), a runaway reaction accompanied by a severe pressure release occurred when Fe₂O₃ was present as an impurity in the system. In this study, we investigated the mechanism of action of Fe₂O₃ on this hydrosilylation by monitoring the thermal behavior of TCS/FDV/Pt-Cat/Fe₂O₃ mixtures with various compositions, using an accelerating rate calorimeter (ARC). In the case of TSC/FDV/Pt-Cat, a typical hydrosilylation composition in the industrial process, heat release, possibly due to hydrosilylation, began at 90 °C. On the other hand, for TCS/FDV/Pt-Cat/Fe₂O, the heat release due to hydrosilylation was hardly observed, but abrupt heat and pressure releases occurred at higher temperatures (>170 °C). Like TCS/FDV/Pt-Cat/Fe₂O₃, TCS/FDV, which contain neither Pt-Cat nor Fe₂O₃, released heat and pressure at high temperatures (>210 °C), while the heat and pressure release rates were comparatively low. From these results, the runaway reaction may occur when hydrosilylation is prevented, and Fe₂O₃ behaves as a negative catalyst for hydrosilylation. In the FT-IR spectrum of TCS/FDV/Pt-Cat/Fe₂O₃ after heating, an absorption peak at approximately 1,710 cm^?1, which may be attributed to a carbonyl group, was observed. Thus, it is considered that the runaway reaction observed during the hydrosilylation results from the action of Fe₂O₃ as a negative catalyst for hydrosilylation as well as as an oxidation catalyst for the by-product generated from the reaction between TCS and FDV.     

Thermal behavior and dismantlability of adhesives containing various inorganic salts

As a fundamental study on the development of dismantlable adhesives containing chemically reactive materials, the thermal behavior and dismantlability of an epoxy adhesive containing one of the twenty-seven inorganic salts (chlorides, perchlorates, and nitrates) were observed. In the thermal behavior measured by the differential scanning calorimetry, epoxy adhesives with inorganic salts containing iron, copper, zinc, and aluminum cations released heats of reaction at lower temperatures than the adhesive alone or the adhesives with other inorganic salts. Since such inorganic salts were considered to be effective candidates as fillers in dismantlable adhesives, the adhesion strengths of their mixtures with the adhesive were observed after heat aging at 270 °C for 30 min. The results showed that both chloride and perchlorate salts specifically decreased the adhesion strength after heating. On the other hand, the effect of nitrate salts on the decrease in adhesion strength was low in comparison with the chloride and perchlorate salts.     

A Synthetic Method for Preparing 3,3-Dialkyl-1,2,3,8-tetrahydroazulen-1-one

The trimethylsilyl enol ether of l-acetylcyclohepta-1,3,5-triene was transformed to 3,3-dialkyl-1,2,3,8-tetrahydroazulen-1-one by a two-step sequence involving the Mukaiyama aldol reaction with ketones and the subsequent Nazarov cyclization.