Morphological phase behaviour under pressure of polycatenar mesogens with a perfluorinated moiety

Two polycatenar materials composed of a four-aromatic-ring core with a perfluorinated moiety attached in one terminal position through either butylene- or pentylene spacer groups, and three tetradecyloxy chains at the other end (abbreviated as 14PC₄F and 14PC₅F), were investigated to study the effect of pressure on the phase transition behaviour. A polarizing optical microscope equipped with a high pressure optical hot stage, was used for the purpose. The T vs. P phase diagrams of 14PC₄F and 14PC₅F were constructed in the pressure region up to 100 MPa. 14PC₄F showed the stable crystal (Cr₁)-columnar tetragonal (Col_tet)-smectic A (SmA)-columnar hexagonal (Col_h)-isoropic liquid (I) phase transition sequence under all pressures. 14PC₅F exhibited the phase sequence metastable crystal (Cr₂)-cubic (Cub)-Col_tet-SmA-I in a melt-cooled sample on heating under pressure. But when the melt-cooled Cr₂ sample was annealed at 52-54°C for 2-3 h, the stable crystal (Cr₁) was formed slowly, giving a stable Cr₁-Cub-Col_tet-SmA-I phase sequence. The temperature region of the stable cubic phase broadened with increasing pressure. Furthermore a new mesophase of 14PC₅F was pressure-induced between the I and SmA phases on cooling at pressures above about 16 MPa. Since the monotropic mesophase exhibited a texture very similar to that of the high temperature Col_h phase of 14PC₄F with planar orientation, the new phase was assigned at a high temperature columnar hexagonal phase of 14PC₅F.     

Xantholipin, a novel inhibitor of HSP47 gene expression produced by Streptomyces sp.

In the course of our screening program to identify inhibitors of HSP47 gene expression, we obtained a novel aromatic substance from Streptomyces sp. named Xantholipin. Its structure was determined based on physicochemical data of Xantholipin and its derivatives. The absolute configuration was also established by the modified Mosher's method.     

Microstructural change due to isochronal annealing in severely plastic-deformed commercial purity aluminium

Microstructural changes, such as the density of grain boundary (GB) and dislocation density, due to isochronal annealing in severely plastic-deformed commercial purity aluminium up to 523 K was evaluated using electrical resistivity measurements and scanning transmission electron microscopy. Eventually, the GB density decreases from about 7.2 × 10⁶ to about 2 × 10⁶ m^?1, whilst the dislocation density decreases from an initial value of around 1.3 × 10¹⁴ m^?2 down to around 4 × 10¹³ m^?2.     

Morphological phase behaviour under pressure of polycatenar mesogens with a perfluorinated moiety

Two polycatenar materials composed of a four‐aromatic‐ring core with a perfluorinated moiety attached in one terminal position through either butylene‐ or pentylene spacer groups, and three tetradecyloxy chains at the other end (abbreviated as 14PC₄F and 14PC₅F), were investigated to study the effect of pressure on the phase transition behaviour. A polarizing optical microscope equipped with a high pressure optical hot stage, was used for the purpose. The T vs. P phase diagrams of 14PC₄F and 14PC₅F were constructed in the pressure region up to 100 MPa. 14PC₄F showed the stable crystal (Cr₁)–columnar tetragonal (Col_tet)–smectic A (SmA)–columnar hexagonal (Col_h)–isoropic liquid (I) phase transition sequence under all pressures. 14PC₅F exhibited the phase sequence metastable crystal (Cr₂)–cubic (Cub)–Col_tet–SmA–I in a melt‐cooled sample on heating under pressure. But when the melt‐cooled Cr₂ sample was annealed at 52–54°C for 2–3 h, the stable crystal (Cr₁) was formed slowly, giving a stable Cr₁–Cub–Col_tet–SmA–I phase sequence. The temperature region of the stable cubic phase broadened with increasing pressure. Furthermore a new mesophase of 14PC₅F was pressure‐induced between the I and SmA phases on cooling at pressures above about 16 MPa. Since the monotropic mesophase exhibited a texture very similar to that of the high temperature Col_h phase of 14PC₄F with planar orientation, the new phase was assigned at a high temperature columnar hexagonal phase of 14PC₅F.     

Direct Synthesis of Chromium Perovskite Oxyhydride with a High Magnetic‐Transition Temperature

We report a novel oxyhydride SrCrO₂H directly synthesized by a high‐pressure high‐temperature method. Powder neutron and synchrotron X‐ray diffraction revealed that this compound adopts the ideal cubic perovskite structure with O^2?/H^? disorder. Surprisingly, despite the non‐bonding nature between Cr 3d t_2g orbitals and the H 1s orbital, it exhibits G‐type spin ordering at T_N≈380 K, which is higher than that of RCrO₃ (R=rare earth) and any chromium oxides. The enhanced T_N in SrCrO₂H with four Cr‐O‐Cr bonds in comparison with RCr³⁺O₃ with six Cr‐O‐Cr bonds is reasonably explained by the tolerance factor. The present result offers an effective strategy to tune octahedral tilting in perovskites and to improve physical and chemical properties through mixed anion chemistry.     

Highly Oxidized States of Phthalocyaninato Terbium(III) Multiple-Decker Complexes Showing Structural Deformations,Biradical Properties and Decreases in Magnetic Anisotropy

Presented here is a comprehensive study of highly oxidized multiple-decker complexes composed of Tb^III and Cd^II ions and two to five phthalocyaninato ligands, which are stabilized by electron-donating n-butoxy groups. From X-ray structural analyses, all the complexes become axially compressed upon ligand oxidation, resulting in bowl-shaped distortions of the ligands. In addition, unusual coexistence of square antiprism and square prism geometries around metal ions was observed in +4e charged species. From paramagnetic ¹H NMR studies on the resulting series of triple, quadruple and quintuple-decker complexes, ligand oxidation leads to a decrease in the magnetic anisotropy, as predicted from theoretical calculations. Unusual paramagnetic shifts were observed in the spectra of the +2e charged quadruple and quintuple-decker complexes, indicating that those two species are actually unexpected triplet biradicals. Magnetic measurements revealed that the series of complexes show single-molecule magnet properties, which are controlled by the multi-step redox induced structural changes.     

Liquid-phase Reductive Deposition as Novel Preparation Method for Highly Dispersive Nickel Catalysts

We have been developing the selective deposition method onto TiO₂ nanoparticles, named as the liquid-phase selective-deposition method, where TiO₂ plays a role of formation center of Ni nanoparticles as well as protection from the aggregative growth of the particles. The concept of this method is to well disperse and stabilize Ni nanoparticles on TiO₂ surface by specific adsorption of Ni precursory complexes and then heterogeneous nucleation on the adsorption sites. The particle size was decreased with increasing the amount of Zn added, thus the catalytically active Ni surface area was increased. The selective deposition onto TiO₂ surface and addition of Zn to the nanoparticle promoted the catalytic activity of Ni–Zn nanoparticle, e.g. the catalytic activity of Ni–Zn/TiO₂ was ca. 10 times higher than that of the unsupported Ni nanoparticles. Ni in the nanocomposite was assigned as metallic, although their surface was oxidized under the atmospheric condition, but Zn and B were deposited as their oxide.