Metal-Induced Structural Switching of a Folded Quinone-Sandwiched Porphyrin

We report the synthesis of a novel quinone-sandwiched porphyrin in which two benzoquinones are connected oppositely at the meso positions of a porphyrin through rigid 3-amido 2,2′-bipyridine linkers. ¹H-NMR and single crystal X-ray analyses revealed that the quinone-sandwiched porphyrin has a folded structure in which the porphyrin unit was inserted into the two quinone moieties via π-stacking. Insertion of a Zn(II) ion into the porphyrin center induced a drastic conformational change which is resulted in coordination of the oxygen atoms of both benzoquinone moieties to the Zn-porphyrin to afford a 6-coordinated structure.     

Alloy design of a cost-effective and castable heat-resistant iron alloy

A new heat-resistant Fe-based cast alloy has been designed making the best use of the CALPHAD method. The objective was to replace the material for precision cast products made from Ni-based superalloys with improved Fe-based alloys originally developed for lower temperature applications.The key to the design is to balance the amount of strengthening ${\gamma }^{\prime }$- Ni₃(Ti,Al) precipitates and brittle $\sigma$ phase, and to simultaneously decrease as-cast microsegregation. Contours of the equal phase fraction were calculated over the isothermal diagrams of the Fe–Ni–Cr–Ti–Al–Nb system, and provided useful guidelines for compositional modifications. The microsegregation was also evaluated by Scheil-type simulation in order to reduce micropores caused by oxidation of the solidifying front.The developed cast Fe-based alloy showed desirable strength at the envisioned service temperatures and filled the open range of heat resistance between Ni-based superalloys and the original alloy.     

Lingual Epithelial Stem Cells and Organoid Culture of Them

As tongue cancer is one of the major malignant cancers in the world, understanding the mechanism of maintenance of lingual epithelial tissue, which is known to be the origin of tongue cancer, is unquestionably important. However, the actual stem cells that are responsible for the long-term maintenance of the lingual epithelium have not been identified. Moreover, a simple and convenient culture method for lingual epithelial stem cells has not yet been established. Recently, we have shown that Bmi1-positive cells, residing at the second or third layer of the epithelial cell layer at the base of the interpapillary pit (IPP), were slow-cycling and could supply keratinized epithelial cells for over one year, indicating that Bmi1-positive cells are long-term lingual epithelial stem cells. In addition, we have developed a novel lingual epithelium organoid culture system using a three-dimensional matrix and growth factors. Here, we discuss current progress in the identification of lingual stem cells and future applications of the lingual culture system for studying the regulatory mechanisms of the lingual epithelium and for regenerative medicine.     

Size of plastic region owing to blunting of the precrack tip andJ lc value in several types of structural steels

In this study, a three-point bendJ _lc fracture-toughness test was carried out using four types of structural steels at room temperature. The values of (γ _p)V, which represent the width of the region where the voids are located just ahead of the crack tip, were measured by Beacham's method [9] with the help of a scanning electron microscope (SEM). The experimental (γ _p) values and the theoretical values obtained using the finite element method (FEM) or calculated fromK at initiation are in good agreement. It was found that there is a certain linear relationship between (γ _p)Vand the stretched zone width (SZW), and an experimental relationship betweenJ _lc andσ _flow·(γ _p)V which may be expressed by the following equation: $$J_{lc} = 44.1 + 0.35\sigma _{{\text{flow}}} \cdot (\gamma _{\text{p}} )V_c KJ$$ whereσ _flow is the average value of the yield stress and the ultimate tensile strength. (γ _p)V _c represents the critical value of (γ _p)V. The numerical constant 44.1 kJ m^?2 is considered to be aJ _lc value for brittle fracture of the material tested, according to the authors' previous results. It is possible to calculateJ _lc if (γ _p)V _c can be measured.     

Power-Transformation for Ordered Categorical Data

We consider in this paper a model of asymmetric power-transformation of response probability explained by linear function of some covariates. This model includes logistic and complementary log-log transformation models as its specific case, so we can use the model to evaluate the appropriateness or the goodness of fit of these models. Then the performances of the asymmetric power-transformation model are evaluated and examined, based on data used in published literatures. And we discuss various issues of diagnoses which may occur in the process of applying the model. Further we consider alternative transformations, and then in comparison with them, we point out the advantages of the asymmetric power-transformation.

     

High-temperature deformation and fracture behaviour of Cu-SiO2 bicrystals

Bicrystals of CU-SiO₂ dispersion-hardened alloys and of pure copper were tensile tested at various temperatures between 450 and 1050 K at a strain rate of 1.5 x 10^–4 sec^–1. In the case of pure copper bicrystals, elongation to fracture did not depend significantly on temperature and the fracture mode was invariably transgranular up to 850 K. On the other hand, the ductility of CU-SiO₂ bicrystals decreased with increase in temperature and the transition in the fracture mode from transgranular to intergranular occurred at around 450 K. SiO₂ particles on grain boundaries play an important role on intergranular fracture by suppressing grain-boundary sliding and also on the retardation of recrystallization during deformation. Two types of Cu-SiO₂ bicrystals having different crystal orientation relationships show quite different deformation and fracture behaviour. This can be explained in terms of the contribution of lattice dislocations to the grain-boundary sliding.     

Some properties of thin aluminium nitride films formed in a glow discharge

The formation of thin AlN films and some of their electrical properties have been investigated. The films were prepared by exposing the surface of evaporated aluminium films to a glow discharge in pure nitrogen gas. It has been confirmed by transmission electron diffraction that the structure of the film is of the wurtzite type, as is that of the bulk material. It was observed that the thickness of the AlN films depends on the voltage of the glow discharge, the distance from the discharge electrode to the films and the treatment time. The electrical properties were measured in the form of a sandwich diode, i.e. Al-AlN-Au. The voltage-controlled negative resistance, which was first discovered in Al-Al₂O₃-metal diodes, has also been observed in this nitride film diode and shows very good reproducibility and stability.     

Crystal growth and structure analysis of twin-free monoclinic hydroxyapatite

Single crystals of hydroxyapatite were grown by a flux method using Ca₃(PO₄)₂ and Ca(OH)₂ under 100 MPa of Ar gas. The crystals obtained had stoichiometric composition of Ca₁₀(PO₄)₆(OH)₂ and some of them were twin-free single crystals. From X-ray diffraction analyses, the space group was confirmed to be monoclinic P2₁/b with cell parameters a=0.9419(3) nm, b=1.8848(6) nm, c=0.6884(2) nm, and =119.98(2)°. The detailed crystal structure was determined with a reliability factor R_w=0.033; the O atoms of OH were located just on the 2₁ axis while the H atoms of OH occupied the positions a little deviated from the 2₁ axis. The origin of this structure was ascribed to the formation of hydrogen bonds between the H atoms of the OH ions and the specific O atoms of the PO₄ ions.     

Preparation of therapeutic phospholipids through porcine pancreatic phospholipase A2-mediated esterification and lipozyme-mediated acidolysis

Highly unsaturated fatty acid-containing phospholipids (HUFA-PL), which serve to increase the deformability of human red blood cells, were prepared through porcine phospholipase A₂-mediated esterification of the lysophosphatidylcholine, which was derived from soy phosphatidylcholine (PC), and by Lipozyme-mediated acidolysis. Through these processes, phospholipase A₂, with formamide as a water mimic, enhanced the incorporation of HUFA into positionsn-2 of PC and suppressed hydrolysis of the synthesized PL. On the other hand, Lipozyme-mediated acidolysis between positionsn-1 of soy PC and HUFA was enhanced by a combination of water and propylene glycol. Simultaneously, the recovered PL products showed decreased hydrolysis of newly synthesized health-beneficial HUFA-PL.