Takahiro Kawamoto

Upregulation of SR-PSOX/CXCL16 and Recruitment of CD8+ T Cells in Cardiac Valves During Inflammatory Valvular Heart Disease

Objective—SR-PSOX/CXCL16 is a transmembrane chemokine and is implicated in activated CD8+ T cell trafficking. In the present study, we examined the expression pattern of SR-PSOX/CXCL16 in the heart and investigated a potential role of SR-PSOX/CXCL16 in inflammatory valvular heart disease. Methods and Results—Initial expression of SR-PSOX/CXCL16 in murine embryos was detected in endothelial cells lining endocardial cushions in the forming heart at E11.5. From mid-gestation to adult, expression of this gene in the heart was exclusively observed in valvular endothelial cells. Examination of SR-PSOX/CXCL16 expression in human cardiac valves demonstrated that SR-PSOX/CXCL16 was strongly expressed in valvular and neocapillary endothelial cells in patients with infective endocarditis. SR-PSOX/CXCL16 expression in neocapillary endothelial cells was also observed in patients with rheumatic and atherosclerotic valvular disease. Moreover, CD8+ T cells were distributed closely to endothelial cells expressing SR-PSOX/CXCL16. In vitro adhesion assays showed that SR-PSOX/CXCL16 induced adhesion of activated CD8+ T cells to vascular cell adhesion molecule-1 (VCAM-1) through very late antigen-4 (VLA-4) activation. Furthermore, SR-PSOX/CXCL16 stimulated interferon-&ggr; (IFN-&ggr;) production by CD8+ T cells. Conclusions—SR-PSOX/CXCL16 may be involved in CD8+ T cell recruitment through VLA-4 activation and stimulation of IFN-&ggr; production by CD8+ T cells during inflammatory valvular heart disease.

Chiral Tetrafluorobenzobarrelene Ligands for the Rhodium-Catalyzed Asymmetric Cycloisomerization of Oxygen- and Nitrogen-Bridged 1,6-Enynes†

The transition-metal-catalyzed cycloisomerization reaction of 1,n-enynes has emerged as an atom-economical process for the preparation of diverse cyclic compounds. Nitrogenand oxygen-bridged enynes are useful starting materials for the construction of heterocyclic building blocks. Since Blum et al. reported the PtCl4-catalyzed transformation of allyl propargyl ethers into 3-oxabicyclo[4.1.0]heptenes in 1995, this type of 6-endo-dig cycloisomerization has been developed by the use of p-acidic metal catalysts such as platinum 5] and gold (Scheme 1). The reaction is thought to be promoted by the

Rhodium-Catalyzed Asymmetric Ring-Opening Alkynylation of Azabenzonorbornadienes

Asymmetric ring-opening alkynylation of meso-azabenzonorbornadienes with (triisopropylsilyl)acetylene giving 2-alkynyl-1-aminodihydronaphthalenes took place in high yields with high enantioselectivity in the presence of a rhodium/(R)-DTBM-segphos catalyst.

Rhodium-catalyzed asymmetric hydroalkoxylation and hydrosulfenylation of diphenylphosphinylallenes

The rhodium-catalyzed intermolecular asymmetric hydroalkoxylation and hydrosulfenylation of diphenylphosphinylallenes gave chiral allylic phosphine oxides substituted with vinyl ether and thioether moieties in high yields with high enantioselectivities.

Role of Hand1/eHAND in the Dorso-Ventral Patterning and Interventricular Septum Formation in the Embryonic Heart

ABSTRACT Molecular mechanisms for the dorso-ventral patterning and interventricular septum formation in the embryonic heart are unknown. To investigate a role of Hand1/eHAND in cardiac chamber formation, we generated Hand1/eHAND knock-in mice where Hand1/eHAND cDNA was placed under the control of the MLC2V promoter. In Hand1/eHAND knock-in mice, the outer curvature of the right and left ventricles expanded more markedly. Moreover, there was no interventricular groove or septum formation, although molecularly, Hand1/eHAND knock-in hearts had two ventricles. However, the morphology of the inner curvature of the ventricles, the atrioventricular canal, and the outflow tract was not affected by Hand1/eHAND expression. Furthermore, expression of Hand1/eHAND in the whole ventricles altered the expression patterns of Chisel, ANF, and Hand2/dHAND but did not affect Tbx5 expression. In contrast, the interventricular septum formed normally in transgenic embryos overexpressing Hand1/eHAND in the right ventricle but not in the boundary region. These results suggested that Hand1/eHAND is involved in expansion of the ventricular walls and that absence of Hand1/eHAND expression in the boundary region between the right and left ventricles may be critical in the proper formation of the interventricular groove and septum. Furthermore, Hand1/eHAND is not a master regulatory gene that specifies the left ventricle myocyte lineage but may control the dorso-ventral patterning in concert with additional genes.

Room-Temperature Polar Ferromagnet ScFeO3 Transformed from a High-Pressure Orthorhombic Perovskite Phase

Multiferroic materials have been the subject of intense study, but it remains a great challenge to synthesize those presenting both magnetic and ferroelectric polarizations at room temperature. In this work, we have successfully obtained LiNbO3-type ScFeO3, a metastable phase converted from the orthorhombic perovskite formed under 15 GPa at elevated temperatures. A combined structure analysis by synchrotron X-ray and neutron powder diffraction and high-angle annular dark-field scanning transmission electron microscopy imaging reveals that this compound adopts the polar R3c symmetry with a fully ordered arrangement of trivalent Sc and Fe ions, forming highly distorted ScO6 and FeO6 octahedra. The calculated spontaneous polarization along the hexagonal c-axis is as large as 100 μC/cm(2). The magnetic studies show that LiNbO3-type ScFeO3 is a weak ferromagnet with TN = 545 K due to a canted G-type antiferromagnetic ordering of Fe(3+) spins, representing the first example of LiNbO3-type oxides with magnetic ordering far above room temperature. A comparison of the present compound and rare-earth orthorhombic perovskites RFeO3 (R = La-Lu and Y), all of which possess the corner-shared FeO6 octahedral network, allows us to find a correlation between TN and the Fe-O-Fe bond angle, indicating that the A-site cation-size-dependent octahedral tilting dominates the magnetic transition through the Fe-O-Fe superexchange interaction. This work provides a general and versatile strategy to create materials in which ferroelectricity and ferromagnetism coexist at high temperatures.

Crystal and electronic structure and magnetic properties of divalent europium perovskite oxides EuMO3 (M = Ti, Zr, and Hf): experimental and first-principles approaches.

A comparative study of the crystal and electronic structure and magnetism of divalent europium perovskite oxides EuMO(3) (M = Ti, Zr, and Hf) has been performed on the basis of both experimental and theoretical approaches playing complementary roles. The compounds were synthesized via solid-state reactions. EuZrO(3) and EuHfO(3) have an orthorhombic structure with a space group Pbnm at room temperature contrary to EuTiO(3), which is cubic at room temperature. The optical band gaps of EuZrO(3) and EuHfO(3) are found to be about 2.4 and 2.7 eV, respectively, much larger than that of EuTiO(3) (0.8 eV). On the other hand, the present compounds exhibit similar magnetic properties characterized by paramagnetic-antiferromagnetic transitions at around 5 K, spin flop at moderate magnetic fields lower than 1 T, and the antiferromagnetic nearest-neighbor and ferromagnetic next-nearest-neighbor exchange interactions. First-principles calculations based on a hybrid Hartree-Fock density functional approach yield lattice constants, band gaps, and magnetic interactions in good agreement with those obtained experimentally. The band gap excitations are assigned to electronic transitions from the Eu 4f to Mnd states for EuMO(3) (M = Ti, Zr, and Hf and n = 3, 4, and 5, respectively).

Modified Faraday rotation in a three-dimensional magnetophotonic opal crystal consisting of maghemite/silica composite spheres

We have prepared a three-dimensional magnetophotonic crystal and observed modulated Faraday rotation around its photonic band gap. The magnetophotonic crystal was prepared by the self-assembly of highly monodispersed silica spheres, which were heavily impregnated with maghemite (γ−Fe2O3) nanoparticles. The slab sample with a thickness of 10u2009μm shows a clear photonic band gap centered at λ=620 nm in optical transmittance. Faraday rotation is notably modified inside the photonic band gap.

Perovskite-Type InCoO3 with Low-Spin Co3+: Effect of In–O Covalency on Structural Stabilization in Comparison with Rare-Earth Series

Perovskite rare-earth cobaltites ACoO3 (A = Sc, Y, La-Lu) have been of enduring interest for decades due to their unusual structural and physical properties associated with the spin-state transitions of low-spin Co3+ ions. Herein, we have synthesized a non-rare-earth perovskite cobaltite, InCoO3, at 15 GPa and 1400 °C and investigated its crystal structure and magnetic ground state. Under the same high-pressure and high-temperature conditions, we also prepared a perovskite-type ScCoO3 with an improved cation stoichiometry in comparison to that in a previous study, where synthesis at 6 GPa and 1297 °C yielded a perovskite cobaltite with cation mixing on the A-site, (Sc0.95Co0.05)CoO3. The two perovskite phases have nearly stoichiometric cation compositions, crystallizing in the orthorhombic Pnma space group. In the present investigation, comprehensive studies on newly developed and well-known Pnma ACoO3 perovskites (A = In, Sc, Y, Pr-Lu) show that InCoO3 does not fulfill the general evolution of crystal metrics with A-site cation size, indicating that InCoO3 and rare-earth counterparts have different chemistry for stabilizing the Pnma structures. Detailed structural analyses combined with first-principles calculations reveal that the origin of the anomaly for InCoO3 is ascribed to the A-site cation displacements that accompany octahedral tilts; despite the highly tilted CoO6 network, the In-O covalency makes In3+ ions reluctant to move from their ideal cubic-symmetry position, leading to less orthorhombic distortion than would be expected from electrostatic/ionic size mismatch effects. Magnetic studies demonstrate that InCoO3 and ScCoO3 are diamagnetic with a low-spin state of Co3+ below 300 K, in contrast to the case of (Sc0.95Co0.05)CoO3, where the high-spin Co3+ ions on the A-site generate a large paramagnetic moment. The present work extends the accessible composition range of the low-spin orthocobaltite series and thus should help to establish a more comprehensive understanding of the structure-property relation.

Preoperative assessment scale for elderly Japanese patients (part I) : basic study design and clinical trial

Background: The aim of the present paper was to propose a general assessment system for elderly patients undergoing surgical operations.