237 research outputs found

    Proposal for Sets of (77)Se NMR Chemical Shifts in Planar and Perpendicular Orientations of Aryl Group and the Applications

    Get PDF
    The orientational effect of p-YC(6)H(4) (Ar) on δ(Se) is elucidated for ArSeR, based on experimental and theoretical investigations. Sets of δ(Se) are proposed for pl and pd employing 9-(arylselanyl)anthracenes (1) and 1-(arylselanyl)anthraquinones (2), respectively, where Se–C (R) in ArSeR is on the Ar plane in pl and perpendicular to the plane in pd. Absolute magnetic shielding tensors of Se (σ(Se)) are calculated for ArSeR (R = H, Me, and Ph), assuming pl and pd, with the DFT-GIAO method. Observed characters are well reproduced by the total shielding tensors (σ (t)(Se)). The paramagnetic terms (σ (P)(Se)) are governed by σ (P)(Se)(xx) + σ (P)(Se)(yy), where the direction of n(P)(Se) is set to the z-axis. The mechanisms of the orientational effect are established both for pl and pd. Sets of δ(Se: 1) and δ(Se: 2) act as the standards for pl and pd, respectively, when δ(Se) of ArSeR are analyzed based on the orientational effect

    Fine Structures of 8-G-1-(p-YC6H4C ≡ CSe)C10H6 (G = H, Cl, and Br) in Crystals and Solutions: Ethynyl Influence and Y- and G-Dependences

    Get PDF
    Fine structures of 8-G-1-(p-YC6H4C ≡ CSe)C10H6 [1 (G = H) and 2 (G = Cl): Y = H (a), OMe (b), Me (c), F (d), Cl (e), CN (f), and NO2 (g)] are determined by the X-ray analysis. Structures of 1, 2, and 3 (G = Br) are called A if each Se–Csp bond is perpendicular to the naphthyl plane, whereas they are B when the bond is placed on the plane. Structures are observed as A for 1a–c bearing Y of nonacceptors, whereas they are B for 1e–g with Y of strong acceptors. The change in the structures of 1e–g versus those of 1a–c is called Y-dependence in 1. The Y-dependence is very specific in 1 relative to 1-(p-YC6H4Se)C10H7 (4) due to the ethynyl group: the Y-dependence in 1 is almost inverse to the case of 4 due to the ethynyl group. We call the specific effect “Ethynyl Influence.” Structures of 2 are observed as B: the A-type structure of 1b changes dramatically to B of 2b by G = Cl at the 8-position, which is called G-dependence. The structures of 2 and 3 are examined in solutions based on the NMR parameters

    Expression of the retinoblastoma protein RbAp48 in exocrine glands leads to Sjögren's syndrome–like autoimmune exocrinopathy

    Get PDF
    Although several autoimmune diseases are known to develop in postmenopausal women, the mechanisms by which estrogen deficiency influences autoimmunity remain unclear. Recently, we found that retinoblastoma-associated protein 48 (RbAp48) induces tissue-specific apoptosis in the exocrine glands depending on the level of estrogen deficiency. In this study, we report that transgenic (Tg) expression of RbAp48 resulted in the development of autoimmune exocrinopathy resembling Sjögren's syndrome. CD4+ T cell–mediated autoimmune lesions were aggravated with age, in association with autoantibody productions. Surprisingly, we obtained evidence that salivary and lacrimal epithelial cells can produce interferon-γ (IFN-γ) in addition to interleukin-18, which activates IFN regulatory factor-1 and class II transactivator. Indeed, autoimmune lesions in Rag2−/− mice were induced by the adoptive transfer of lymph node T cells from RbAp48-Tg mice. These results indicate a novel immunocompetent role of epithelial cells that can produce IFN-γ, resulting in loss of local tolerance before developing gender-based autoimmunity

    Angiomyolipoma of the tunica dartos of the scrotum in infancy

    Get PDF
    AbstractA 12-month-old boy presented with left scrotal swelling. The mass was irregular, soft, fleshy, and nontender. It adhered to the scrotal skin and gradually enlarged. Operative findings revealed a mass fixed to the scrotal fundus and diagnosed as angiomyolipoma. This is apparently the first report of scrotal angiomyolipoma in infancy

    Relationship Between Balance Recovery From a Forward Fall and Lower-Limb Rate of Torque Development

    Get PDF
    The authors examined the relationship between the maximum recoverable lean angle via the tether-release method with early- or late-phase rate of torque development (RTD) and maximum torque of lower-limb muscle groups in 56 young healthy adults. Maximal isometric torque and RTD at the hip, knee, and ankle were recorded. The RTD at 50-ms intervals up to 250 ms from force onset was calculated. The results of a stepwise multiple regression analysis, early RTD for hip flexion, and knee flexion were chosen as predictive variables for the maximum recoverable lean angle. The present study suggests that some of the early RTD in the lower limb muscles, but not the maximum isometric torque, can predict the maximum recoverable lean angle

    Synthesis, structural, spectroscopic and electrochemical studies of carborane substituted naphthyl selenides

    Full text link
    [EN] New unsymmetrical selenides bearing an o-carborane and a naphthalene ring as the substituents were prepared by the cleavage of the corresponding diselenides. The compounds were characterized by means of spectroscopic and analytical methods. Se-77 NMR signals of the selenium atoms attached to the carbon atoms of the carborane cages are shifted downfield in comparison to those bonded only to the aromatic rings, indicating an electron withdrawing effect of the o-carboranyl substituent. Compounds 1-(2-R-1,2-dicarba-closo-carboranyl)naphthyl selenides (R = Me, 1; Ph, 2) were characterized by means of single crystal X-ray diffraction. The influence of the electronic nature of the substituents attached to the selenium atoms on the structural parameters and packing properties of naphthyl selenides are discussed. Theoretical calculations and cyclic voltammetry (CV) studies were carried out to compare the bonding nature of carboranyl and analogous aryl selenium compounds. Cyclic voltammetry studies of naphthyl carboranyl mono and diselenides have shown that the carboranyl fragment polarizes the Se lone pair making it less prone to generate a Se-Se bond.This work was supported by the Japan-Spain Research Cooperative Program, Joint Project, 2004JP0102 from Japan Society for the Promotion of Science (JSPS) and CSIC, CICYT (CTQ2010-16237) and the Generalitat de Catalunya, 2009/SGR/00279. Dr O. Guzyr is grateful to Ministerio Education, Cultura y Deporte for grant SAB2003-0122.Guzyr, O.; Viñas, C.; Wada, H.; Hayashi, S.; Nakanishi, W.; Teixidor, F.; Vaca Puga, A.... (2011). Synthesis, structural, spectroscopic and electrochemical studies of carborane substituted naphthyl selenides. Dalton Transactions. 40(13):3402-3411. https://doi.org/10.1039/c0dt01658fS34023411401

    偏光分解顕微鏡を用いたアルコール性肝線維症の線維化の量的・質的評価系の開発

    Get PDF
    Liver fibrosis is assessed mainly by conventional staining or second harmonic generation (SHG) microscopy, which can only provide collagen content in fibrotic area. We propose to use polarization-resolved SHG (PR-SHG) microscopy to quantify liver fibrosis in terms of collagen fiber orientation and crystallization. Liver samples obtained from autopsy cases with fibrosis stage of F0–F4 were evaluated with an SHG microscope, and 12 consecutive PR-SHG images were acquired while changing the polarization azimuth angle of the irradiated laser from 0° to 165° in 15° increments using polarizer. The fiber orientation angle (φ) and degree (ρ) of collagen were estimated from the images. The SHG-positive area increased as the fibrosis stage progressed, which was well consistent with Sirius Red staining. The value of φ was random regardless of fibrosis stage. The mean value of ρ (ρ-mean), which represents collagen fiber crystallinity, varied more as fibrosis progressed to stage F3, and converged to a significantly higher value in F4 than in other stages. Spatial dispersion of ρ (ρ-entropy) also showed increased variation in the stage F3 and decreased variation in the stage F4. It was shown that PR-SHG could provide new information on the properties of collagen fibers in human liver fibrosis
    corecore