57 research outputs found

    Synthesis and NMR Contact Shift of Paramagnetic Tris(tropolonato)vanadium(III)

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    A paramagnetic complex of tris(tropolonato)vanadium(Ⅲ) was prepared and a 1H-NMR spectrum of the complex was studied. From a consideration of the signs and magnitudes of paramagnetic shifts, it was concluded that the shifts were primarily due to unpaired electron delocalization via metal to ligand parallel spin transfer

    Photoassisted Dehydrogenation of 2-Propanol in the Liquid Phase with Hydrido (phosphonite) cobalt (I)

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    Hydrido (phosphonite) cobalt(I) [CoH{PPh(OEt)_2}_4], (CoHL_4) (L=PPh(OEt)_2) under Pyrex-filtered photoirradiation catalyzed dehydrogenation reaction of 2-propanol in the liquid phase, with release of acetone. The turn-over number evaluated for the dehydrogenation for 1h at 82℃ was 4.6, and the quantum yields for the reaction at 366nm were determined to be about 0.015 at 60 and 82℃. The dehydrogenation was characterized as a photoassisted-type catalytic reaction, and the photogenerated hydrido transient CoHL_3 was attributed to a key-role-playing intermediate in the catalytic cycle of the dehydrogenation

    cAMP-responsive element in TATA-less core promoter is essential for haploid-specific gene expression in mouse testis

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    Promoters, including neither TATA box nor initiator, have been frequently found in testicular germ cell-specific genes in mice. These investigations imply that unique forms of the polymerase II transcription initiation machinery play a role in selective activation of germ cell-specific gene expression programs during spermatogenesis. However, there is little information about testis-specific core promoters, because useful germ cell culture system is not available. In this study, we characterize the regulatory region of the haploid-specific Oxct2b gene in detail by using in vivo transient transfection assay in combination with a transgenic approach, with electrophoretic mobility shift and chromatin immunoprecipitation assays. Expression studies using mutant constructs demonstrate that a 34 bp region, which extends from −49 to −16, acts as a core promoter in an orientation-dependent manner. This promoter region includes the cAMP-responsive element (CRE)-like sequence TGACGCAG, but contains no other motifs, such as a TATA box or initiator. The CRE-like element is indispensable for the core promoter activity, but not for activator in testicular germ cells, through the binding of a testis-specific CRE modulator transcription factor. These results indicate the presence of alternative transcriptional initiation machinery for cell-type-specific gene expression in testicular germ cells

    Neuromagnetic Activation of Primaryand Secondary Somatosensory Cortex Following Tactile-on and Tactile-off Stimulation

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    Objective Magnetoencephalography (MEG) recordings were performed to investigate the cortical activation following tactile-on and tactile-off stimulation. Methods We used a 306-ch whole-head MEG system and a tactile stimulator driven by a piezoelectric actuator. Tactile stimuli were applied to the tip of right index finger. The interstimulus interval was set at 2000 ms, which included a constant stimulus of 1000 ms duration. Results Prominent somatosensory evoked magnetic fields were recorded from the contralateral hemisphere at 57.5 ms and 133.0 ms after the onset of tactile-on stimulation and at 58.2 ms and 138.5 ms after the onset of tactile-off stimulation. All corresponding equivalent current dipoles (ECDs) were located in the primary somatosensory cortex (SI). Moreover, long-latency responses (168.7 ms after tactile-on stimulation, 169.8 ms after tactile-off stimulation) were detected from the ipsilateral hemisphere. The ECDs of these signals were identified in the secondary somatosensory cortex (SII). Conclusions The somatosensory evoked magnetic fields waveforms elicited by the two tactile stimuli (tactile-on and tactile-off stimuli) with a mechanical stimulator were strikingly similar. These mechanical stimuli elicited both contralateral SI and ipsilateral SII activities. Significance Tactile stimulation with a mechanical stimulator provides new possibilities for experimental designs in studies of the human mechanoreceptor system

    NO Reduction Cycle on Dinuclear Ruthenium Complexes having Hydrotris(pyrazolyl)borato

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    ナノダイナミクス国際シンポジウム 平成22年1月21日(木) 於長崎大学Nagasaki Symposium on Nano-Dynamics 2010 (NSND2010), January 21, 2010, Nagasaki University, Nagasaki, Japan, Invited Lectur

    Methylation of a nitrosylruthenium complex bearing a hydridotris(pyrazolyl)borate ligand

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    Reaction of [TpRuCl2(NO)] (1) (Tp = HB(pyrazol-1-yl) 3) with dimethylzinc, Zn(Me)2, gave rise to a dimethyl complex [TpRu(Me)2(NO)] (2) and a monomethyl complex [TpRuCl(Me)(NO)] (3) in good yields, while the use of a Grignard reagent, MeMgCl, as the alkylating agents led to isolation of 2 in low yield. Complexes 2 and 3 were confirmed by single-crystal X-ray diffraction analyses. Treatment of 2 with triflic acid, CF3SO3H, afforded a triflato complex [TpRu(Me){OS(O)2CF3}(NO)] (4)

    Management of postoperative hemorrhage associated with factor VIII inhibitor: report of a case

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    This report presents a case that was successfully treated for acquired factor VIII inhibitor after extensive visceral surgery. A 71-year-old male who underwent surgery for bile duct cancer had active bleeding in the abdominal drainage tube on postoperative day (POD) 5, and prolonged activated partial thromboplastin time (aPTT) was detected (83.1 s) on POD 7. An extensive coagulation work-up revealed factor VIII deficiency (1 %), and a diagnosis of an acquired factor VIII deficiency was established when a factor VIII inhibitor of 8 Bethesda units was demonstrated. The patient was treated with activated prothrombin complex concentrate (aPCCs) and bloody discharge was stopped within 3 days. Inhibitor elimination was started using prednisolone on POD 20; rituximab, was administered on POD 74 and 81. Factor VIII inhibitor had disappeared by POD 124, and factor VIII (72 %) and aPTT recovered to 45.9 s. This case report demonstrated the efficacy of aPCCs and rituximab in the treatment of acquired hemophilia associated with visceral surgery. © 2012 Springer

    Reactions of (polypyrazolylborato)(benzonitrile)rutheniums with terminal alkynes: Reactivity changeover by triethylamine toward arylalkyne polymerization or formation of (arylmethyl)(carbonyl) complexes

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    Reactions of (κ 3-polypyrazolylborato)(benzonitrile) rutheniums [RuCl{B(4-Ypz) 4}(PhCN) 2] {4-Ypz; 4-bromo-1-pyrazolyl (Y = Br) and 1-pyrazolyl (Y = H) groups} with terminal alkynes were studied. For the reactions with arylalkynes HC≡C(aryl) in the presence of NEt 3, (arylmethyl)(carbonyl)rutheniums [Ru{CH 2(aryl)}{B(4-Ypz) 4}(CO)(PhCN)] were yielded, indicating alkyne C≡C bond cleavage, whereas in the absence of NEt 3, arylalkyne polymerization proceeded instead of the (arylmethyl)ruthenium formation. Reasonably attributed reaction mechanism shows significant role of the vinylidene intermediates "Ru=C=CH(aryl)"

    Reductive N–N coupling of NO molecules on transition metal complexes leading to N2O

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    Nitric oxide reductase (NOR) type reactions (2NO + 2e- + 2H+ → N2O + H2O) on transition metal complexes not involving NO disproportionation (3NO → N2O + NO2) are reviewed. The former has little reported, although the latter is very common reaction. The formation of N2O indicates that N-N coupling of two NO molecules is an essential step. A few examples of N-N coupling on transition metal complexes have been structurally characterized, including several examples of hyponitrite (O-N{double bond, long}N-O)2- complexes and only one diruthenium complex bearing neutral (O{double bond, long}N-N{double bond, long}O) binding mode. Protonation or heating their complexes led to elimination of N2O. In the examination of the NOR-type reaction, only a few functional model complexes for the active site of the metalloenzyme have been developed. These complexes also showed NOR activity. Finally, an NO reduction cycle in the diruthenium system is described
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