7 research outputs found

    Rhodium-Catalyzed Decarboxylative and Dehydrogenative Coupling of Maleic Acids with Alkynes and Alkenes

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    The dehydrogenative coupling of maleic acids with alkynes proceeds smoothly accompanied by decarboxylation under rhodium catalysis to produce variously substituted α-pyrone derivatives. The catalyst system is also applicable to the coupling with 1,3-diynes and alkenes

    Porphyrins Sheathed in Quadrupolar Solvation Spheres of Hexafluorobenzene: Solvation-Induced Fluorescence Enhancement and Conformational Confinement

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    Hexafluorobenzene (C<sub>6</sub>F<sub>6</sub>) strongly solvated the porphyrin ring via a quadrupolar interaction. The solvation sphere of C<sub>6</sub>F<sub>6</sub> hindered the thermal fluctuations near the porphyrin ring and evoked remarkable photoelectronic properties of the porphyrins such as fluorescence enhancement and spectral sharpening due to confined torsional planarity

    Siloxy Group-Induced Highly Efficient Room Temperature Phosphorescence with Long Lifetime

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    The design and development of organic phosphors that exhibit efficient emission at room temperature but do not contain precious metals such as iridium and platinum have attracted increasing attention. We report herein highly efficient green phosphorescence-emitting 1,4-dibenzoyl-2,5-bis­(siloxy)­benzene crystals in air at room temperature. Remarkable luminescence quantum yields of 0.46 to 0.64 and long lifetimes ranging from 76.0 to 98.3 ms were observed. X-ray diffraction analysis of the single crystals revealed that there were several intermolecular interactions causing suppression of intramolecular motion, thereby minimizing nonradiative decay of the triplet excited state. Comparison with the corresponding 2,5-bis­(dimethylphenylsilylmethyl) and 2,5-bis­(trimethylsilyl) derivatives revealed that the siloxy groups are essential for efficient room temperature phosphorescence. Density functional calculations suggested that σ–n conjugation was operative in the siloxy moieties. Electron spin resonance measurement indicated that the radiative process included generation of the triplet diradical species, whose electron distribution was very similar to that of naphthalene. The present study largely expands the possibilities for the molecular design of precious metal- and halogen-free organic phosphors exhibiting efficient room temperature phosphorescence

    Group 14 Dithienometallole-Linked Ethynylene-Conjugated Porphyrin Dimers

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    The considerably conjugated π systems of the group 14 dithienometallole-linked ethynylene-conjugated porphyrin dimers (<b>1M</b>s) were described based on comprehensive experimental and theoretical studies. The electronic absorption spectra of <b>1M</b> displayed a large splitting in the Soret band and a red-shifted Q-band, indicating that the dithienometallole spacer was effective in facilitating the porphyrin–porphyrin electronic coupling. Torsional planarization behaviors of <b>1M</b> were observed in the time-resolved fluorescence spectra. Density functional theory (DFT) calculations revealed that the dithienometallole spacer is an ideal partner for the ethynylene-conjugated porphyrin to produce fully delocalized highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels due to their similar HOMO and LUMO levels. Finally, <b>1M</b> exhibited a strong propensity for the quinoidal–cummulenic conjugation in the dithienometallole spacer when in a photoexcited state

    DataSheet_1_Assessment of type I interferon signatures in undifferentiated inflammatory diseases: A Japanese multicenter experience.pdf

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    PurposeUpregulation of type I interferon (IFN) signaling has been increasingly detected in inflammatory diseases. Recently, upregulation of the IFN signature has been suggested as a potential biomarker of IFN-driven inflammatory diseases. Yet, it remains unclear to what extent type I IFN is involved in the pathogenesis of undifferentiated inflammatory diseases. This study aimed to quantify the type I IFN signature in clinically undiagnosed patients and assess clinical characteristics in those with a high IFN signature.MethodsThe type I IFN signature was measured in patients’ whole blood cells. Clinical and biological data were collected retrospectively, and an intensive genetic analysis was performed in undiagnosed patients with a high IFN signature.ResultsA total of 117 samples from 94 patients with inflammatory diseases, including 37 undiagnosed cases, were analyzed. Increased IFN signaling was observed in 19 undiagnosed patients, with 10 exhibiting clinical features commonly found in type I interferonopathies. Skin manifestations, observed in eight patients, were macroscopically and histologically similar to those found in proteasome-associated autoinflammatory syndrome. Genetic analysis identified novel mutations in the PSMB8 gene of one patient, and rare variants of unknown significance in genes linked to type I IFN signaling in four patients. A JAK inhibitor effectively treated the patient with the PSMB8 mutations. Patients with clinically quiescent idiopathic pulmonary hemosiderosis and A20 haploinsufficiency showed enhanced IFN signaling.ConclusionsHalf of the patients examined in this study, with undifferentiated inflammatory diseases, clinically quiescent A20 haploinsufficiency, or idiopathic pulmonary hemosiderosis, had an elevated type I IFN signature.</p
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