On-surface synthesis and characterization of nitrogen-substituted undecacenes.

Heteroatom substitution in acenes allows tailoring of their remarkable electronic properties, expected to include spin-polarization and magnetism for larger members of the acene family. Here, we present a strategy for the on-surface synthesis of three undecacene analogs substituted with four nitrogen atoms on an Au(111) substrate, by employing specifically designed diethano-bridged precursors. A similarly designed precursor is used to synthesize the pristine undecacene molecule. By comparing experimental features of scanning probe microscopy with ab initio simulations, we demonstrate that the ground state of the synthesized tetraazaundecacene has considerable open-shell character on Au(111). Additionally, we demonstrate that the electronegative nitrogen atoms induce a considerable shift in energy level alignment compared to the pristine undecacene, and that the introduction of hydro-aza groups causes local anti-aromaticity in the synthesized compounds. Our work provides access to the precise fabrication of nitrogen-substituted acenes and their analogs, potential building-blocks of organic electronics and spintronics, and a rich playground to explore π-electron correlation.

The efficacy and toxicity of 4-day chemotherapy with methotrexate, etoposide and actinomycin D in patients with choriocarcinoma and high-risk gestational trophoblastic neoplasia.

OBJECTIVE: This study aimed to evaluate the efficacy and toxicity of 4-day chemotherapy with methotrexate, etoposide, and actinomycin D (MEA) for patients who were diagnosed with choriocarcinoma and high-risk gestational trophoblastic neoplasia (GTN). METHODS: Between January 1999 and December 2015, 29 patients were treated with 4-day MEA after being diagnosed with choriocarcinoma or high-risk GTN. Complete remission to 4-day MEA and adverse effects were retrospectively evaluated. RESULTS: The complete remission rates were 79.3% (23/29) and 87.5% (21/24) in all patients and in those who received 4-day MEA as first-line therapy, respectively. Of six patients who developed drug resistance to 4-day MEA, three patients showed complete remission by other treatments, while the other three patients died of the disease. The major adverse effects were leukocytopenia, anemia, and nausea. Of 23 patients who were cured with 4-day MEA, treatment was changed to the etoposide and actinomycin D (EA) regimen in 14 patients, because of leukocytopenia, hepatotoxicity, and stomatitis. Among 20 patients who required hormonal therapy, 15 patients showed normal menstrual cycles after therapy. Five patients had nine conceptions (seven term live births and two spontaneous abortions). No babies were premature or had low birth weight nor did they have congenital anomalies. CONCLUSION: The results suggest that the efficacy and the adverse effects of 4-day MEA for choriocarcinoma and high-risk GTN may be the same level as EMA/CO. However, further study will be needed for determining the criteria of changing the treatment regimen from 4-day MEA to the EA regimen.

Cyclic AMP signaling enhances lipopolysaccharide sensitivity and interleukin-33 production in RAW264.7 macrophages.

While it has been suggested that IL-33 plays pathogenic roles in various disorders, the factors that stimulate IL-33 production are poorly characterized. In the present study, the effect of cyclic adenosine monophosphate (cAMP) signaling on IL-33 production in RAW264.7 macrophages in response to various doses of LPS was examined. High-dose LPS treatment induced IL-33 and TNF protein production in RAW264.7 macrophages. In contrast, low-dose LPS failed to induce IL-33 production while significantly inducing TNF production. In the presence of the membrane-permeable cAMP analog 8-Br-cAMP, low-dose LPS induced vigorous IL-33 production. This phenomenon was consistent with amounts of mRNA. Similarly, the cAMP-increasing agent adrenaline also enhanced the sensitivity of RAW264.7 macrophages to LPS as demonstrated by IL-33 production. The protein kinase A (PKA) inhibitor H89 blocked the effects of 8-Br-cAMP and adrenaline on IL-33 production, suggesting that PKA is involved in IL-33 induction. Taken together, cAMP-mediated signaling pathway appears to enhance the sensitivity of RAW264.7 macrophages to LPS with respect to IL-33 production. Our findings suggest that stress events and the subsequent secretion of adrenaline enhance macrophage production via IL-33; this process may be associated with the pathogenesis of various disorders involving IL-33.

Photoinduced reduction and heat-induced oxidation of silver in transparent RSiO(3/2) and RSiO(3/2)-TiO(2) films.

Photoinduced reduction, resulting in nanoparticle formation, and heat-induced oxidation of doped silver have been demonstrated in silsesquioxane (RSiO(3/2)) and RSiO(3/2)-TiO(2) films (R = methyl, vinyl, and glycidoxypropyl) synthesized via the sol-gel method. The occurrence of redox behavior in the doped silver, i.e. formation and dissociation of silver nanoparticles (AgNPs) in the films, was confirmed by UV-Vis spectroscopy, IR spectroscopy, X-ray diffraction and transmission electron microscopy. The films containing vinyl and glycidoxypropyl organic functional groups were found to effectively reduce silver ions upon UV irradiation, whereas the film containing the methyl group substituent did not. Incorporation of a TiO(2) component into the RSiO(3/2) films caused thermal dissociation of the AgNPs. The formation and dissociation of AgNPs in the films was reversible by reiterating the cycle of UV irradiation and heat treatment.

[Collage work characteristics and personality].

The purpose of this study was to investigate the relationship between personality and characteristics in collage work. Seventy undergraduates filled the Yatabe-Guilford (YG) personality test and produced a piece of collage work. The YG personality types were not different in terms of collage work characteristics. However, emotional adaptation and introvert/extrovert scores were reflected in the number of cuttings used in the piece. General activity score was reflected in the number of vehicle pictures used. Those who used an eye picture had a tendency to be depressed and lacking in confidence. Those who used a "stone circle" picture tended to be more emotionally adapted and extroverted. The results suggested a possibility that personality traits were reflected in specific characteristics in collage work.