Concise Synthesis of Isocoumarins through Rh-Catalyzed Direct Vinylene Annulation: Scope and Mechanistic Insight

Transition-metal-catalyzed activation of inert C–H bonds and subsequent C–C bond formation have emerged as pow-erful synthetic tools for the synthesis of elaborate cyclic molecules. In this report, we introduce an efficient synthetic method of 3,4-unsubstituted isocoumarins adopting an electron deficient CpERh complex as the catalyst. The use of vinylene carbonate as a vinylene transfer reagent enables the direct construction of isocoumarins from readily available benzoic acids, without any external oxidants as well as bases. The reaction mechanism is evaluated by computational analysis to find an unprecedented “rhodium shift” event within the catalytic cycle.Mihara G., Ghosh K., Nishii Y., et al. Concise Synthesis of Isocoumarins through Rh-Catalyzed Direct Vinylene Annulation: Scope and Mechanistic Insight. Organic Letters. 22(14), 5706-5711, (2020), 17 July 2020; ©2020 American Chemical Society. https://doi.org/10.1021/acs.orglett.0c02112

Rhodium-catalyzed annulative coupling of isothiazoles with alkynes through n-s bond cleavage

A Rh(III)-catalyzed annulative coupling of 3,5-diarylisothiazoles and alkynes is reported. The N–S bond in the isothi-azole ring acts as an internal oxidant to regenerate the Rh(III) species in combination with an external Cu(II) oxidant, and the corre-sponding 1:2 coupling products are obtained. The remarkable difference in the reaction outcome between isothiazoles and the relevant isoxazoles has been investigated by DFT calculations, revealing that the relative stability of the enolate intermediates dictates the product selectivity.Mihara G., Noguchi T., Nishii Y., et al. Rhodium-catalyzed annulative coupling of isothiazoles with alkynes through n-s bond cleavage. Organic Letters. 22(2), 661-665, (2020), 17 January 2020; ©2020 American Chemical Society. https://doi.org/10.1021/acs.orglett.9b04437

Irinotecan Plus Mitomycin C as Second-Line Chemotherapy for Advanced Gastric Cancer Resistant to Fluoropyrimidine and Cisplatin: A Retrospective Study

Background. S-1 plus cisplatin has been established to be standard first-line chemotherapy for advanced gastric cancer in Japan. The optimal second-line treatment refractory to S-1 plus cisplatin remains unclear. Methods. We retrospectively studied the efficacy, toxicity, and survival of irinotecan plus mitomycin C in patients with advanced gastric cancer refractory to a fluoropyrimidine plus cisplatin. Results. Twenty-four patients were studied. Prior chemotherapy was S-1 plus cisplatin in 15 patients, S-1 plus cisplatin and docetaxel in 8, and 5-fluorouracil plus cisplatin with radiotherapy in 1. The overall response rate was 17.4%. The median overall survival was 8.6 months, and the median progression-free survival was 3.6 months. Grade 3 or 4 toxicities included leukopenia (33%), neutropenia (50%), anemia (33%), thrombocytopenia (4%), anorexia (13%), diarrhea (4%), and febrile neutropenia (13%). Conclusion. A combination of irinotecan and mitomycin C is potentially effective in patients with advanced gastric cancer refractory to a fluoropyrimidine plus cisplatin

シニクコウ シンシュツエキ チュウ ノ バイオマーカー オ モチイタ シシュウビョウ シンダン

Periodontal diseases cause an inflammation and degradation of periodontal tissues and missing of teeth. The incidence rate of periodontal diseases is high in middle-aged and elderly people. A reasonable diagnosis of periodontal diseases is very important to keep teeth, however, conventional examinations of periodontal diseases is not necessarily exact and objective. Gingival crevicular fluid (GCF) is an exudate secreted from periodontal tissues and contains many components including proteolytic enzymes, inflammatory cytokines, blood-associated proteins, cellular and bacterial fragments. Because some proteins in GCF are related to inflammation, tissue degradation and bone metabolism, those proteins have been studying as a diagnostic marker of periodontal diseases. GCF is noninvasively collected using a sterile paper strip and biomarkers are determined using enzyme-linked immunosorbent assay (ELISA) and enzyme activity assay. We identified calprotectin, an inflammationrelated protein, in GCF and calprotectin level in GCF from periodontitis sites was significantly higher than that of healthy control. Calprotectin level in GCF was positively correlated to gingival index and other biomarkers and decreased by periodontal treatments. Resistin is an adipocytokine and its level increases in some inflammatory diseases. Resistin level in GCF from periodontitis sites was high compared to the level of healthy control samples. Procollagen type I C-terminal peptide (PICP) is a biomarker for bone metabolism and its level was high in GCF collected from periodontitis sites. These results suggested that calprotectin, resistin and PICP are useful biomarkers for periodontal diseases. On the other hand, we showed that glycated albumin (GA), a marker of diabetes mellitus (DM), was contained in GCF and GA level in GCF from DM patients was significantly higher than that of non-DM individuals. Components in GCF may be biomarkers of systemic diseases as well as periodontal diseases and their determination will be useful diagnostic examination of some diseases. Recently, we have been studying the determining system of GCF calprotectin, including microchip ELISA, surface plasmon resonance assay and immuno-chromatography assay. When GCF biomarkers are determined using the determining systems, we will simply, exactly and objectively diagnose periodontal diseases at our dental offices

Monitor of All-sky X-ray Image (MAXI)

Abstract. Monitor of All-sky X-ray Image (MAXI) is the first astrophysical payload which will be mounted on the Japanese Experiment Module (JEM) Exposed Facility in 2004. It is an X-ray all-sky monitor with unprecedented sensitivity to watch the activities of the X-ray sources in the whole sky in every 90 minutes. MAXI is boxshaped in 0.8 x 1.0 x 1.85 m with the weight of 500 kg. The mission life will be at least 2 years. MAXI has two fan-like field of views (FOV), 160 x 1.5 degree each. The X-ray instruments are Gas Slit Camera (GSC) and Solid-state Slit Camera (SSC). The GSC uses gas one-dimensional position sensitive proportional counters with 5340 cm 2 effective area in total and the SSC uses CCDs with 200 cm 2 . Both are capable to detect one-dimensional image, which is used to obtain the locations of the X-ray sources in the FOV along the long direction. Together with the scan which determine the other direction, MAXI can scan almost all sky with a precision of better than 1 degree in the energy range of 0.5-30 keV. The CCD is electrically cooled to -60°C and the camera body is radiatively cooled to -20°C. The CCD chip itself and the radiators may suffer contamination problem. The continuous Ethernet down link will enable us to alert the astronomers in all over the world to the appearance of X-ray transients, novae, bursts, flares etc. We made a test counter and test chips in 1998. Those are being tested in RIKEN, NASDA and Osaka-university. In this paper the test results will be presented, as well as the general description of the MAXI mission

Rice TOGO Browser: A Platform to Retrieve Integrated Information on Rice Functional and Applied Genomics

The Rice TOGO Browser is an online public resource designed to facilitate integration and visualization of mapping data of bacterial artificial chromosome (BAC)/P1-derived artificial chromosome (PAC) clones, genes, restriction fragment length polymorphism (RFLP)/simple sequence repeat (SSR) markers and phenotype data represented as quantitative trait loci (QTLs) onto the genome sequence, and to provide a platform for more efficient utilization of genome information from the point of view of applied genomics as well as functional genomics. Three search options, namely keyword search, region search and trait search, generate various types of data in a user-friendly interface with three distinct viewers, a chromosome viewer, an integrated map viewer and a sequence viewer, thereby providing the opportunity to view the position of genes and/or QTLs at the chromosomal level and to retrieve any sequence information in a user-defined genome region. Furthermore, the gene list, marker list and genome sequence in a specified region delineated by RFLP/SSR markers and any sequences designed as primers can be viewed and downloaded to support forward genetics approaches. An additional feature of this database is the graphical viewer for BLAST search to reveal information not only for regions with significant sequence similarity but also for regions adjacent to those with similarity but with no hits between sequences. An easy to use and intuitive user interface can help a wide range of users in retrieving integrated mapping information including agronomically important traits on the rice genome sequence. The database can be accessed at http://agri-trait.dna.affrc.go.jp/