Palladium-Catalyzed Cross-Coupling Reaction of Diarylmethanol Derivatives with Diborylmethane

A palladium-catalyzed cross-coupling reaction of diarylmethanol derivatives with diborylmethane has been developed. The reaction proceeds chemoselectively to deliver the corresponding homobenzylic boronates in good yields.Asai K., Miura M., Hirano K.. Palladium-Catalyzed Cross-Coupling Reaction of Diarylmethanol Derivatives with Diborylmethane. Journal of Organic Chemistry. 87(11), 7436-7445, (2022), 3 June 2022; © 2022 American Chemical Society. https://doi.org/10.1021/acs.joc.2c00715

Divergent synthesis of isonitriles and nitriles by palladium- catalyzed benzylic substitution with TMSCN

Ligand-controlled palladium-catalyzed divergent synthesis of isonitriles and nitriles from benzylic carbonates and TMSCN has been developed. The BINAP- or DPEphos-ligated palladium catalyst selectively provides the corresponding benzylic isonitriles, whereas their regioisomers, benzylic nitriles, are formed exclusively under phosphine ligand-free conditions. Mechanistic studies reveal that isonitrile is the primary product under both conditions, but it is isomerized into nitrile in the absence of ancillary phosphine ligands.Hirano K., Miura M., Asai K.. Divergent synthesis of isonitriles and nitriles by palladium- catalyzed benzylic substitution with TMSCN. Journal of Organic Chemistry. 85(19), 12703-12714, (2020), 2 October 2020; © 2020 American Chemical Society. https://doi.org/10.1021/acs.joc.0c01861

Palladium-Catalyzed Benzylic Silylation of Diarylmethyl Carbonates with Silylboranes under Base-Free Conditions

A palladium-catalyzed benzylic silylation of diarylmethyl carbonates with silylboranes has been developed. The reaction proceeds smoothly even under external base-free conditions, and the corresponding benzylic silanes are formed in good to high yields. The obtained benzyl silane derivatives can work as the benzylic nucleophiles by the action of a suitable fluoride source and react with some carbon electrophiles to deliver the corresponding benzylic C−C cross-coupled products. Additionally, while still preliminary, the allylic silylation of the isoelectronic allylic carbonates is also achieved.Asai K., Hirano K., Miura M.. Palladium-Catalyzed Benzylic Silylation of Diarylmethyl Carbonates with Silylboranes under Base-Free Conditions. European Journal of Organic Chemistry 2022, e202101535 (2022); https://doi.org/10.1002/ejoc.202101535

Involvement of Nitric Oxide in a Rat Model of Carrageenin-Induced Pleurisy

Some evidence indicates that nitric oxide (NO) contributes to inflammation, while other evidence supports the opposite conclusion. To clarify the role of NO in inflammation, we studied carrageenin-induced pleurisy in rats treated with an NO donor (NOC-18), a substrate for NO formation (L-arginine), and/or an NO synthase inhibitor (S-(2-aminoethyl) isothiourea or NG-nitro-L-arginine). We assessed inflammatory cell migration, nitrite/nitrate values, lipid peroxidation and pro-inflammatory mediators. NOC-18 and L-arginine reduced the migration of inflammatory cells and edema, lowered oxidative stress, and normalized antioxidant enzyme activities. NO synthase inhibitors increased the exudate formation and inflammatory cell number, contributed to oxidative stress, induced an oxidant/antioxidant imbalance by maintaining high O2−, and enhanced the production of pro-inflammatory mediators. L-arginine and NOC-18 reversed the proinflammatory effects of NO synthase inhibitors, perhaps by reducing the expression of adhesion molecules on endothelial cells. Thus, our results indicate that NO is involved in blunting—not enhancing—the inflammatory response

Proactive Received Power Prediction Using Machine Learning and Depth Images for mmWave Networks

This study demonstrates the feasibility of the proactive received power prediction by leveraging spatiotemporal visual sensing information toward the reliable millimeter-wave (mmWave) networks. Since the received power on a mmWave link can attenuate aperiodically due to a human blockage, the long-term series of the future received power cannot be predicted by analyzing the received signals before the blockage occurs. We propose a novel mechanism that predicts a time series of the received power from the next moment to even several hundred milliseconds ahead. The key idea is to leverage the camera imagery and machine learning (ML). The time-sequential images can involve the spatial geometry and the mobility of obstacles representing the mmWave signal propagation. ML is used to build the prediction model from the dataset of sequential images labeled with the received power in several hundred milliseconds ahead of when each image is obtained. The simulation and experimental evaluations using IEEE 802.11ad devices and a depth camera show that the proposed mechanism employing convolutional LSTM predicted a time series of the received power in up to 500 ms ahead at an inference time of less than 3 ms with a root-mean-square error of 3.5 dB

The usefulness of a new gait symmetry parameter derived from Lissajous figures of tri-axial acceleration signals of the trunk

textabstractThis cross-country study adopts a competing theories approach in which both a value perspective and a social capital perspective are used to understand the relation between religion and a country’s business ownership rate. We distinguish among four dimensions of religion: belonging to a religious denomination, believing certain religious propositions, bonding to religious practices, and behaving in a religious manner. An empirical analysis of data from 30 OECD countries with multiple data points per country covering the period 1984–2010 suggests a positive relationship between religion and business ownership based on those dimensions that reflect the internal aspects of religiosity (i.e., believing and behaving). We do not observe a significant association for those dimensions that reflect more external aspects of religion (i.e., belonging and bonding). These results suggest that the social capital perspective prevails the value perspective, at least when internal aspects of religiosity are concerned. More generally, our study demonstrates the importance of distinguishing between different dimensions of religion when investigating the link between religion and entrepreneurship

The Lightest Higgs Boson Mass in Pure Gravity Mediation Model

We discuss the lightest Higgs boson mass in the minimal supersymmetric Standard Model with "pure gravity mediation". By requiring that the model provides the observed dark matter density, we find that the lightest Higgs boson is predicted to be below 132GeV. We also find that the upper limit on the lightest Higgs boson mass becomes 128GeV, if we further assume thermal leptogenesis mechanism as the origin of baryon asymmetry of universe. The interrelations between the Higgs boson mass and the gaugino masses are also discussed.Comment: 18 pages, 5 figures, minor correction

経皮静脈サンプリングで責任腫瘍を同定した腫瘍性骨軟化症の一例

We report a case of 57-year-old-female with progressive bone pain and proximal dominant muscle weakness. Laboratory test revealed hypophosphatemia with decreased TmP/GFR, high bone-type ALP and elevated levels of FGF23. Radiograph and CT examination revealed multiple fracture with decreased levels of bone mineral density. She also had 2 cm of subcutaneous elastic soft tumor which located on the base of left big toe. Moreover, somatostatin receptor scintigraphy revealed increase uptake in the tumor with high suspicion of the culprit tumor of tumor-induced osteomalacia （TIO）. To verify that the tumor generates FGF23, we performed percutaneous venous blood sampling. The FGF23 level in the left dorsal vein of foot was highest those in other veins. These results strongly suggested that the tumor produced FGF23 and was the culprit tumor for the disorder. The patient underwent resection of the tumor. One day after surgery, the serum FGF23 level in a peripheral vein decreased to less than the measurement sensitivity, while serum phosphate improved to normal range. Two months of following surgery, clinical and biochemical examinations confirmed the successful of operation. Although it is sometimes difficult to detect the culprit tumors in TIO cases, a combination of localization studies may improve diagnostic accuracy of the culprit tumors. Furthermore, percutaneous peripheral venous sampling would be clinically useful for cases who have the responsible tumor located on limbs, hands and feet