Pd-Catalyzed Allylic Substitution of Azo-Ene Adducts Enables Net Allylic C-H Alkylation of Allylic Alcohols

We present a protocol for a regioselective allylic C–H alkylation of allylic alcohols, consisting of a sequential azo-ene reaction and attendant Pd-catalyzed allylic substitution with Grignard reagents. Notable features of this work include: (1) regioselective C(sp³)-C(sp³) bond formation is achieved under Pd-catalysis, and (2) the allylic substitution proceeds with retention of configuration at the electrophilic allylic carbon as well as the olefin geometry

非平衡グリーン関数法の誘起核分裂反応への応用

京都大学新制・課程博士博士(理学)甲第25803号理博第5114号京都大学大学院理学研究科物理学・宇宙物理学専攻(主査)教授 萩野 浩一, 准教授 金田 佳子, 教授 杉本 茂樹学位規則第4条第1項該当Doctor of ScienceKyoto UniversityDFA

Circulating galectin-9 as a novel prognosticator in patients with intrahepatic cholangiocarcinoma undergoing surgical resection

Background: Intrahepatic cholangiocarcinoma (ICC) is a rare but highly malignant liver cancer. Surgical resection provides the best long-term survival, yet poor prognosis requires improved treatments. Galectin-9 (GAL9) has gained attention for its role in tumor biology. This study investigated circulating galectin-9 (cGAL9) levels in ICC patients undergoing resection, along with tumor tissue characteristics. Methods: GAL9 expression levels in circulating and tumor cells were measured using enzyme-linked immunosorbent assay and immunohistochemistry (IHC) in 91 ICC surgical patients. The mRNA expression levels of candidate genes were analyzed in 44 available frozen tissue samples. Results: The optimal cGAL9 cutoff was 12.0 ng/ml using minimum P value approach. Higher cGAL9 levels linked to multiple tumors (P = 0.046), poorer overall survival (OS), and recurrence-free survival (RFS). Tumor cell GAL9 expression by IHC did not correlate with OS or RFS. cGAL9 levels did not correlate with tumor cell expression in IHC analyses or GAL9 mRNA in resected specimens. However, cGAL9 levels correlated with mRNA levels of glycolysis markers (glucose transporter 1 and hypoxia inducible factor 1 alpha). Conclusions: Preoperative cGAL9 serves as a novel prognosticator for ICC patients after surgical resection. Its association with glycolysis highlights the potential for therapeutic guidance

Seismic source mechanism of the tsunami near the Sofu Seamount on October 8, 2023

On October 8, 2023, between 18:50 and 22:00, a cluster of earthquakes occurred near Sofu Seamount, and a tsunami advisory was issued for the surrounding areas. Previous studies showed that the main source of this tsunami was an uplift near the Sofu Seamount and the tsunami could be simulated by the summation of the multiple sources over time. To clarify the seismic mechanism of this volcanic activity, we performed the seismic waveform inversion and cross-correlation analysis. We obtained the source-time function of the 13 repeated earthquakes and found that the source mechanism of the tsunamigenic event was a force symmetric about the vertical axis, such as single-force, isotropic, or vertical compensated-linear-vector-dipole (CLVD) mechanisms. We also found that there were low-frequency harmonic signals between earthquakes, which do not come with clear body waves. We interpreted these signals as a caldera collapse and resonance of the magma reservoir. The repeated earthquakes can be interpreted as the vertical movement of the rock column, supplying magma to the magma chamber and causing the uplift of the caldera floor that excited tsunamis. The harmonic signals between earthquakes may be the resonance at the magma reservoir associated with the magma migration. We assumed that the edifice subsided slowly between earthquakes and repeated this inflation-deflation cycle along with the earthquakes

Foreword (Special Issue : Deception)

本特集号は、二〇二四年四月二〇日に開催した史学研究会例会の報告をもとにしている

Amaterasuite, Sr₄Ti₆Si₄O₂₃(OH)Cl, a new mineral from jadeitite, a representative stone of Japan

新鉱物・アマテラス石の発見 --日本の国石「ヒスイ」から見つかった新種の鉱物-- . 京都大学プレスリリース. 2025-08-07.Amaterasuite is a new mineral found in jadeitite, a representative stone of Japan, and was thus named after Amaterasu Omikami, one of the most important goddesses in Japanese mythology, as a tribute to Japanese stone culture. The new mineral was found in the Osayama mountain area, Osa-osakabe, Niimi City, Okayama Prefecture, Japan. Amaterasuite appears as bundles consisting of needle- to plate-shaped crystals as large as 150 µm around rutile. The Mohs hardness is 6. Its tenacity is brittle, and its calculated density is 4.0 g·cm⁻³. Under plane-polarized light, the mineral is pleochroic, changing from blue to brown. The empirical formula, calculated on the basis of 23 O + 2 (OH,Cl) atoms per formula unit, is (Sr₃.₃₂Ba₀.₆₄)Σ₃.₉₆(Ti₅.₇₃Fe₀.₁₆Nb₀.₀₂)Σ₅.₉₁Si₄.₁₅O₂₃(OH)₀.₉₅Cl₁.₀₅; thus, its ideal formula is Sr₄Ti₆Si₄O₂₃(OH)Cl. The unit-cell parameters refined by powder X-ray diffraction using 80 peaks with large d-values are a = 5.85558(2) Å, b = 20.43960(8) Å, c = 33.28240(12) Å, and V = 3983.43(3) ų (Z = 8) in the orthorhombic Fddd space group. The structure of amaterasuite from the metajadeitite area was fully identified as amaterasuite-4O, which is characterized by its dual nature, encapsulating two types (A and B) within a unit cell. The occupancy rates of the A and B types were estimated to be ∼ 85 and ∼ 15%, respectively. The refined site occupancies at the SrA and BaB sites indicate a strong site preference for Sr, similar to the preferential site occupancies in synthetic titanosilicate compounds

アプタマーを標的リガンドとして用いた抗腫瘍薬送達システムの設計

京都大学新制・課程博士博士(薬科学)甲第25936号薬科博第202号京都大学大学院薬学研究科薬科学専攻(主査)教授 樋口 ゆり子, 教授 山下 富義, 教授 寺田 智祐学位規則第4条第1項該当Doctor of Pharmaceutical SciencesKyoto UniversityDFA

Caspase-mediated cleavage of a scaffold protein, MPRIP, yields a truncated form that is involved in repetitive bleb formation

Membrane blebbing is a hallmark of apoptotic cell death. However, the molecular mechanism that regulates this event has not been fully elucidated. To understand this underlying mechanism, we developed visualization systems suitable for spatiotemporal analysis. By monitoring the plasma membrane labeled with a fluorescent protein and reconstructing the image data as three-dimensional (3D) volumes based on the rendering technique, we observed that dying cells exhibit cycles of bleb formation at the same region of the cell surface. In addition, a Förster Resonance Energy Transfer (FRET)-based biosensor incorporating a regulatory myosin light chain (RMLC) displayed phosphorylation at the base of the retracting bleb, and dephosphorylation before re-expansion, implying the involvement of not only a kinase but also a phosphatase in the regulation of RMLC. To extend these observations, we focused on a scaffold protein, myosin phosphatase Rho interacting protein (MPRIP), which interacts with RhoA and myosin phosphatase targeting subunit 1 (MYPT1), involved in activation of Rho-associated coiled-coil kinase-I (ROCK-I) or protein phosphatase 1 (PP1), respectively. We found that MPRIP is cleaved both in dying cells and in an in vitro cleavage assay in a caspase-dependent manner. A cleaved C-terminal peptide fragment maintains the interaction with MYPT1. Cytological analysis showed that this fragment forms a complex with MYPT1 and myosin after translocating to the cytoplasm. These results suggest that this complex formation promotes the dephosphorylation of RMLC. Collectively, our study indicates that repetitive bleb formation, which is unique to apoptosis, is regulated by both phosphorylation and dephosphorylation of RMLC through MPRIP in a coordinated manner

Cooperative transportation of an object with a nonholonomic constraint by a swarm robot

In this paper, we propose a distributed controller for the cooperative transportation of an object with a nonholonomic constraint by a swarm robot. Because an object with passive wheels fixed to it does not slide along the axle direction, its velocity constraint is nonholonomic. We set the center of rotation of the object as a control point of the entire system. To derive the control point of an object with passive fixed wheels, we analyze dynamics of the object. Then we design a distributed cooperative transportation controller considering the nonholonomic constraint of an object with passive fixed wheels based on a kinematic model. We divide the distributed controller into two steps. In the first step, each robot derives the desired velocity and angular velocity of the object to achieve its desired position and orientation. In the second step, each robot calculates its desired velocity to achieve the object’s desired velocity and angular velocity. Each robot moves and pushes the object using the distributed controller, and can transport it to the desired position and orientation. We verify the effectiveness of the proposed controller in dynamic simulations and real robot experiments