凝縮相における振電相互作用に関する理論的研究

京都大学新制・課程博士博士(工学)甲第25014号工博第5191号新制||工||1991(附属図書館)京都大学大学院工学研究科分子工学専攻(主査)教授 佐藤 徹, 教授 田中 庸裕, 教授 佐藤 啓文学位規則第4条第1項該当Doctor of Philosophy (Engineering)Kyoto UniversityDGA

Model Building of Metal Oxide Surfaces and Vibronic Coupling Density as a Reactivity Index: Regioselectivity of CO2_2 Adsorption on Ag-loaded Ga2_2O3_3

The step-by-step hydrogen-terminated (SSHT) model is proposed as a model for the surfaces of metal oxides. Using this model, it is found that the vibronic coupling density (VCD) can be employed as a reactivity index for surface reactions. As an example, the regioselectivity of CO$_2$ adsorption on the Ag-loaded Ga$_2$O$_3$ photocatalyst surface is investigated based on VCD analysis. The cluster model constructed by the SSHT approach reasonably reflects the electronic structures of the Ga$_2$O$_3$ surface. The geometry of CO$_2$ adsorbed on the Ag-loaded Ga$_2$O$_3$ cluster has a bent structure, which is favorable for its photocatalytic reduction to CO.Comment: 18 pages, 11 figure

Localised surface plasmon resonance inducing cooperative Jahn–Teller effect for crystal phase-change in a nanocrystal

結晶中の電子の集団的な運動が原子を動かすプラズモン誘起原子変位を初めて発見 --見えない光学センサーなど新技術の実現に期待--. 京都大学プレスリリース. 2023-08-01.The Jahn–Teller effect, a phase transition phenomenon involving the spontaneous breakdown of symmetry in molecules and crystals, causes important physical and chemical changes that affect various fields of science. In this study, we discovered that localised surface plasmon resonance (LSPR) induced the cooperative Jahn–Teller effect in covellite CuS nanocrystals (NCs), causing metastable displacive ion movements. Electron diffraction measurements under photo illumination, ultrafast time-resolved electron diffraction analyses, and theoretical calculations of semiconductive plasmonic CuS NCs showed that metastable displacive ion movements due to the LSPR-induced cooperative Jahn–Teller effect delayed the relaxation of LSPR in the microsecond region. Furthermore, the displacive ion movements caused photo-switching of the conductivity in CuS NC films at room temperature (22 °C), such as in transparent variable resistance infrared sensors. This study pushes the limits of plasmonics from tentative control of collective oscillation to metastable crystal structure manipulation

Role of Catalyst Support and Regioselectivity of Molecular Adsorption on a Metal Oxide Surface: NO Reduction on Cu/{\gamma}-alumina

The role of catalyst support and regioselectivity of molecular adsorption on a metal oxide surface is investigated for the NO reduction on a Cu/{\gamma}-alumina heterogeneous catalyst. For the solid surface, computational models of the {\gamma}-alumina surface are constructed based on the Step-by-Step Hydrogen Termination (SSHT) approach. Dangling bonds, which appear by cutting the crystal structure of a model, are terminated stepwise with H atoms until the model has an appropriate energy gap. The obtained SSHT models exhibit the realistic infrared (IR) and ultraviolet-visible (UV/Vis) spectra. Vibronic coupling density (VCD), as a reactivity index, is employed to elucidate the regioselectivity of the Cu adsorption on the {\gamma}-alumina and that of the NO adsorption on the Cu/{\gamma}-alumina in place of the frontier orbital theory that could not provide clear results. We discovered that the highly dispersed Cu atoms are loaded on Lewis-basic O atoms, which is known as anchoring effect, located in the tetrahedral sites of the {\gamma}-alumina surface. The role of the {\gamma}-alumina support is to raise the frontier orbital of the Cu catalyst, which in turn gives rise to the electron back-donation from the Cu/{\gamma}-alumina to NO. In addition, the penetration of the VCD distribution of the Cu/{\gamma}-alumina into the {\gamma}-alumina support indicates that the excessive reaction energies dissipate into the support after the NO adsorption and reduction. In other words, the support plays the role of a heat bath. The NO reduction on the Cu/{\gamma}-alumina proceeds even in an oxidative atmosphere because the Cu-NO bond is strongly bounded compared to the Cu-O2 bond

SBRT FOR CENTRAL LUNG TUMORS WITH 56 Gy/7 fr

Stereotactic body radiotherapy (SBRT) for centrally‑located lung tumors remains a challenge because of the increased risk of treatment‑related adverse events (AEs), and uncertainty around prescribing the optimal dose. The present study reported the results of central tumor SBRT with 56 Gy in 7 fractions (fr) at the University of Tokyo Hospital. A total of 35 cases that underwent SBRT with or without volumetric‑modulated arc therapy consisting of 56 Gy/7 fr for central lung lesions between 2010 and 2016 at the University of Tokyo Hospital were reveiwed. A central lesion was defined as a tumor within 2 cm of the proximal bronchial tree (RTOG 0236 definition) or within 2 cm in all directions of any critical mediastinal structure. Local control (LC), overall survival (OS), and AEs were investigated. The Kaplan‑Meier method was used to estimate LC and OS. AEs were scored per the Common Terminology Criteria for Adverse Events Version 4.0. Thirty‑five patients with 36 central lung lesions were included. Fifteen lesions were primary non‑small cell lung cancer (NSCLC), 13 were recurrences of NSCLC, and 8 had oligo‑recurrences from other primaries. Median tumor diameter was 29 mm. Eighteen patients had had prior surgery. At a median follow‑up of 13.1 months for all patients and 18.3 months in surviving patients, 22 patients had died, ten due to primary disease (4 NSCLC), while three were treatment‑related. The 1‑ and 2‑year OS were 57.3 and 40.4%, respectively, and median OS was 15.7 months. Local recurrence occurred in only two lesions. 1‑ and 2‑year LC rates were both 96%. Nine patients experienced grade ≥3 toxicity, representing 26% of the cohort. Two of these were grade 5, one pneumonitis and one hemoptysis. Considering the background of the subject, tumor control of our central SBRT is promising, especially in primary NSCLC. However, the safety of SBRT to central lung cancer remains controversial

Successful laparoscopic resection of virilizing ovarian steroid cell tumor, not otherwise specified, in a 22-year-old woman: a case report and evaluation of the steroidogenic pathway

Objective: Ovarian steroid cell tumor (SCT) is a rare tumor with steroid-producing ability. We report a 22-year-old woman with secondary amenorrhea and hirsutism caused by an ovarian SCT-not otherwise specified (NOS), who underwent successfully laparoscopic resection of the tumor. Case report: A 22-year-old null gravida woman presented to a hospital, having amenorrhea for 18 months and increasing facial hair. Physical examination revealed obesity (body mass index, 37.3 kg/m2) with evident facial and trunk hair. Total and free serum testosterone, and dehydroepiandrosterone sulfate levels were found to be elevated. Levels of serum adrenocorticotropic hormone, gonadotropins, cortisol, aldosterone, and ovarian steroids were observed to be within reference intervals. Although polycystic ovaries were not found, a hyperechogenic solid tumor (3 cm) was detected on transvaginal ultrasonography. Laparoscopic resection of the tumor was performed. One month post-surgery, total and free testosterone levels were observed to have decreased, and menstruation resumed two months thereafter. The patient was histologically diagnosed with ovarian SCT-NOS. Expression of ovarian steroidogenic enzymes, which are related to hyperandrogenism, was observed. No disease recurrence has been reported for more than 5 years post-surgery

Development of Gas Multiplier Counters (GMCs) Onboard the 6U CubeSat X-Ray Observatory NinjaSat

We report the development of Gas Multiplier Counters (GMCs) onboard the 6U CubeSat X-ray observatory NinjaSat, scheduled to be launched in October 2023. GMC is a 1U-size non-imaging gas X-ray detector sensitive to 2–50 keV X-rays, and two identical GMCs are mounted on NinjaSat. GMC consists of a gas cell filled with a xenon/argon/dimethyl ether (75%/24%/1%) gas mixture with a pressure of 1.2 atm at 0◦C, a high voltage supply and analog signal processing board, a digital signal processing board, an X-ray collimator of a 2.1◦ field of view, and an iron-55 calibration source. The most significant feature of the GMC is its large effective area of 32 cm2 at 6 keV, which is more than two orders of magnitude larger than the X-ray detectors onboard previously launched CubeSats. We have achieved this at a low cost and in a short development time by employing a gas detector that can easily increase its effective area and using a space-proven gas electron multiplier. GMC was characterized with X-rays from an X-ray generator in a laboratory and monochromatic X-rays on the BL-14A beamline at the KEK synchrotron radiation facility. In this paper, we present the design of GMC and the preliminary results of the detector calibration

NinjaSat: 6U CubeSat Observatory for Bright X-Ray Sources

NinjaSat is a 6U CubeSat observatory designed for long-term monitoring of bright X-ray sources, such as binary systems between normal stars and black holes or neutron stars. NinjaSat is the first Japanese CubeSat dedicated to astronomical observation, and it is also a mission to demonstrate that even a small satellite, which can be developed quickly and inexpensively, unlike large satellites, can perform excellent scientific observations. NinjaSat realizes the world’s highest X-ray sensitivity in CubeSat missions by using gas X-ray detectors filling the entire space allocated for science payloads. The fabrication of the flight model payloads began in 2021, and testing at the payload component level was completed in August 2022; as of April 2023, the payloads were integrated into the Nano Avionics 6U bus (M6P) in Lithuania. After four months of testing, the payload will be stored in the Exolaunch deployer in August and launched by the SpaceX Transporter-9 mission in October 2023. This paper will describe the scientific objectives, satellite structure, payloads, and operations of NinjaSat

Development of Radiation Belt Monitors for the 6U CubeSat X-Ray Observatory NinjaSat

NinjaSat is a 6U CubeSat-sized X-ray observatory to be launched into the low Earth orbit at an altitude of 550 km, and is scheduled for launch this October. NinjaSat is equipped with two 1U-sized gas X-ray detectors (GMC) and is expected to operate mainly for astronomical observations of bright X-ray objects in the sky, such as neutron stars and black holes. Since high voltages are applied to the gas cells of GMC, two radiation belt monitors (RBM) will also be installed to protect GMC from electrical discharges potentially caused by excessively high rate of charged particles. NinjaSat RBM will play a fail-safe function in the voltage suppression operation of GMC in the auroral zone and South Atlantic Anomaly, and also protect GMC from charged particles such as protons and electrons that arrive unexpectedly due to solar flares or other low-Earth orbit radiation events. RBM uses a 9 mm x 9 mm Si-PIN photodiode as a charged particle sensor. By taking advantage of the difference in sensor response to protons and electrons, the sensor is designed to simultaneously count charged particle rates at multiple energy thresholds so that GMC protection function will operate even if either the proton or electron rate increases. RBM can count up to about 10 kcps with almost no loss of counts, and proton beam tests have confirmed that the response performance is sufficient to protect GMC against excessively high charged particle rates above 10 Mcps without choking the circuitry. The flight models of the RBM have passed the thermal vacuum and vibration tests last year. The developed RBM occupies only about 6% of the 1U CubeSat size in volume and weighs only 70g. In addition, since the RBM uses inexpensive, commercially available sensors, it could be installed on small satellites other than NinjaSat with relatively small development resources