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

Ultrafast isomerization-induced cooperative motions to higher molecular orientation in smectic liquid-crystalline azobenzene molecules

The photoisomerization of molecules is widely used to control the structure of soft matter in both natural and synthetic systems. However, the structural dynamics of the molecules during isomerization and their subsequent response are difficult to elucidate due to their complex and ultrafast nature. Herein, we describe the ultrafast formation of higherorientation of liquid-crystalline (LC) azobenzene molecules via linearly polarized ultraviolet light (UV) using ultrafast time-resolved electron diffraction. The ultrafast orientation is caused by the trans-to-cis isomerization of the azobenzene molecules. Our observations are consistent with simplified molecular dynamics calculations that revealed that the molecules are aligned with the laser polarization axis by their cooperative motion after photoisomerization. This insight advances the fundamental chemistry of photoresponsive molecules in soft matter as well as their ultrafast photomechanical applications

Relationship between Response to Interferon Therapy and Detection of Hepatitis C Virus RNA by Differential Flotation Centrifugation

We purified an apurinic/apyrimidinic (AP) endonuclease from mouse ascites sarcoma (SR-C3H/He) cells. The enzyme showed nicking activity on acid-depurinated DNA but not on untreated, intact DNA. It also showed priming activity for DNA polymerase on both acid-depurinated and bleomycin-damaged DNA. The priming activity on bleomycin-damaged DNA was two times higher than that on an acid-depurinated DNA. The enzymatic properties indicate that the enzyme is a class II AP endonuclease having DNA 3' repair diesterase activity. The purified enzyme has a molecular weight of 39,000 as determined by sodium dodecyl sulfate-polyacrylamide gel electrophoresis. The optimal pH for AP endonuclease activity was 8.0 in 50 mM Tris-HCl buffer. The AP endonuclease activity depended on divalent cation such as Mg2+ and Co2+ ions, and was inhibited by 2 mM EDTA with no addition of the divalent cation. An appropriate concentration of sodium or potassium salt stimulated the activity. Partial digestion of the AP endonuclease with Staphylococcus aureus V8 protease produced 4 major peptide fragments which may be used for protein sequencing.</p

Photoinduced dynamics during electronic transfer from narrow to wide bandgap layers in one-dimensional heterostructured materials

Electron transfer is a fundamental energy conversion process widely present in synthetic, industrial, and natural systems. Understanding the electron transfer process is important to exploit the uniqueness of the low-dimensional van der Waals (vdW) heterostructures because interlayer electron transfer produces the function of this class of material. Here, we show the occurrence of an electron transfer process in one-dimensional layer-stacking of carbon nanotubes (CNTs) and boron nitride nanotubes (BNNTs). This observation makes use of femtosecond broadband optical spectroscopy, ultrafast time-resolved electron diffraction, and first-principles theoretical calculations. These results reveal that near-ultraviolet photoexcitation induces an electron transfer from the conduction bands of CNT to BNNT layers via electronic decay channels. This physical process subsequently generates radial phonons in the one-dimensional vdW heterostructure material. The gathered insights unveil the fundamentals physics of interfacial interactions in low dimensional vdW heterostructures and their photoinduced dynamics, pushing their limits for photoactive multifunctional applications

Tsunami run-up heights of the 2003 Tokachi-oki earthquake

Tsunami height survey was conducted immediately after the 2003 Tokachi-oki earthquake. Results of the survey show that the largest tsunami height was 4 m to the east of Cape Erimo, around Bansei-onsen, and locally at Mabiro. The results also show that the tsunami height distribution of the 2003 Tokachi-oki earthquake is clearly different from that of the 1952 Tokachi-oki earthquake, suggesting the different source areas of the 1952 and 2003 Tokachioki earthquakes. Numerical simulation of tsunami is carried out using the slip distribution estimated by Yamanaka and Kikuchi (2003). The overall pattern of the observed tsunami height distribution along the coast is explained by the computed ones although the observed tsunami heights are slightly smaller. Large later phase observed at the tide gauge in Urakawa is the edge wave propagating from Cape Erimo along the west coast of the Hidaka area.The 2003 Tokachi-oki earthquak

Tricarboxylic acid cycle activity suppresses acetylation of mitochondrial proteins during early embryonic development in Caenorhabditis elegans

The tricarboxylic acid (TCA) cycle (or citric acid cycle) is responsible for the complete oxidation of acetyl-CoA and formation of intermediates required for ATP production and other anabolic pathways, such as amino acid synthesis. Here, we uncovered an additional mechanism that may help explain the essential role of the TCA cycle in the early embryogenesis of Caenorhabditis elegans. We found that knockdown of citrate synthase (cts-1), the initial and rate-limiting enzyme of the TCA cycle, results in early embryonic arrest, but that this phenotype is not because of ATP and amino acid depletions. As a possible alternative mechanism explaining this developmental deficiency, we observed that cts-1 RNAi embryos had elevated levels of intracellular acetyl-CoA, the starting metabolite of the TCA cycle. Of note, we further discovered that these embryos exhibit hyperacetylation of mitochondrial proteins. We found that supplementation with acetylase-inhibiting polyamines, including spermidine and putrescine, counteracted the protein hyperacetylation and developmental arrest in the cts-1 RNAi embryos. Contrary to the hypothesis that spermidine acts as an acetyl sink for elevated acetyl-CoA, the levels of three forms of acetylspermidine, N1-acetylspermidine, N8-acetylspermidine, and N1,N8-diacetylspermidine, were not significantly increased in embryos treated with exogenous spermidine. Instead, we demonstrated that the mitochondrial deacetylase sirtuin 4 (encoded by the sir-2.2 gene) is required for spermidine\u27s suppression of protein hyperacetylation and developmental arrest in the cts-1 RNAi embryos. Taken together, these results suggest the possibility that during early embryogenesis, acetyl-CoA consumption by the TCA cycle in C. elegans prevents protein hyperacetylation and thereby protects mitochondrial function

フェムト秒X線回折法を用いた超高速格子ダイナミクスの直接観察

京都大学0048新制・課程博士博士(工学)甲第15725号工博第3339号新制||工||1505(附属図書館)28270京都大学大学院工学研究科原子核工学専攻(主査)教授 伊藤 秋男, 教授 河合 潤, 准教授 松尾 二郎学位規則第4条第1項該当Doctor of Philosophy (Engineering)Kyoto UniversityDFA

Photo-induced lattice softening of excited-state VO2

In this letter, we demonstrated the photoexcitation of metallic phase vanadium dioxide (VO_2) with time-resolved x-ray diffraction measurements. Through the photoexcitation, the metallic phase VO_2 transitioned to the similar transient state, which was presented in the insulator to metal phase transition in the time-scale of ∼10 ps. This transient state was accessed only by the photoexcitation and not through further thermal excitation. The presence of the transient state could be an important factor in any further application of the phase transition phenomena

Characterization of structural dynamics of VO2 thin film on c-Al2O3 using in-air time-resolved x-ray diffraction

The lattice motion and displacement of atoms in the unit cell in vanadium dioxide (VO2) grown on c-Al2O3 were characterized by static and time-resolved x-ray diffraction (XRD) measurements. The monoclinic-tetragonal phase transition of the VO2 unit cell and the twist motion of vanadium atoms in the unit cell were observed. The time-resolved XRD measurements were performed in air using a tabletop high-repetition femtosecond laser. The results obtained from the time-resolved XRD measurements suggested that the unit cell of the low-temperature monoclinic VO2 transformed into the high-temperature tetragonal phase extremely rapidly (within 25 ps); however, the atoms in the unit cell fluctuated or vibrated about the center of the tetragonal coordinates, which abated within ∼100 ps. Thus, the time-resolved XRD measurements of the Bragg angle, intensity, and width of the diffraction lines simultaneously revealed the phase transition of VO2 and the atomic motion in the unit cell