Relationship between the water quality of three main rivers and geology of Okayama Prafecture

Concentrations of inorganic major components (Ca2+, Mg2+, Na+, K+, ΣFe, AI3+, HCO3, SO4, CI-, NO3, F- and SiO2) were measured in 57 water samples from three main rivers, the Yoshii, Asahi and Takahashi Rivers and their tributaries. The water quality is discussed in relation to the geological environment in the drainage basin of three rivers. The following results were obtained from the investigation. The degree of influence of rocks on the water quality was limestone≫basic rocks>clastic rocks>andesite>rhyolite>gramite. The influence of geology is clear in the riverhead but it is obscure in the downstream. The concentration of each component increases generally from the upper stream to the lower stream but that of SiO2 only decreases in the lower stream. Kaolinite is a stable mineral as a weathering prodouct from the ion compositions of three rivers. In a rough estimation, Yoshii, Asahi and Takahashi Rivers weather 303,000t, 433,000t and 1,033,000t of the rocks respectively from their basins in a year. The syrface of their basins are scraoed off 0.06mm, 0.11mm and 0.15mm respectively in a year

スマート適応制御システムの設計

広島大学(Hiroshima University)博士(工学)Doctor of Engineeringdoctora

Production of Insect Toxin Beauvericin From Entomopathogenic Fungi Cordyceps Militaris by Heterologous Expression of Global Regulator

Cordyceps militaris is one of entomopathogenic fungi species that is well known to be a traditional medicine in China for decades. Although the pharmaceutical and/or toxic properties of C. militaris has attracted attention as a promising resource for finding bioactive compounds, only a few substances including cordycepin have been reported so far. In the previous report heterologous expression of LaeA, a global regulator for secondary metabolites production in fungi, has been succeeded in C. militaris. The LaeA-engineered transformants are proved to produce new and/or elevated production of secondary metabolites, as detected by HPLC analysis. In order to further characterize the secondary metabolites that were being significantly produced by LaeA transformant, HPLC profiling and structure elucidation by proton NMR were conducted in two target compounds, designated as compound 1 and compound 2. Compound 1 possessed the highly similar characters to insect toxin beauvericin in UV spectrum, molecular weight, and retention time in HPLC analysis. Proton NMR analysis revealed that compound 1 had the same proton signals as beauvericin

Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2

Complexation-induced axial chirality around an N-P bond occurs upon the predominant coordination of the N-phosphinoyl group in the N-phosphine oxide-substituted imidazolinylidene (SPoxIm) to B(C6F5)3. (Ra) and (Sa) atropisomers of (κ-O-SPoxIm)B(C6F5)3 were observed independently in the single-crystal lattice and the optimized gas-phase structure. Experimental and theoretical studies confirmed that this axial chirality arises from the restricted rotation around the N-P bond, caused by the steric repulsion between the C5-H atoms of the imidazolinylidene ring and the C6F5 rings on the B(C6F5)3 unit. Conversely, this axial chirality was not certainly observed via the complexation between SPoxIm and Al(C6F5)3. The carbene carbon atoms in (κ-O-SPoxIm)E(C6F5)3 (E = B, Al) remain sufficiently nucleophilic to react with CO2, and the phosphinoylation of CO2 with SPoxIm proceeds far more rapidly in the presence of a catalytic amount of Al(C6F5)3 than in the absence of Al(C6F5)3Asada T., Hoshimoto Y., Kawakita T., et al. Axial chirality around N-P bonds induced by complexation between E(C6F5)3 (E = B, Al) and an N-phosphine oxide-substituted imidazolinylidene: A key intermediate in the catalytic phosphinoylation of CO2. Journal of Organic Chemistry 85, 14333 (2020); https://doi.org/10.1021/acs.joc.9b03210

Room-Temperature Reversible Chemisorption of Carbon Monoxide on Nickel(0) Complexes

Chemisorption on organometallic-based adsorbents is crucial for the controlled separation and long-term storage of gaseous molecules. The formation of covalent bonds between the metal centers in the adsorbents and the targeted gases affects the desorption efficiency, especially when the oxidation state of the metal is low. Herein, we report a pressure-responsive nickel(0)-based system that is able to reversibly chemisorb carbon monoxide (CO) at room temperature. The use of N-heterocyclic carbene ligands with hemi-labile N-phosphine oxide substituents facilitates both the adsorption and desorption of CO on nickel(0) via ligand substitution. Ionic liquids were used as the reaction medium to enhance the desorption rate and establish a reusable system. These results showcase a way for the sustainable chemisorption of CO using a zero-valent transition-metal complex.Yamauchi Y., Hoshimoto Y., Kawakita T., et al. Room-Temperature Reversible Chemisorption of Carbon Monoxide on Nickel(0) Complexes. Journal of the American Chemical Society , (2022); https://doi.org/10.1021/jacs.2c02870

A boron-transfer mechanism mediating the thermally induced revival of frustrated carbene–borane pairs from their shelf-stable adducts

Chemists have designed strategies that trigger the conformational isomerization of molecules in response to external stimuli, which can be further applied to regulate the complexation between Lewis acids and bases. We have recently developed a system in which frustrated carbene–borane pairs are revived from shelf-stable but external-stimuli-responsive carbene–borane adducts comprised of N-phosphine-oxide-substituted imidazolylidenes (PoxIms) and triarylboranes. Herein, we report the detailed mechanism on this revival process. A thermally induced borane-transfer process from the carbene carbon atom to the N-phosphinoyl oxygen atom initiates the transformation of the carbene–borane adduct. Subsequent conformational isomerization via the rotation of the N-phosphinoyl group in PoxIm moieties eventually leads to the revival of frustrated carbene–borane pairs that can cleave H2. We believe that this work illustrates an essential role of dynamic conformational isomerization in the regulation of the reactivity of external-stimuli-responsive Lewis acid-base adducts that contain multifunctional substituents.Hoshimoto Y., Sakuraba M., Kinoshita T., et al. A boron-transfer mechanism mediating the thermally induced revival of frustrated carbene–borane pairs from their shelf-stable adducts. Communications Chemistry 4, 137 (2021); https://doi.org/10.1038/s42004-021-00576-1

High resting metabolic rates with low thermal dependence induce active dives in overwintering Pacific juvenile loggerhead turtles

UTokyo FOCUS Articles掲載「三陸のウミガメは寒冷地仕様 高い休止代謝速度と低い温度依存性によって冬季でも活動性を維持」https://www.u-tokyo.ac.jp/focus/ja/articles/a_00627.htmlUTokyo FOCUS Articles "Cold never bothered me anyway Pacific sea turtles\u27 metabolisms stay active over winter" https://www.u-tokyo.ac.jp/focus/en/articles/z0508_00003.htm

Strategic Utilization of Multifunctional Carbene for Direct Synthesis of Carboxylic–Phosphinic Mixed Anhydride from CO2

Direct synthesis of carboxylic–phosphinic mixed anhydrides has been achieved by treating carbon dioxide with N-phosphine oxide-substituted imidazolylidenes (PoxIms) that contain both nucleophilic carbene and electrophilic phosphorus moieties. This novel mixed anhydride was efficiently derivatized into an ester, an amide, and an unsymmetrical ketone via transformation into its corresponding imidazolium salt followed by a dual substitution reaction. The presented work used well-designed multifunctional carbene reagents to establish a novel utility for carbon dioxide in organic synthesis.Hoshimoto Y., Asada T., Hazra S., et al. Strategic Utilization of Multifunctional Carbene for Direct Synthesis of Carboxylic–Phosphinic Mixed Anhydride from CO2. Angewandte Chemie - International Edition 55, 16075 (2016); https://doi.org/10.1002/anie.201609710

The 3′-Phosphoadenosine 5′-Phosphosulfate Transporters, PAPST1 and 2, Contribute to the Maintenance and Differentiation of Mouse Embryonic Stem Cells

Recently, we have identified two 3′-phosphoadenosine 5′-phosphosulfate (PAPS) transporters (PAPST1 and PAPST2), which contribute to PAPS transport into the Golgi, in both human and Drosophila. Mutation and RNA interference (RNAi) of the Drosophila PAPST have shown the importance of PAPST-dependent sulfation of carbohydrates and proteins during development. However, the functional roles of PAPST in mammals are largely unknown. Here, we investigated whether PAPST-dependent sulfation is involved in regulating signaling pathways required for the maintenance of mouse embryonic stem cells (mESCs), differentiation into the three germ layers, and neurogenesis. By using a yeast expression system, mouse PAPST1 and PAPST2 proteins were shown to have PAPS transport activity with an apparent Km value of 1.54 µM or 1.49 µM, respectively. RNAi-mediated knockdown of each PAPST induced the reduction of chondroitin sulfate (CS) chain sulfation as well as heparan sulfate (HS) chain sulfation, and inhibited mESC self-renewal due to defects in several signaling pathways. However, we suggest that these effects were due to reduced HS, not CS, chain sulfation, because knockdown of mouse N-deacetylase/N-sulfotransferase, which catalyzes the first step of HS sulfation, in mESCs gave similar results to those observed in PAPST-knockdown mESCs, but depletion of CS chains did not. On the other hand, during embryoid body formation, PAPST-knockdown mESCs exhibited abnormal differentiation, in particular neurogenesis was promoted, presumably due to the observed defects in BMP, FGF and Wnt signaling. The latter were reduced as a result of the reduction in both HS and CS chain sulfation. We propose that PAPST-dependent sulfation of HS or CS chains, which is regulated developmentally, regulates the extrinsic signaling required for the maintenance and normal differentiation of mESCs