In situ TREXS Observation of Surface Reduction Reaction of NiO Film with ∼2 nm Surface Sensitivity

X‐ray absorption fine structure (XAFS) spectroscopy is one of the most widely used methods at synchrotron radiation facilities. XAFS gives us information on chemical states and local structures. Fundamentally, XAFS is bulk sensitive, not surface sensitive. If a surface sensitive XAFS method was available, surface chemical reactions can be observed under realistic conditions. Here, we report the development and present status of a type of surface sensitive x‐ray spectroscopy, which is named total reflection x‐ray spectroscopy, TREXS.     

Finding Degradation Trigger Sites of Structural Materials for Airplanes Using X‐Ray Microscopy

Macroscopic properties of carbon fiber‐reinforced plastic (CFRP) and environmental barrier coating (EBC), widely used for airplanes, can be deteriorated by local cracks or degradation (“trigger sites”). We have tried to find these trigger sites using x‐ray microscopy (XM), which can provide the 2D or 3D images of the chemical states and microstructures. Crack initiation in CFRP was observed in a non‐destructive manner in multi‐scales (nm‐mm). 3D chemical‐state mapping of Yb in EBC was achieved with high resolution (<50 nm). In addition to XM, in‐situ observations at high temperatures were conducted for obtaining complementary information. X‐ray absorption spectroscopy (XAS) and x‐ray diffraction (XRD) analysis were performed simultaneously up to 1773 K. Dynamic XAS with short time‐resolution (<10 ns) was conducted to investigate changes in the local structure of metal. These approaches can help us identify degradation trigger sites in the materials.     

A new aliphatic ester of hydroxysalicylic acid from fermented Carica papaya L. preparation with a potential hair growth stimulating activity

Abstract

An aliphatic ester of hydroxysalicylic acid (6), reported for the first time from a natural source in addition to five known compounds were isolated from the fermented Carica papaya L. preparation, a commercialized functional food. The known compounds were identified as 5-hydroxymethylfurfuraldehyde (1), trans-caffeic acid (2), butyl 4-hydroxybenzoate (butylparaben) (3), lycopene (4), benzyl isothiocyanate (5). Compounds 1 and 3 were reported for the first time from Papaya fruits through this study. The new compound showed a moderate antioxidant activity and a potent hair growth stimulating activity in vitro.     

Phloroglucinol derivatives and a chromone glucoside from the leaves of Myrtus communis

Seven new phloroglucinol derivatives, myrtucommunins A–D (1–4), 6-methylisomyrtucommulone B (5), 4-methylmyrtucommulone B (6), and 2-isobutyryl-4-methylphloroglucinol 1-O-β-d-glucopyranoside (7), and one new chromone derivative, undulatoside A 6′-O-gallate (8), were isolated from the leaves of Myrtus communis (Myrtaceae). Myrtucommunins A–D (1–4) were conjugates of polymethylated acylphloroglucinol and flavonol rhamnoside. The absolute configurations of the rhamnosyl moieties for 1–4 were confirmed to be l in each case by HPLC analyses, while those of the aglycones were assigned by comparisons of the experimental and TDDFT calculated ECD spectra. 6-Methylisomyrtucommulone B (5) and 4-methylmyrtucommulone B (6) were assigned as 6/6/6 tricyclic acylphloroglucinol derivatives with a racemic nature. Antimicrobial activities of 1–8 and related known compounds were evaluated.     

11C-Cyanation of Aryl Fluorides via Nickel and Lithium Chloride-Mediated C−F Bond Activation

Aryl fluorides are expected to be useful as radiolabeling precursors due to their chemical stability and ready availability. However, direct radiolabeling via carbon-fluorine (C−F) bond cleavage is a challenging issue due to its significant inertness. Herein, we report a two-phase radiosynthetic method for the ipso-¹¹C-cyanation of aryl fluorides to obtain [¹¹C]aryl nitriles via nickel-mediated C−F bond activation. We also established a practical protocol that avoids the use of a glovebox, except for the initial preparation of a nickel/phosphine mixture, rendering the method applicable for general PET centers. This method enabled the efficient synthesis of diverse [¹¹C]aryl nitriles from the corresponding aryl fluorides, including pharmaceutical drugs. Stoichiometric reactions and theoretical studies indicated a significant promotion effect of lithium chloride on the oxidative addition, affording an aryl(chloro)nickel(II) complex, which serves as a precursor for rapid ¹¹C-cyanation.     

Palladium-catalyzed direct arylation of aryl(azaaryl)methanes with aryl halides providing triarylmethanes

Direct arylation of aryl(azaaryl)methanes with aryl halides takes place at the benzylic position in the presence of a hydroxide base under palladium catalysis to yield triarylmethanes.     

Existing condition and migration property of ions in lithium electrolytes with ionic liquid solvent

Ionization conditions of each ionic species in lithium ionic liquid electrolytes, LiTFSI/BMI-TFSI and LiTFSI/BDMI-TFSI, were confirmed based on the diffusion coefficients of the species measured by the pulsed gradient spin-echo (PGSE) NMR technique. We found that the diffusion coefficient ratios of the cation and anion species D(Li)(obs)/D(F)(obs) of the lithium salt and D(H)(obs)/D(F)(obs) of the ionic liquid solvent were effective guides to evaluate the ionization condition responsible for their mobility. Lithium ions were found to be stabilized, forming the solvated species as Li(TFSI)3(2-). TFSI- anion coordination could be relaxed by the dispersion of silica to form a gel electrolyte, LiTFSI/BDMI-TFSI/silica. It is expected that the oxygen sites on the silica directly attract Li+, releasing the TFSI- coordination. The lithium species, loosing TFSI- anions, kept a random walk feature in the gel without the diffusion restriction attributed from the strong chemical and morphological effect as that in the gel with the polymer. We can conclude that the silica dispersion is a significant approach to provide the appropriate lithium ion condition as a charge-transporting species in the ionic liquid electrolytes.     

Physical and theoretical aspects of a new vacuum arc controltechnology-self arc diffusion by electrode: SADE

Our new vacuum arc control technology SADE doubles the high current interruption capability of our conventional axial magnetic field technology. First, we describe the vacuum arc motion behavior recorded by a high speed charge-coupled device video camera. This arc behavior is closely related to axial magnetic field intensity. In particular, it depends on the profile of the externally generated axial magnetic field. The anode spot is likely to move to the highest magnetic field intensity. Second, we describe analytical results for concentration of vacuum arc at the anode side contact surface. This analysis implies the possibility of an ideal magnetic field profile and intensity for vacuum arc control. Finally, we describe experimental results for vacuum arc control compared with the physical and theoretical results mentioned above, and we show a practical electrode configuration for vacuum interrupters and its application in a high current interruption experiment     

A compact permanent‐magnet system for measuring magnetic circular dichroism in resonant inelastic soft X‐ray scattering

A compact and portable magnet system for measuring magnetic dichroism in resonant inelastic soft X‐ray scattering (SX‐RIXS) has been developed at the beamline BL07LSU in SPring‐8. A magnetic circuit composed of Nd–Fe–B permanent magnets, which realised ～0.25 T at the center of an 11 mm gap, was rotatable around the axis perpendicular to the X‐ray scattering plane. Using the system, a SX‐RIXS spectrum was obtained under the application of the magnetic field at an angle parallel, nearly 45° or perpendicular to the incident X‐rays. A dedicated sample stage was also designed to be as compact as possible, making it possible to perform SX‐RIXS measurements at arbitrary incident angles by rotating the sample stage in the gap between the magnetic poles. This system enables facile studies of magnetic dichroism in SX‐RIXS for various experimental geometries of the sample and the magnetic field. A brief demonstration of the application is presented.     

An estimation of the column efficiency made by analyzing tailing peak profiles

It has been shown previously that most columns are not radially homogeneous but exhibit radial distributions of the mobile phase flow velocity and the local efficiency. Both distributions are best approximated by fourth-order polynomial, with the velocity in the column center being maximum for most packed columns and minimum for monolithic columns. These distributions may be an important source of tailing of elution peaks. The numerical calculation of elution peaks shows how peak tailing is related to the characteristics of these two distributions. An approach is proposed that permits estimations of the true efficiency and of the degree of column radial heterogeneity by inversing this calculation and using the tailing profiles of the elution peaks that are experimentally measured. This method was applied in two concrete cases of tailing peak profiles that had been previously reported and were analyzed by applying this new inverse approach. The results obtained prove its validity and demonstrate that this numerical method is effective for deriving the true column efficiency from experimental tailing profiles.