High-throughput evaluation of half-metallicity of CoMnSi Heusler alloys using composition-spread films and spin-integrated hard X-ray photoelectron spectroscopy.

We demonstrate high-throughput evaluation of the half-metallicity of CoMnSi Heusler alloys by spin-integrated hard X-ray photoelectron spectroscopy (HAXPES) of composition-spread films performed with high-brilliance synchrotron radiation at NanoTerasu, which identifies the optimum composition showing the best half-metallicity. Co Mn Si composition-spread thin films for  = 10-40% with a thickness of 30 nm are fabricated on MgO(100) substrates using combinatorial sputtering technique. The 2-ordering and (001)-oriented epitaxial growth of CoMnSi are confirmed by X-ray diffraction for  = 18-40%.

Hydrogen-induced Sulfur Vacancies on the MoS Basal Plane Studied by Ambient Pressure XPS and DFT Calculations.

Sulfur vacancy on an MoS basal plane plays a crucial role in device performance and catalytic activity; thus, an understanding of the electronic states of sulfur vacancies is still an important issue. We investigate the electronic states on an MoS basal plane by ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) and density functional theory calculations while heating the system in hydrogen. The AP-XPS results show a decrease in the intensity ratio of S 2p to Mo 3d, indicating that sulfur vacancies are formed.

Science electives in high school will improve nutrition knowledge but not enough to make accurate decisions.

Background/objectives: Nutrition knowledge has been reported to have a weak positive effect on healthy eating behavior. This study aimed to determine if there was a difference in nutrition knowledge depending on the choice of science subject in high school and whether that affected the actual eating habits of college students in Japan.

Subjects/methods: The subjects were 514 college students, the majority first-year students, in 3 cities in Japan.

Surface Exchange Reaction of Mixed Conductive LaCaFeO during Oxygen Evolution and Incorporation as Traced by Operando X-ray Photoelectron Spectroscopy.

High oxygen permeability of mixed conductive LaCaFeO (LCF) is applicable to pure oxygen gas generators and cathodes for solid oxide fuel cells, etc.; however, lower surface exchange reactions at temperatures below 800 °C reduce permeability. To understand the microscopic surface reaction mechanism, operando soft X-ray photoelectron spectroscopy of an LCF film surface was conducted during the evolution and incorporation of oxygen.

Hole Dynamics in Photoexcited Hematite Studied with Femtosecond Oxygen K-edge X-ray Absorption Spectroscopy.

Hematite (α-FeO) is a photoelectrode for the water splitting process because of its relatively narrow bandgap and abundance in the earth's crust. In this study, the photoexcited state of a hematite thin film was investigated with femtosecond oxygen K-edge X-ray absorption spectroscopy (XAS) at the PAL-XFEL in order to follow the dynamics of its photoexcited states. The 200 fs decay time of the hole state in the valence band was observed via its corresponding XAS feature.

Femtosecond Charge Density Modulations in Photoexcited CuWO.

Copper tungstate (CuWO) is an important semiconductor with a sophisticated and debatable electronic structure that has a direct impact on its chemistry. Using the PAL-XFEL source, we study the electronic dynamics of photoexcited CuWO. The Cu L X-ray absorption spectrum shifts to lower energy upon photoexcitation, which implies that the photoexcitation process from the oxygen valence band to the tungsten conduction band effectively increases the charge density on the Cu atoms.

Direct observation of the electronic states of photoexcited hematite with ultrafast 2p3d X-ray absorption spectroscopy and resonant inelastic X-ray scattering.

Hematite, α-FeO, is an important semiconductor for photoelectrochemical water splitting. Its low charge carrier mobility and the presence of midgap states provide favourable conditions for electron-hole recombination, hence affecting the semiconductor's photoelectrochemical efficiency. The nature of the excited state and charge carrier transport in hematite is strongly debated.

Reversible low-temperature redox activity and selective oxidation catalysis derived from the concerted activation of multiple metal species on Cr and Rh-incorporated ceria catalysts.

The ceria-based catalyst incorporated with Cr and a trace amount of Rh (CrRhCeO) was prepared and the reversible redox performances and oxidation catalysis of CO and alcohol derivatives with O at low temperatures (<373 K) were investigated. In situ X-ray absorption fine structure (XAFS), ambient-pressure X-ray photoelectron spectroscopy (AP-XPS), high angle annular dark-field scanning transmission electron microscopy (HAADF-STEM)-EDS/EELS and temperature-programmed reduction/oxidation (TPR/TPO) revealed the structures and redox mechanisms of three metals in CrRhCeO: dispersed Rh species (<1 nm) and CrO nanoparticles (∼1 nm) supported on CeO in CrRhCeO were transformed to Rh nanoclusters, Cr(OH) species and CeO with two Ce-oxide layers at the surface in a concerted activation manner of the three metal species with H.

Strong Hydrogen Bonds at the Interface between Proton-Donating and -Accepting Self-Assembled Monolayers on Au(111).

Hydrogen-bonding heterogeneous bilayers on substrates have been studied as a base for new functions of molecular adlayers by means of atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), infrared reflection absorption spectroscopy (IRAS), and density functional theory (DFT) calculations. Here, we report the formation of the catechol-fused bis(methylthio)tetrathiafulvalene (HCat-BMT-TTF) adlayer hydrogen bonding with an imidazole-terminated alkanethiolate self-assembled monolayer (Im-SAM) on Au(111). The heterogeneous bilayer is realized by sequential two-step immersions in solutions for the individual Im-SAM and HCat-BMT-TTF adlayer formations.

Parameter determination procedure for extended Hückel approximation and its application for solid-state electrolytes.

A determination procedure of transferable tight-binding parameters of extended Hückel approximation with charge self-consistency is explained, which is applicable to both molecules and crystalline solids. The parameters are adjusted by optimizing evaluation functions, compared with reference results of energy levels or band structure calculated by, for example, the density functional theory. By introducing the evaluation function, the automatic optimization of the parameters for small molecules and clusters is achieved, which makes it easy to determine an accurate parameter set and a wide application of the TB scheme.

An augmentation suture technique for arthroscopic rotator cuff repair.

The double-row suture technique and the suture-bridge technique have been used for rotator cuff repair to decrease the occurrence of retears. However, when only the degenerated tendon end is sutured, the risk of retear remains. The augmentation suture technique is a new procedure that connects the intact medial tendon to the lateral greater tuberosity, and this approach may protect the initial repair site.

Electron-Hole Recombination Time at TiO2 Single-Crystal Surfaces: Influence of Surface Band Bending.

Photocatalytic activity is determined by the transport property of photoexcited carriers from the interior to the surface of photocatalysts. Because the carrier dynamics is influenced by a space charge layer (SCL) in the subsurface region, an understanding of the effect of the potential barrier of the SCL on the carrier behavior is essential. Here we have investigated the relaxation time of the photoexcited carriers on single-crystal anatase and rutile TiO2 surfaces by time-resolved photoelectron spectroscopy and found that carrier recombination, taking a nanosecond time scale at room temperature, is strongly influenced by the barrier height of the SCL.

New soft X-ray beamline BL07LSU at SPring-8.

A new soft X-ray beamline, BL07LSU, has been constructed at SPring-8 to perform advanced soft X-ray spectroscopy for materials science. The beamline is designed to achieve high energy resolution (E/ΔE> 10000) and high photon flux [>10(12) photons s(-1) (0.01% bandwidth)(-1)] in the photon energy range 250-2000 eV with controllable polarization.

Modified ab externo method for introducing 2 polypropylene loops for scleral suture fixation of intraocular lenses.

We describe a method that enables the introduction of 2 suture loops for scleral fixation of an intraocular lens (IOL) by a single ab externo procedure. A long needle carrying a polypropylene suture loop is inserted through the scleral fixation site and docked with a hollow needle inserted through the opposite fixation site. The hollow needle pulls the suture needle out, but the suture loop end is left external.

Highly compressed two-dimensional form of water at ambient conditions.

The structure of thin-film water on a BaF(2)(111) surface under ambient conditions was studied using x-ray absorption spectroscopy from ambient to supercooled temperatures at relative humidity up to 95%. No hexagonal ice-like structure was observed in spite of the expected templating effect of the lattice-matched (111) surface. The oxygen K-edge x-ray absorption spectrum of liquid thin-film water on BaF(2) exhibits, at all temperatures, a strong resemblance to that of high-density phases for which the observed spectroscopic features correlate linearly with the density.

Nanophthalmos: quantitative analysis of anterior chamber angle configuration before and after cataract surgery.

Background/aims: To analyse quantitatively the anterior segment configuration in eyes with nanophthalmos before and after cataract surgery.

Methods: This was a retrospective, non-comparative, interventional case series. Eleven eyes in eight patients with nanophthalmos who underwent phacoemulsification and intraocular lens implantation were identified from the department's surgical log, and their clinical records were retrospectively reviewed.

Development of soft x-ray time-resolved photoemission spectroscopy system with a two-dimensional angle-resolved time-of-flight analyzer at SPring-8 BL07LSU.

We have developed a soft x-ray time-resolved photoemission spectroscopy system using synchrotron radiation (SR) at SPring-8 BL07LSU and an ultrashort pulse laser system. Two-dimensional angle-resolved measurements were performed with a time-of-flight-type analyzer. The photoemission spectroscopy system is synchronized to light pulses of SR and laser using a time control unit.

Structural inhomogeneity of interfacial water at lipid monolayers revealed by surface-specific vibrational pump-probe spectroscopy.

We report vibrational lifetime measurements of the OH stretch vibration of interfacial water in contact with lipid monolayers, using time-resolved vibrational sum frequency (VSF) spectroscopy. The dynamics of water in contact with four different lipids are reported and are characterized by vibrational relaxation rates measured at 3200, 3300, 3400, and 3500 cm(-1). We observe that the water molecules with an OH frequency ranging from 3300 to 3500 cm(-1) all show vibrational relaxation with a time constant of T(1) = 180 ± 35 fs, similar to what is found for bulk water.

Ultrafast inter- and intramolecular vibrational energy transfer between molecules at interfaces studied by time- and polarization-resolved SFG spectroscopy.

We present experimental results on femtosecond time-resolved surface vibrational spectroscopy aimed at elucidating the sub-picosecond reorientational dynamics of surface molecules. The approach, which relies on polarization- and time-resolved surface sum frequency generation (SFG), provides a general means to monitor interfacial reorientational dynamics through vibrations inherent in surface molecules in their electronic ground state. The technique requires an anisotropic vibrational excitation of surface molecules using orthogonally polarized infrared excitation light.

Autocatalytic water dissociation on Cu(110) at near ambient conditions.

Autocatalytic dissociation of water on the Cu(110) metal surface is demonstrated on the basis of X-ray photoelectron spectroscopy studies carried out in situ under near ambient conditions of water vapor pressure (1 Torr) and temperature (275-520 K). The autocatalytic reaction is explained as the result of the strong hydrogen-bond in the H2O-OH complex of the dissociated final state, which lowers the water dissociation barrier according to the Brønsted-Evans-Polanyi relations. A simple chemical bonding picture is presented which predicts autocatalytic water dissociation to be a general phenomenon on metal surfaces.

Design and synthesis of DPP-IV inhibitors lacking the electrophilic nitrile group.

A series of (4beta-substituted)-L-prolylpyrrolidine analogs lacking the electrophilic nitrile function were synthesized and their dipeptidyl peptidase IV (DPP-IV) inhibitory activity and duration of ex vivo activity were evaluated. Structural optimization of a N-(3-phenyl-1,2,4-thiadiazol-5-yl)piperazine analog 8, which was found by high-speed analog synthesis, was carried out to improve the potency and duration of action. A representative compound 26 was evaluated to assess its effect on the plasma glucose level after the oGTT (oral glucose tolerance test) in normal rats.

Discovery of long-acting N-(cyanomethyl)-N-alkyl-L-prolinamide inhibitors of dipeptidyl peptidase IV.

Details of structure-activity relationships (SAR) for P2 moiety of a P1 2-cyanopyrrolidine dipeptidyl peptidase IV (DPP-IV) inhibitor 4a including stereochemistry are presented. Based on this information, a series of P1 (N-alkyl)aminoacetonitrile analogs 9-20 possessing optimal P2 structure were synthesized and evaluated as inhibitors of DPP-IV. Among them, a representative compound 11, N-(cyanomethyl)-N-ethyl-L-prolinamide, was further evaluated to determine its effect on the plasma glucose level.

Design and synthesis of new potent dipeptidyl peptidase IV inhibitors with enhanced ex vivo duration.

A series of 5beta-methylprolyl-2-cyanopyrrolidine analogs were synthesized and evaluated as DPP-IV inhibitors, and the duration of their ex vivo activity was assessed. Comparison of their potency and duration of action was done among three different species. The mode of binding was investigated, and the effect on the plasma glucose level was evaluated.

Design and synthesis of long-acting inhibitors of dipeptidyl peptidase IV.

A series of (4-substituted prolyl)prolinenitriles were synthesized and evaluated as inhibitors of dipeptidylpeptidase IV (DPP-IV). Among those tested, the 4beta-[4-(hydroxyphenyl)prolyl]prolinenitriles showed a potent inhibitory activity with a long duration of action. Metabolic formation of the corresponding phenol glucuronates was found to contribute to their long duration of action.