Azimuthal-rotation sample holder for molecular orientation analysis.

In this study, an azimuthal-rotation sample holder compatible with scanning transmission X-ray microscopy was developed. This holder exhibits improvement in the accuracy of rotation angles and reduces the displacement of the rotation axes during azimuthal rotation by using a crossed roller bearing. To evaluate the performance of the holder, the authors investigated the dependence of the optical density around the C K-edge absorption of π-orbital-oriented domains in natural spherical graphite on the rotational angle by using linearly horizontally and vertically polarized undulator radiation. Based on the dependence of the optical density ratio between C 1s → π* and 1s → σ* excitation on the polarization angle of the X-rays, the average two-dimensional orientation angle of the π orbital in each position in a natural spherical graphite sample was visualized.

A surface sensitive hard X-ray spectroscopic method applied to observe the surface layer reduction reaction of Co oxide to Co metal.

A simple and easy surface sensitive spectroscopic method using hard X-rays has been developed and applied to observe the surface oxide reduction reaction. The method named TREXS, Total REflection X-ray Spectroscopy, records the total reflection of incident X-rays at sample surfaces. The surface reduction reaction of Co oxide (Co3O4) to Co metal was successfully observed by in situ TREXS measurements with a surface sensitivity of ∼2 nm. The in situ TREXS measurements were performed under H2 flow of N2 balanced atmospheric pressure with increasing temperature. This method, in situ TREXS, will be a suitable and powerful tool to observe a variety of surface chemical reactions and consequently to understand catalytic processes under realistic operating conditions.

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.

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.

The challenge of constructing an international XAFS database.

The present state of XAFS databases, particularly in Japan, and proposals for future directions are presented. International collaboration is important for enlarging the database for further development of XAFS spectroscopy.

A call for a round robin study of XAFS stability and platform dependence at synchrotron beamlines on well defined samples.

Round robin studies have been used across fields of science for quality control testing and to investigate laboratory dependencies and cross-platform inconsistencies as well as to drive forward the improvement of understanding of experimental systems, systematic effects and theoretical limitations. Here, following the Q2XAFS Workshop and Satellite to IUCr Congress 2017 on `Data Acquisition, Treatment, Storage - quality assurance in XAFS spectroscopy', a mechanism is suggested for a suitable study across XAFS (X-ray absorption fine-structure) beamlines and facilities, to enable each beamline to cross-calibrate, provide representative test data, and to enable collaborative cross-facility activities to be more productive.

Prediction of tortuosity, permeability, and pore radius of water-saturated unconsolidated glass beads and sands.

Tortuosity, permeability, and pore radius, which are parameters in the Biot model, are important for analyzing the elastic wave propagation in water-saturated unconsolidated marine sands. In this study, the formation factor and permeability are measured for 34 kinds of water-saturated glass beads and sands with uniformly sized grains and 73 kinds of water-saturated sands with distributed sized grains. Using these measured data, the empirical equations for the formation factor, cementation exponent, and tortuosity are obtained. The pore shape factor, k0, in the Kozeny-Carman model and pore shape factor, a, in the Revil-Cathles (RC) model are derived. The Hazen, Kozeny-Carman, and RC models are compared for the measured permeability results. Furthermore, the relationship between the tortuosity and permeability is shown. Finally, the ratio of the effective pore radius to effective mean grain diameter is derived.

Gritty Surface Sample Holder Invented To Obtain Correct X-ray Absorption Fine Structure Spectra for Concentrated Materials by Fluorescence Yield.

A gritty surface sample holder has been invented to obtain correct XAFS spectra for concentrated samples by fluorescence yield (FY). Materials are usually mixed with boron nitride (BN) to prepare proper concentrations to measure XAFS spectra. Some materials, however, could not be mixed with BN and would be measured in too concentrated conditions to obtain correct XAFS spectra. Consequently, XAFS spectra will be incorrect typically with decreased intensities of the peaks. We have invented the gritty surface sample holders to obtain correct XAFS spectra even for concentrated materials for FY measurements. Pure Cu and CuO powders were measured mounted on the sample holders, and the same spectra were obtained as transmission spectra of properly prepared samples. This sample holder is useful to measure XAFS for any concentrated materials.

X-ray analyzer-based phase-contrast computed laminography.

X-ray analyzer-based phase-contrast imaging is combined with computed laminography for imaging regions of interest in laterally extended flat specimens of weak absorption contrast. The optics discussed here consist of an asymmetrically cut collimator crystal and a symmetrically cut analyzer crystal arranged in a nondispersive (+, -) diffraction geometry. A generalized algorithm is given for calculating multi-contrast (absorption, refraction and phase contrast) images of a sample. Basic formulae are also presented for laminographic reconstruction. The feasibility of the method discussed was verified at the vertical wiggler beamline BL-14B of the Photon Factory. At a wavelength of 0.0733 nm, phase-contrast sectional images of plastic beads were successfully obtained. Owing to strong circular artifacts caused by a sample holder, the field of view was limited to about 6 mm in diameter.

Clinical practice guidelines for therapeutic drug monitoring of arbekacin: a consensus review of the Japanese Society of Chemotherapy and the Japanese Society of Therapeutic Drug Monitoring.

Arbekacin (ABK) was approved and widely used in Japan for treatment of patients infected with MRSA, and TDM was introduced in clinical practice. The Japanese Society of Chemotherapy and the Japanese Society of Therapeutic Drug Monitoring decided to develop a clinical practice guidelines for TDM of ABK for the following reasons. First, although the daily dose of 150-200 mg was approved in Japan, recent PK-PD studies revealed that higher serum concentration is required to achieve better clinical efficacy and several findings concerning the usefulness of higher dosage regimen have obtained recently. Second, although maximal concentrations that obtained immediately after the end of administration (Cmax) was generally adopted, the serum concentration at 1 h after initiation of administration [peak serum concentration (Cpeak)] proved to be more suitable as an efficacy indicator of aminoglycosides. Lastly, as ABK is approved only in Japan, no international practice guideline for TDM has not been available in ABK to date. This guideline evaluated the scientific data associated with serum ABK monitoring and provided recommendations based on the available evidence. Potential limitations of this guideline, however, include the findings that few prospective clinical trials of TDM of ABK are available in the treatment of MRSA infections and that most of the published literature describes observational studies.

Grain-size dependence of shear wave speed dispersion and attenuation in granular marine sediments.

The author has shown that measured shear wave speed dispersion and attenuation in water-saturated silica sand can be predicted by using a gap stiffness model incorporated into the Biot model (the BIMGS model) [Kimura, J. Acoust. Soc. Am. 134, 144-155 (2013)]. In this study, the grain-size dependence of shear wave speed dispersion and attenuation in four kinds of water-saturated silica sands with different grain sizes is measured and calculated. As a result, the grain-size dependence of the aspect ratio in the BIMGS model can be validated and the effects of multiple scattering for larger grain sizes are demonstrated.

Shear wave speed dispersion and attenuation in granular marine sediments.

The reported compressional wave speed dispersion and attenuation could be explained by a modified gap stiffness model incorporated into the Biot model (the BIMGS model). In contrast, shear wave speed dispersion and attenuation have not been investigated in detail. No measurements of shear wave speed dispersion have been reported, and only Brunson's data provide the frequency characteristics of shear wave attenuation. In this study, Brunson's attenuation measurements are compared to predictions using the Biot-Stoll model and the BIMGS model. It is shown that the BIMGS model accurately predicts the frequency dependence of shear wave attenuation. Then, the shear wave speed dispersion and attenuation in water-saturated silica sand are measured in the frequency range of 4-20 kHz. The vertical stress applied to the sample is 17.6 kPa. The temperature of the sample is set to be 5 °C, 20 °C, and 35 °C in order to change the relaxation frequency in the BIMGS model. The measured results are compared with those calculated using the Biot-Stoll model and the BIMGS model. It is shown that the shear wave speed dispersion and attenuation are predicted accurately by using the BIMGS model.

Geological records of transient fluid drainage into the shallow mantle wedge.

Pore fluid pressure on subduction zone megathrusts is lowered by fluid drainage into the overlying plate, affecting subduction zone seismicity. However, the spatial and temporal scales of fluid flow through suprasubduction zones are poorly understood. We constrain the duration and velocity of fluid flow through a shallow mantle wedge based on the analyses of vein networks consisting of high-temperature serpentine in hydrated ultramafic rocks from the Oman ophiolite. On the basis of a diffusion model and the time-integrated fluid flux, we show that the channelized fluid flow was short-lived (2.1 × 10-1 to 1.1 × 101 years) and had a high fluid velocity (2.7 × 10-3 to 4.9 × 10-2 meters second-1), which is close to the propagation velocities of seismic events in present-day subduction zones. Our results suggest that the drainage of fluid into the overlying plate occurs as episodic pulses, which may influence the recurrence of megathrust earthquakes.

Oxidation-induced nanolite crystallization triggered the 2021 eruption of Fukutoku-Oka-no-Ba, Japan.

Nanometer-sized crystals (nanolites) play an important role in controlling eruptions by affecting the viscosity of magmas and inducing bubble nucleation. We present detailed microscopic and nanoscopic petrographic analyses of nanolite-bearing and nanolite-free pumice from the 2021 eruption of Fukutoku-Oka-no-Ba, Japan. The nanolite mineral assemblage includes biotite, which is absent from the phenocryst mineral assemblage, and magnetite and clinopyroxene, which are observed as phenocrysts. The boundary between the nanolite-bearing brown glass and nanolite-free colorless glass is either sharp or gradational, and the sharp boundaries also appear sharp under the transmitted electron microscope. X-ray absorption fine structure (XAFS) analysis of the volcanic glass revealed that the nanolite-free colorless glass records an oxygen fugacity of QFM + 0.98 (log units), whereas the nanolite-bearing brown glass records a higher apparent oxygen fugacity (~ QFM + 2). Thermodynamic modelling using MELTS indicates that higher oxygen fugacities increase the liquidus temperature and thus induced the crystallization of magnetite nanolites. The hydrous nanolite mineral assemblage and glass oxygen fugacity estimates suggest that an oxidizing fluid supplied by a hot mafic magma induced nanolite crystallization in the magma reservoir, before the magma fragmentation. The oxidation-induced nanolite crystallization then enhanced heterogeneous bubble nucleation, resulting in convection in the magma reservoir and triggering the eruption.

Formation and oxidation mechanisms of Pd-Zn nanoparticles on a ZnO supported Pd catalyst studied by in situ time-resolved QXAFS and DXAFS.

Formation and oxidation processes of PdZn nanoparticles on ZnO were successfully observed by means of in situ time-resolved X-ray absorption fine structure spectroscopy (XAFS), and the analysis of data on near-edge (XANES) and extended (EXAFS) structures revealed detailed changes in Pd during both processes. PdZn nanoparticles were formed on ZnO through a two-step scheme under a hydrogen atmosphere. The first process was the formation of metallic Pd nanoparticles, which was quickly finished within 1 s. The second process was the formation of PdZn nanoparticles, which took several tens of minutes. Oxidation of the PdZn nanoparticles also consisted of two processes. Zn atoms were oxidized prior to Pd atoms and the metallic Pd nanoparticles surrounded by ZnO were formed afterwards. Oxidation of the metallic Pd nanoparticles was scarce and very slow. According to the results of kinetic analyses, the metallic Pd surrounded by ZnO was a stable species under the oxidative atmosphere.

Exploration of optimal teicoplanin dosage based on pharmacokinetic parameters for the treatment of intensive care unit patients infected with methicillin-resistant Staphylococcus aureus.

Severely ill intensive care unit (ICU) patients are frequently at risk of developing methicillin-resistant Staphylococcus aureus (MRSA) infections. It is generally accepted that a trough level of >10 µg/mL teicoplanin (TEC) is appropriate for most such infections. The present study was designed to determine how TEC exposure and patient characteristics affect microbiological response in the treatment of MRSA infections. All patients studied were admitted to Aichi Medical University Hospital ICU between May 2005 and April 2010. Fifty-nine patients were prescribed TEC and 33 of those patients used to treat MRSA infection. Outcome was classified as either cure or failure, and logistic regression analysis was performed to determine which covariates, including severity, significantly influenced the microbiological response. Satisfactory outcomes were obtained in 19 of the 33 patients. Although the cured and failed groups showed adequate trough concentrations, the area under the serum concentration curve (AUC(0-24)) on the third day was significantly higher for the cured group (897.6 ± 71.7) than for the failed group (652.9 ± 83.4) (p < 0.05). The results suggested that at least 800 µg h/mL TEC AUC(0-24) were required to obtain microbiological cure. The higher AUC(0-24), the better the outcome. In our study, higher initial AUC(0-24) was associated with a better microbiological outcome, which demonstrates the importance of the loading dose of TEC, especially for ICU patients. Moreover, the present findings are useful for optimizing the individual dose of TEC using AUC(0-24) in the treatment of MRSA-infected patients.

[Clinical investigation of arbekacin sulfate based on Cmax/MIC].

We examined the peck concentration (Cmax)/minimal inhibitory concentration (MIC) and the clinical efficacy in methicillin-resistant Staphylococcus aureus (MRSA) pneumonia and Gram-positive cocci bacteremia. We evaluated arbekacin (ABK) on 22 cases of pneumonia and 10 cases of bacteremia in Aichi Medical University Hospital between August 2008 and July 2011, retrospectively. In pneumonia cases, Cmax/MIC was 16.4 +/- 2.8 in the effective group, and was 17.6 +/- 4.5 in the not effective group, the significant differences were not accepted (p = 0.8). The dosage of ABK was 4.7 +/- 1.4 mg/kg/dose in the effective group and was 4.3 +/- 0.7 mg/kg/dose in the not effective group. In bacteremia cases, Cmax/MIC was 24.2 +/- 13.9 in the effective group and 12.9 +/- 3.9 in the not effective group about clinical efficacy, and the high tendency was accepted by the effective group (p < 0.05). The dosage of ABK was 3.4 +/- 1.1 mg/kg/dose in the effective group, and 3.0 +/- 0.6 mg/kg/dose in the not effective group. In this examination, the significant difference was not observed in clinical efficacy and Cmax/MIC in the pneumonia cases. Although it was reported that clinical efficacy of ABK was given Cmax/MIC at eight or more, in this examination, all cases was eight or more at Cmax/MIC, and the clinical effect was 40.9%. On Cmax/MIC of ABK, clinical effective group was higher than not effective group in bacteremia cases, it was suggested that the administration design should make that Cmax/MIC at least about 14 or more would be necessary.

Velocity dispersion and attenuation in granular marine sediments: comparison of measurements with predictions using acoustic models.

The large velocity dispersion recently reported could be explained by a gap stiffness model incorporated into the Biot model (the BIMGS model) proposed by the author. However, at high frequencies, some measured results have been reported for negative velocity dispersion and attenuation proportional to the first to fourth power of frequency. In this study, first, it is shown that the results of velocity dispersion and attenuation calculated using the BIMGS model are consistent with the results measured in two kinds of water-saturated sands with different grain sizes, except in the high-frequency range. Then, the velocity dispersion and attenuation in six kinds of water-saturated glass beads and four kinds of water-saturated silica sands with different grain sizes are measured in the frequency ranges of 80-140 and 300-700 kHz. The measured results are compared with those calculated using the BIMGS model plus some acoustic models. It is shown that the velocity dispersion and attenuation are well predicted by using the BIMGS model in the range of kd ≤ 0.5 (k: wavenumber in water, d: grain diameter) and by using the BIMGS model plus multiple scattering effects in the range of kd ≥ 0.5 in which negative velocity dispersion appears.

[A Survey of the Use of Direct Oral Anticoagulants in Patients' Possession at the Time of Hospitalization].

The dose of direct oral anticoagulants (DOACs) must be determined based on package insert recommendations. There are reports on the rate of inappropriate DOAC dose usage defined as a dose deviating from the approved dose in the package insert but no reports on factors that led to such deviations. Thus, patients who were admitted to the Suzuka Kaisei Hospital between 1 April 2016 and 31 March 2017 were chosen as subjects. Moreover, the factors that during hospitalization led to dose deviation from the package-insert DOAC dose were retrospectively examined. The characteristics of patients administered doses deviating from the package insert were compared with those of patients in the appropriate-dose group. The finding was that the proportion concomitantly administered antiplatelet agents was higher in the underdose group. In contrast, deviations from the recommended dose did not occur when DOACs were combined with CYP3A4 inhibitors or P-glycoprotein (P-gp) inhibitors. It was suggested that increase in the risk of hemorrhage by antiplatelet agents in combination with oral anticoagulants could explain deviations from the stipulated DOAC dose. In addition, a higher proportion of patients in the overdose group showed depressed Ccr, and gastrointestinal bleeding. In future, it will be necessary to propose principle-based dose changes for patients administered doses deviating from the package insert. If an underdose is administered, it is important to make a dose change that takes the concomitant drugs into consideration.

[Clinical implication of therapeutic drug monitoring on voriconazole from the aspect of the analysis for CYP2C19 gene].

Three microsome enzymes are involved in voriconazole (VRCZ) metabolism, CYP2C19, CYP3A4 and CYP2C9, and subjects classified as poor metabolizers (PM), which would include about 20% of Japanese population, had higher serum VRCZ concentrations than other subjects. Also, because VRCZ appears hepatotoxicity and visual disturbance in side effect, VRCZ must be done therapeutic drug monitoring (TDM). This study evaluated the three cases which administered VRCZ to analysis for CYP2C19 gene. This study evaluated VRCZ trough concentration and side effect in the fifteen cases which administered VRCZ to analysis for TDM in Aichi University Hospital. Also, the administering design of VRCZ followed drug information in the three cases. Correlation of VRCZ trough concentration and dosage was weak in fifteen cases. In case 1, although patient is not PM, trough concentration of VRCZ showed high concentration (8.43 microg/mL) after 4 days of starting administration and appeared side effects of illusion and optical illusion. In case 2, although patient is PM, trough concentration of VRCZ showed 5.53 microg/mL and 8.61 microg/mL after 4 days and 7 days of starting administration, respectively, also liver function (AST, ALT and others) rised slightly. In case 3, although patient is not PM, trough concentration of VRCZ after the 5 days and 12 days of starting administration showed 3.2 microg/mL and 3.25 microg/mL, respectively, also maintained therapeutic trough lebel. In this result, it was thought that pharmacokinetics of VRCZ was unstable comparatively and concentration of VRCZ varied generally among individuals regardless of the CYP2C19 genotype. Therefore, it was important to an individual patient to improve a clinical effect, and to decrease the adverse event from the initial administering design, and is necessary to do the administering design afterwards while doing TDM at many times.