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A 72-year-old man undergoing chemotherapy with 4 cycles of gemcitabine and nabpaclitaxel for pancreatic ductal adenocarcinoma, diagnosed 5 months previously, presented to the emergency department with sudden difficulty moving his [...]

Water dynamics in the hydration layers of biomolecules play crucial roles in a wide range of biological functions. A hydrated protein contains multiple components of diffusional and vibrational dynamics of water and protein, which may be coupled at ∼0.1-THz frequency (10-ps timescale) at room temperature. However, the microscopic description of biomolecular functions based on various modes of protein-water-coupled motions remains elusive. A novel approach for perturbing the hydration dynamics in the subterahertz frequency range and probing them at the atomic level is therefore warranted. In this study, we investigated the effect of klystron-based, intense 0.1-THz excitation on the slow dynamics of ubiquitin using NMR-based measurements of hydrogen-deuterium exchange. We demonstrated that the subterahertz irradiation accelerated the hydrogen-deuterium exchange of the amides located in the interior of the protein and hydrophobic surfaces while decelerating this exchange in the amides located in the surface loop and short 310helix regions. This subterahertz-radiation-induced effect was qualitatively contradictory to the increased-temperature-induced effect. Our results suggest that the heterogeneous water dynamics occurring at the protein-water interface include components that are nonthermally excited by the subterahertz radiation. Such subterahertz-excited components may be linked to the slow function-related dynamics of the protein.

The optical and X-and γ-ray induced scintillation characteristics of Tb-doped SrY2O4single crystals using the floating zone technique were evaluated. Under UV and X-rays, several lines in the range of 350 to 650 nm were observed in all the prepared crystals, which were attributed to the Tb3+ions. In the pulse area spectra of a 137Cs γ-ray source, the full-energy absorption peak was confirmed using a 1.0% Tb-doped crystal, and the light yield was estimated to be 12,000 photons/MeV.

Arsenic (As) is a major impurity contaminated in metal refinery wastewaters. To immobilize As ions, we have previously reported microbial scorodite (FeAsO4·2H2O) crystallization using the thermo-acidophilic iron-oxidizing archaeon, Acidianus brierleyi. In order to extend the applicable range of As (III)-bearing metal refinery wastewaters (especially for dilute As (III) concentrations of 250–1500 ppm), this study investigated the effect of several factors possibly affecting the bioscorodite crystallization efficiency; (i) [Fe (II)]ini/[As (III)]ini molar ratio at different target As (III) concentrations, (ii) initial pH, and (iii) seed scorodite with different morphologies. The [Fe (II)]ini/[As (III)]ini molar ratio strongly affected the bioscorodite crystallization efficiency at each target As (III) concentration. Whilst the [Fe (II)]ini/[As (III)]ini molar ratio of 1.4 was most effective at 500–1500 ppm As (III), the optimal molar ratios for treating more dilute concentrations (< 500 ppm) were shown to be relatively higher. However, further increasing the [Fe (II)]ini/[As (III)]ini molar ratio resulted in formation of unwanted potassium jarosite (KFe3(OH)6(SO4)2) together with scorodite. Lowering the initial pH from 1.5 to 1.2 resulted in earlier scorodite nucleation, but lesser overall As immobilization. Feeding chemical-and bio-scorodite seed crystals differently affected the reaction speed and the stability of newly-precipitated bioscorodite. The TCLP test indicated that scorodite formed on bioscorodite seeds is more stable than that formed on chemically-synthesized scorodite seeds.

Storage phosphor materials can be used to record an incident radiation dose, and they are often used for personal dose monitoring applications and imaging plates (IPs). Conventionally, the storage phosphors for IPs are mainly used in the form of powders and needle crystals while IPs using translucent ceramics have recently attracted much attention. In this paper, we review the recent studies of translucent ceramic storage phosphors for IPs in addition to conventional storage phosphors.

The effect of different concentrations of Cu (II) on microbial scorodite (FeAsO4⋅2H2O) formation was investigated by using thermo-acidophilic iron-oxidizing archaeon, Acidianus brierleyi. In the presence of 8-16 mM Cu (II) microbial Fe (II) oxidation and cell growth was only marginal. Its As (III) oxidation ability was especially severely inhibited by the presence of Cu (II), consequently disabling scorodite formation. However, when scorodite seed crystals were fed, Ac. brierleyi readily oxidized Fe (II) and As (III) even in the presence of 8.0 mM Cu (II), forming crystalline scorodite within 24 days in shake flasks. All Cu (II) remained in the solution phase during scorodite crystallization, with or without the presence of seed crystals. Increasing the seed crystal concentration (from 0.015 to 0.15%) slightly improved the As immobilization (from 96 to 98%). This study demonstrated that scorodite can be crystallized from the model As (III)-bearing wastewater containing Cu (II).

The purpose of this study is to investigate the fatigue characteristic and fatigue fracture mechanism of the high V-Cr-Ni spheroidal carbide cast iron (SCI-VCrNi) with spheroidal vanadium carbide (VC) dispersed within austenitic stainless matrix microstructure. The SCI-VCrNi that has high hardness was developed by 10mass%V adding to 18-8 stainless steel with spheroidal VC is distributed in the matrix. Firstly from the plane bending, the fatigue limit σw has been found to the 358MPa of SCI-VCrNi. Secondly, fracture surface observations were performed to clarify the fatigue mechanism of SCI-VCrNi. The fracture surface of SCI-VCrNi was so rough that the beach mark could not be observed. So, SEM was employed to observe, the fatigue fracture surface which showed a particular fatigue pattern. Also, many fracture cracks of VC were observed. In addition, the secondary cracks are shown at the interface between VC and the matrix. It can be suggested that the bondability between VC and the matrix is strong, and therefore, the propagation of cracks was delayed by the breakage of VC.

Spheroidal carbides cast irons (SCIs) are used in severe conditions where often occur erosion and due to their excellent wear resistance characteristics. In this study, three kinds of SCIs with a variation in matrices are tested and evaluated as shredding blade of uniaxial rotary glass shredder in recycling factories where often occurs extreme abrasion with the crushed glass. They are SCI-VCrNi, SCI-VMn, and SCI-Vw with hard (2400Hv) spheroidal vanadium carbides (VC). As a result, SCI-Vw reveals excellent wear resistance, approximately 1/12 of wear removal in weight, compare to other two materials of SCI-VCrNi and SCI-VMn. Spheroidal carbides nodularity(70%) and volume fraction of VCs(approximately 20%) are similar in three kinds of SCIs. The hardness of matrix of SCI-Vw (800Hv) is greater than that of SCI-VCrNi (320Hv) and SCI-VMn (380Hv). Therefore the experimental results are interpreted that hardness of matrix are dominant factor for abrasion. Based on this experimental study, SCI-Vw is an effective material for abrasion occurred on the blade of the glass shredder.

A quantitative nondestructive Bragg-edge imaging technique for power-storage degradation was developed using commercial prismatic-shaped lithium-ion battery cells. The C or Li atoms/ions column density [cm−2] images for five phases of the negative electrode material (graphite, Li0.04C6, Li0.2C6, Li0.5C6, and Li1.0C6) with a 1 mm spatial resolution were obtained by considering the crystalline orientation for both fresh and fatigue cells. In the fresh cell, most of the graphite was uniformly converted to Li1.0C6by charging, and in the fatigue cell, the graphite changed to various phases (especially, Li1.0C6and Li0.5C6) by charging, and their spatial distributions were nonuniform.

We have designed a compact optical cell for studying the absorption and circular dichroism (CD) of a solution sample in the vacuum ultraviolet (VUV) region using a temperature control unit. The cell size was 34 mm in diameter and 14 mm in length. Such compactness was obtained by coating the VUV scintillator onto the outside of the back window. Because this scintillator converts the transmitted VUV light to visible light, the outside of this cell is operated under atmospheric pressure. The temperature of the sample solution was maintained in the range of 5°C to 80°C using a temperature control unit with a Peltier thermoelectric element. Changes in the sample temperature were observed by monitoring the absorption intensity of water. Through the study of VUV‐CD spectra of ammonium camphor‐10‐sulfonate aqueous solutions and the transmitted spectrum of an empty cell, it was concluded that this cell unit has sufficient performance for use in VUV spectroscopy. Chirality, 2008. © 2008 Wiley‐Liss, Inc.

We have developed an improved circular dichroism (CD) and linear dichroism (LD) simultaneous measurement system for the vacuum ultraviolet (VUV) region by polarization modulation techniques using a four‐period Onuki‐type crossed undulator as a polarized light source. The system has been constructed at the VUV beamline BL‐5 in the electron storage ring TERAS, at AIST. Our improvements, in particular the adoption of an optical chopper as the detection method of incident light, have resulted in a flat baseline and a consequent simplification of the Mueller matrix calculation for our optical system. Based on the Mueller matrix calculation, we have successfully measured real VUV‐CD and LD spectra of leucine films for wavelengths down to 160 nm with absolute optical constants. The obtained spectra show good consistency with spectra measured by conventional methods. © 2006 Wiley‐Liss, Inc. Chirality

There are two distinct subtypes of multiple sclerosis in Asians, opticospinal (OS-multiple sclerosis) and conventional (C-multiple sclerosis). In OS-multiple sclerosis, selective and severe involvement of the optic nerves and spinal cord is characteristic, though its mechanisms are unknown. The present study aimed to find out possible differences in the cytokine/chemokine profiles in CSF between OS-multiple sclerosis and C-multiple sclerosis and to delineate the relationships between these profiles and neuroimaging and pathological features. Sixteen cytokines/chemokines, namely interleukin (IL)-1β, IL-2, IL-4, IL-5, IL-6, IL-7, IL-8, IL-10, IL-12 (p70), IL-13, IL-17, interferon (IFN)-γ, tumour necrosis factor (TNF)-α, granulocyte colony-stimulating factor (G-CSF), monocyte chemoattractant protein-1 (MCP-1) and macrophage inflammatory protein-1β (MIP-1β), were measured simultaneously in CSF supernatants from 40 patients with relapsing–remitting multiple sclerosis (20 OS-multiple sclerosis and 20 C-multiple sclerosis) at relapse and 19 control patients with spinocerebellar degeneration (SCD), together with intracellular production of IFN-γ and IL-4 in CSF CD4+ T cells. In CSF supernatants relative to controls, IL-17, MIP-1β, IL-1β and IL-13 were only significantly increased in OS-multiple sclerosis patients, while TNF-α was only significantly increased in C-multiple sclerosis patients, using a cut-off level of 1 pg/ml. IL-8 was significantly elevated in both OS-multiple sclerosis and C-multiple sclerosis patients. MCP-1 was significantly decreased in both OS-multiple sclerosis and C-multiple sclerosis patients, while IL-7 was only significantly decreased in C-multiple sclerosis patients. IL-17, IL-8 and IL-5 were significantly higher in OS-multiple sclerosis patients than in C-multiple sclerosis patients. The increases in IL-17 and IL-8 in OS-multiple sclerosis were still significant even after exclusion of the patients undergoing various immunomodulatory therapies. Assays of intracellular cytokine production revealed that both the IFN-γ+IL-4− T-cell percentage and intracellular IFN-γ/IL-4 ratio in CSF cells were significantly greater in C-multiple sclerosis patients than in controls. Contrarily, OS-multiple sclerosis patients showed not only a significantly greater percentage of IFN-γ+IL-4− T cells than controls but also a significantly higher percentage of IFN-γ−IL-4+ T cells than C-multiple sclerosis patients. Among the cytokines elevated in multiple sclerosis, only IL-8 showed a significant positive correlation with the Expanded Disability Status Scale of Kurtzke score. Both the length of the spinal cord lesions on MRI and the CSF/serum albumin ratio had a significant positive correlation with IL-8 and IL-17 in multiple sclerosis, in which the spinal cord lesions were significantly longer in OS-multiple sclerosis than in C-multiple sclerosis. Three of six spinal cord specimens from autopsied OS-multiple sclerosis cases demonstrated numerous myeloperoxidase-positive neutrophils infiltrating necrotic lesions. These findings strongly suggest that in OS-multiple sclerosis, in addition to the Th1 cell upregulation seen in C-multiple sclerosis, intrathecal activation of the IL-17/IL-8 axis inducing heavy neutrophil infiltration contributes to extensive spinal cord lesion formation.

Alkyl(2,6-dimethoxyphenyl)tellurium dihalides, RArTeX₂ [Ar = 2,6-(MeO)₂C₆H₃; X = Cl 2a–c, Br 3a–c, I 4a–c; R = Me a, Et b, i-Pr c] were prepared by the reactions of alkyl 2,6-dimethoxyphenyl telluride, RArTe 1, with SOCl₂, Br₂ or I₂, respectively. The rotational barrier ΔG‡ of the Ar-group around the Te–C bond in 2a–c, 3a–c and 4a–c estimated by variable temperature 1H NMR spectra was dependent on the alkyl (R) group as well as on the halogen atoms. It decreased in the order R = Me > Et > i-Pr as well as X = Cl > Br > I. The 125Te resonances of 1 were observed at higher magnetic fields than those of RPhTe, and those of 1a–c, 2a–c, 3a–c and 4a–c shifted to lower magnetic field in the order R = Me > Et > i-Pr. The X-ray crystallographic analyses of 2a–c, 3a, 3b and 4a showed that the geometry around tellurium was pseudo-trigonal bipyramidal with the alkyl group, the Ar group and a lone pair of electrons in the equatorial positions and with two halogen atoms in the apical positions. Whereas each of the Te–C(Ar) bond distances were very similar [2.10 ± 0.01 Å], the Te–C(R) bonds of 2a–c were longer than Te–C(Ar) and increased in length in the order R = Me < Et < i-Pr. The C(Ar)–Te–C(R) bond angles also increased in the order R = Me < Et < i-Pr. These molecules were bridged by intermolecular Te⋯X bonding to form dimers or polymers. Based on these results and VSEPR theory, the dependence of the rotational barrier ΔG‡ of the Ar-group in RArTeX₂ on the R-group is discussed.

Tris(2,6-dimethoxyphenyl)telluronium chloride hydrate, [R₃Te]Cl·nH₂O 1a [R = 2,6-(MeO)₂C₆H₃, n = 2–2.5] was prepared by the reaction of RLi and TeCl₄. It decomposed in hot 0.1 M hydrochloric acid to give R₂TeCl₂ 3a, exclusively, from which R₂TeX₂ (X = Br 3b, I 3c or SCN 3d) were derived by halogen exchange. The X-ray crystallographic analyses of 3a–3d showed that these compounds have a twofold axis (except for 3d) with essentially pseudo-trigonal bypyramidal co-ordination with two R groups and a lone pair of electrons occupying the equatorial sites and two halogen atoms the apical sites. The thiocyanate groups in 3d bind to tellurium atom via sulfur. No intermolecular Te  · · ·  X secondary bond was observed for 3a–d. The Te–C bond distances of 3a–c [2.09 ± 0.01 Å] are somewhat shorter than those reported for phenyl derivatives, and those of 3d [2.042(3) and 2.073(2) Å] are the shortest ever reported. The C–Te–C bond angle is much larger [107.6(2)–104.37(9)°] than those reported. The X–Te–X bond angles are very close to 180°. The Te  · · ·  O distances of 3a–d [2.880–3.323 Å] are significantly shorter than the sum of the O and Te van der Waals radii [3.60 Å]. The ¹H NMR spectra of 3a–3c were halogen-, solvent-, and temperature-dependent showing that the rotation of R–Te bonds was restricted due to the barrier between R groups and halogen atoms. The activation energies ΔG^‡ decreased in the order 3a (90 kJ mol⁻¹ in DMSO-d₆) > 3b (80 kJ mol⁻¹ in DMSO-d₆) > 3d (≥65 kJ mol⁻¹ in CDCl₃) > 3c (60 kJ mol⁻¹ in CDCl₃) ≥ 3d (59 kJ mol⁻¹ in CD₃CN).

Hydrotalcite-like compounds (HT), layered double hydroxides with a few kinds of interlayer anions (X=CO32−, Cl−, and NO3−) were allowed to react with acrylate anions in order to prepare a novel inorganic–organic interstratified layered material by anion exchange. When HT–CO3was used the anion exchange reaction did not occur. When HT–NO3was employed the reaction proceeded to form a HT–acrylate intercalation compound. The formation of the intercalation compound from HT–Cl was observed only under a reaction condition using a concentrated acrylate solution. When the intercalation compound was heated at 80 °C with the addition of an initiator, the interlayer acrylate anions were polymerized to form a HT–polyacrylate intercalation compound.

Oxygen K‐edge X‐ray absorption near edge structures (XANES) spectra of amino acids (glycine, L‐α‐alanine, β‐alanine, L‐serine, L‐asparic acid and L‐tyrosine) were measured. Several peaks of XANES spectra were successfully assigned on the basis of DV‐Xα calculation.

Binary Ce-Ir alloys nominally containing 83, 78, 75, and 67 at% Ir were grown via arc melting in order to clarify the optimum composition for a Ce-Ir system to be used as photocathode material. Scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), and X-ray diffraction (XRD) analysis were employed to characterize the microstructure and phase composition of these alloys. The results of the XRD analyses and SEM/EDX measurements indicated that single-phase homogeneous crystals composed of CeIr2 grains were successfully grown in the sample with an iridium content amounting to 67 at%. Through quantum efficiency (QE) measurements, it was revealed that the QE of the Ce-67 at% Ir alloy (CeIr2 phase) is a few times higher than that of the other Ce-Ir alloys.

Laser processing is a common method used to shape various structures of biodegradable polymers. In this study, we demonstrate PLLA processing with intense deep ultraviolet (DUV) pulses at 266 nm and compare the processing properties using a nanosecond DUV laser. Results allow comparison of the single-shot ablation thresholds and multiple-shot morphology of both the femtosecond and nanosecond DUV laser. For sing-shot experiments, the ablation threshold of femtosecond laser is, at least, one order of magnitude lower than that of nanosecond laser. For multiple-shot experiments, the result provides superior quality of the crater morphology in the DUV femtosecond regime.

To investigate cytokine/chemokine changes in amyotrophic lateral sclerosis (ALS), we simultaneously measured 16 cytokine/chemokines (interleukin [IL]-1β, IL-2, IL-4, IL-5, IL-6, IL-7, IL-8, IL-10, IL-12 [p70], IL-13, IL-17, interferon-γ, tumor necrosis factor-α, granulocyte colony stimulating factor [G-CSF], macrophage chemoattractant protein-1 [MCP-1], and macrophage inflammatory protein-1β) in cerebrospinal fluid (CSF) and sera from 37 patients with sporadic ALS and 33 controls using a multiplexed fluorescent bead-based immunoassay. We also conducted immunohistochemical analyses from 8 autopsied ALS cases and 6 nonneurologic disease controls as well as cell culture analyses of relevant cytokines and their receptors. We found that concentrations of G-CSF and MCP-1 were significantly increased in ALS CSF compared with controls. In spinal cords, G-CSF was expressed in reactive astrocytes in ALS cases but not controls, whereas G-CSF receptor expression was significantly decreased in motor neurons of spinal cords from ALS cases. Biologically, G-CSF had a protective effect on the NSC34 cell line under conditions of both oxidative and nutritional stress. We suggested that G-CSF has potentially neuroprotective effects on motor neurons in ALS and that downregulation of its receptor might contribute to ALS pathogenesis. On the other hand, MCP-1 correlated with disease severity, which may aggravate motor neuron damage.