Molecular motion of syndiotactic poly(α-methylstyrene) in solution studied by carbon-13 n.m.r. relaxation measurements

The carbon-13 n.m.r. spin-lattice relaxation times, nuclear Overhauser enhancement factor (NOE), and line widths have been measured for a syndiotactic poly(α-methylstyrene) in solutions in toluene-d₈ and o-dichlorobenzene-d₄ as a function of temperature from 40° to 163δC. The single correlation time model of relaxation is inadequate to explain the data of spin-lattice relaxation time and NOE. But, within experimental error, these relaxation data in two solvents over a full temperature range can be interpreted in terms of either the Cole-Cole or the log-χ² distributions of correlation times, or a conformational jump model proposed by Monnerie et al. The internal rotation of the methyl group is relatively rapid, while that of the phenyl ring is slow and practically overshadowed by the backbone segmental reorientation over the temperature range examined. The solvent dependence of relaxation data was discussed.     

Synovial osteochondromatosis of the temporo-mandibular joint

A rare case of synovial osteochondromatosis of the temporo-mandibular joint is presented. Important diagnostic information can be obtained by CT, MRI, 99m Tc bone scan and aspiration biopsy. Observation using a light microscope showed mild cellular atypia, but the hallmarks characteristic of chondrosarcoma were not found. Observation using an electron microscope showed the mature chondrocytes contained a well-developed rough endoplasmic reticulum. Histological evaluation indicated that the present case was benign synovial osteochondromatosis in an early stage.     

Grafting of polyesters onto carbon black. III. Polymerization of β-propiolactone initiated by quaternary ammonium carboxylate groups on the surface of carbon black

By use of carbon black containing quaternary ammonium carboxylate (COO^?N⁺R₄) groups as catalyst, the anionic ring opening polymerization of β-propiolactone (PL) was carried out at 50°C. Although carbon black itself was unable to initiate the polymerization of PL, carbon black containing COO^?N⁺R₄ groups, which was prepared by the reaction of carboxyl groups with corresponding quaternary ammonium hydroxide, was found to be able to initiate the polymerization. The carbon black obtained from the polymerization gave a stable colloidal dispersion in an organic solvent, and it was confirmed that the polyester formed was effectively grafted onto the surface. In addition, the effect of quaternary ammonium countercation on the polymerization was investigated.     

Study on Lubricant Depletion Induced by Laser Heating in Thermally Assisted Magnetic Recording Systems: Effect of Lubricant Thickness and Bonding Ratio

In this study, we have carried out fundamental research on lubricant depletion due to laser heating in thermally assisted magnetic recording. In particular, we investigated the effects of lubricant film thickness and lubricant bonding ratio on lubricant depletion. Conventional lubricants Zdol2000 and Ztetraol2000 were used. The lubricant depletion characteristics due to laser heating were found to depend largely on the lubricant film thickness and material. That is, for films thicker than one monolayer, the lubricant depletion depth increased with the laser-irradiation duration, whereas the thickness of the lubricant after laser irradiation on the diamond-like carbon (DLC) films tended to remain at a constant film thickness of one monolayer. The lubricant depletion width gradually increased as the laser irradiation duration increased. The increasing trends for the lubricant depletion width were quantitatively very similar and almost independent of the initial lubricant film thickness. However, for lubricant films with thicknesses less than one monolayer, the lubricant depletion depth was very small. The lubricant depletion width increased remarkably to several hundred micrometers as the laser irradiation duration increased. The lubricant depletion depth and width were much smaller for Ztetraol2000 than Zdol2000. In addition, the lubricant-bonding ratio was found to greatly affect the lubricant depletion characteristics due to laser heating. In other words, the lubricant depletion depth and width decreased as the bonding ratio increased. The lubricant depletion mechanism involves the evaporation of mobile lubricant molecules when the maximum attained temperature is less than 100 °C. Another suggested lubricant depletion mechanism involves the thermocapillary stress effect, which is induced by the disk surface temperature gradient resulting from the non-uniformity of the laser spot intensity distribution.     

Development of a homogeneous competitive immunoassay for phosphorylated protein antigen based on the enhanced fluorescence resonance energy transfer technology

We describe a homogeneous competitive immunoassay for a phosphorylated protein antigen. The assay takes advantage of the enhanced fluorescence resonance energy transfer (FRET) technology, which has a unique characteristic that the FRET signal is increased by the specific interaction of two fluorolabeled leucine zippers. We chose extracellular signal-regulated kinase (ERK) as a model antigen and constructed two molecular probes in which either anti-phosphorylation site antibody or the antigen peptide was chemically conjugated to the enhanced FRET probes. While these molecular probes indicated sufficient FRET signal without antigen, they displayed a significant change in the fluorescent spectrum by mixing with phosphorylated antigens. With this competitive enhanced FRET immunoassay, a phosphorylated ERK concentration within the range from 15 nM to 250 nM could be determined. Because the assay is very simple, it would be applied to not only in vitro assay but also in vivo detection of protein phosphorylation.     

Validation of MAAP model enhancement for Fukushima Dai-ichi accident analysis with Phenomena Identification and Ranking Table (PIRT)

The Modular Accident Analysis Program (MAAP) model enhancement items to improve the simulation capability for molten corium behavior in the accidents at the Fukushima Dai-ichi nuclear power plants were validated with the Phenomena Identification and Ranking Table (PIRT). The importance ranks of the identified phenomena were evaluated for each time phase through brainstorming and discussion with the experts in the Atomic Energy Society of Japan and the members of the MAAP model enhancement project. When the current MAAP evaluation models were reviewed with the PIRT, it is found that 95 of the 386 high-ranked phenomena were not considered in MAAP 5.0.1. While 62 of these phenomena will have been addressed in the MAAP enhancement project and 25 others are not suitable to be analyzed by MAAP, 8 important phenomena should be considered in post-MAAP enhancement project with additional experiments or fundamental studies.     

Novel Enantiocomplementary C2‐Symmetric Chiral Bis(imidazoline) Ligands: Highly Enantioselective Friedel–Crafts Alkylation of Indoles with Ethyl 3,3,3‐Trifluoropyruvate

Enantioselective Friedel–Crafts alkylations of a variety of indoles with ethyl 3,3,3‐trifluoropyruvate catalyzed by novel chiral m‐phenylenebis(imidazoline)‐copper(II) complexes or the bis(imidazoline)‐achiral acid combination afforded products with high enantioselectivity. Both enantiomers of indole derivatives can be prepared with high enantioselectivities by tuning the N‐substituents of the imidazoline.     

Functional analyses of neutrophil-like differentiated cell lines under a hyperglycemic condition

Diabetic patients are prone to severe bacterial infections. The functional alterations of neutrophils by hyperglycemia are thought to be partially responsible for such infections. In this study, we investigated the functional changes of neutrophil-like differentiated cell lines (dHL-60, dTHP-1, and dNB-4) by treatment with 5.5 mM, 11 mM, or 35 mM of glucose. In dHL-60 cells, the incubation with high glucose (35 mM) resulted in the enhancement of cell aggregation, the suppression of cellular fragility, the induction of reactive-oxygen species (ROS) production by phorbol myristate acetate (PMA) stimulation, and the impairment of phagocytosis. In dTHP-1 cells, the treatment with higher glucose generated the suppression of cellular fragility and extremely impaired phagocytosis (by 35 mM), and induced ROS production due to PMA stimulation (by 11 mM). Furthermore, the higher glucose exposure to dNB-4 cells enlarged intracellular vacuoles (by 35 mM) and induced ROS production due to PMA stimulation (by 11 mM). Since the ROS generation of those cells was enhanced only after PMA stimulation under the higher glucose conditions, glucose may have a priming effect rather than a triggering effect. These extraordinary sensitivities caused by the higher glucose treatments may reflect the dysfunction or overactivation of neutrophils.     

Construction of Cellulose Binding Domain Fusion FMN-Dependent NADH-Azoreductase and Glucose 1-Dehydrogenase for the Development of Flow Injection Analysis with Fusion Enzymes Immobilized on Cellulose

The cellulose binding domain (CBD) of cellulosome-integrating protein A from Clostridium thermocellum NBRC 103400 was genetically fused to FMN-dependent NADH-azoreductase (AZR) and glucose 1-dehydrogenase (GDH) from Bacillus subtilis. The fusion enzymes, AZR-CBD and CBD-GDH, were expressed in Escherichia coli Rosetta-gami B (DE3). The enzymes were purified from cell-free extracts, and the specific activity of AZR-CBD was 15.1 U/mg and that of CBD-GDH was 22.6 U/mg. AZR-CBD and CBD-GDH bound strongly to 0.5 % swollen cellulose at approximately 95 and 98 % of the initial protein amounts, respectively. After immobilization onto the swollen cellulose, AZR-CBD and CBD-GDH retained their catalytic activity. Both enzymes bound weakly to 0.5 % microcrystalline cellulose, but the addition of a high concentration of microcrystalline cellulose (10 %) improved the binding rate of both enzymes. A reactor for flow injection analysis was filled with microcrystalline cellulose-immobilized AZR-CBD and CBD-GDH. This flow injection analysis system was successfully applied for the determination of glucose, and a linear calibration curve was observed in the range of approximately 0.16–2.5 mM glucose, with a correlation coefficient, r, of 0.998.     

Solidification microstructure-dependent hydrogen generation behavior of Al–Sn and Al–Fe alloys in alkaline medium

This work deals with the development of quantitative correlations of hydrogen evolution performance with solidification microstructural and thermal parameters in Al–1Sn, Al–2Sn, Al–1Fe, and Al-1.5Fe [wt.%] alloys. The cellular growth as a function of growth and cooling rates is evaluated using power type experimental laws, which allow determining representative intervals of microstructure length scale for comparison purposes with the results of immersion tests in 5 wt%NaOH solution. For both Al alloys systems, hydrogen evolution becomes slower as the alloy solute content increased. However, for a given alloy composition, whereas a more homogeneous distribution of Sn-rich particles promotes faster hydrogen generation using Al–Sn alloys, coarsening of Al₆Fe IMCs (intermetallic compounds) fibers favors hydrogen production using Al–Fe alloys. When solidification conditions that result in a range of cellular spacings within 16 and 19 μm are considered, the specific hydrogen production of the Al-1wt.%Fe alloy is higher than that of the other studied alloys.