Pd-catalyzed hydrosilylation polymerization of a dihydrosilane with diyne/triyne mixed systems affording crosslinked silylene-divinylene polymers and their properties

Treatment of a dihydrosilane (methylphenylsilane, 1) with mixtures of a diyne (p- or m-diethynylbenzene, 2a or 2b) and a triyne (1,3,5-triethynylbenzene, 3a or B,B′,B″-triethynyl-N,N′,N″-trimethylborazine, 3b; 1:2:3=100:95:5, 100:90:10, 100:80:20) in the presence of Pd-PCy₃ (Cy=cyclohexyl) catalyst gave new crosslinked silylenedivinylene polycarbosilanes. In TGA the resulting crosslinked polymers tended to show higher Td₅ values and higher char yields than the corresponding linear polymers. On the other hand, UV/vis absorption spectra of the crosslinked polymers obtained in the reactions of 2a or 2b with 3a exhibited increased broad peaks around 390 nm for 2a or 360 nm for 2b. Coincidently, their fluorescence spectra showed significant increase of the emission peaks in 400-550 nm. The crosslinked polymer derived from 2a and 3b, however, showed decrease of the absorption peak around 390 nm and profound depression of fluorescence peaks in 400-550 nm.     

Calibration method for a carbon nanotube field-effect transistor biosensor

An easy calibration method based on the Langmuir adsorption theory is proposed for a carbon nanotube field-effect transistor (NTFET) biosensor. This method was applied to three NTFET biosensors that had approximately the same structure but exhibited different characteristics. After calibration, their experimentally determined characteristics exhibited a good agreement with the calibration curve. The reason why the observed characteristics of these NTFET biosensors differed among the devices was that the carbon nanotube (CNT) that formed the channel was not uniform. Although the controlled growth of a CNT is difficult, it is shown that an NTFET biosensor can be easy calibrated using the proposed calibration method, regardless of the CNT channel structures.     

Label-free protein biosensor based on aptamer-modified carbon nanotube field-effect transistors

We have fabricated label-free protein biosensors based on aptamer-modified carbon nanotube field-effect transistors (CNT-FETs) for the detection of immunoglobulin E (IgE). After the covalent immobilization of 5'-amino-modified 45-mer aptamers on the CNT channels, the electrical properties of the CNT-FETs were monitored in real time. The introduction of target IgE at various concentrations caused a sharp decrease in the source-drain current, and a gradual saturation was observed at lower concentrations. The amount of the net source-drain current before and after IgE introduction on the aptamer-modified CNT-FETs increased as a function of IgE concentration. The detection limit for IgE was determined as 250 pM. We have also prepared CNT-FET biosensors using a monoclonal antibody against IgE (IgE-mAb). The electrical properties of the aptamer- and antibody-modified CNT-FETs were compared. The performance of aptamer-modified CNT-FETs provided better results than the ones obtained using IgE-mAb-modified CNT-FETs under similar conditions. Thus, we suggest that the aptamer-modified CNT-FETs are promising candidates for the development of label-free protein biosensors.     

Effects of photo-induced graft polymerization of 2-methacryloyloxyethyl phosphorylcholine on physical properties of cross-linked polyethylene in artificial hip joints

Osteolysis caused by wear particles from polyethylene in the artificial hip joints is a serious issue. We have used photo-induced radical graft polymerization to graft 2-methacryloyloxyethyl phosphorylcholine (MPC) polymer onto the surface of cross-linked polyethylene (CLPE-g-MPC) in order to reduce friction and wear at the bearing surface of the joint. The physical and mechanical properties of CLPE and CLPE-g-MPC were not significantly different, expect that the friction coefficient of untreated CLPE cups was 0.0075, compared with 0.0009 for CLPE-g-MPC cup, an 88% reduction. After 3.0 × 10⁶ cycles in the hip joint simulator test, we could not observe any wear of CLPE-g-MPC cups. We concluded that the advantage of photo-induced radical graft polymerization technique was that the grafted MPC polymer gave a high lubricity only on the surface and has no effect on the bulk properties of the CLPE substrate.     

Prevention of melanin formation by yeast cerebroside in B16 mouse melanoma cells

The effects of plant and yeast cerebrosides on melanin formation were examined in B16 mouse melanoma cells. Addition of yeast cerebroside significantly reduced melanin content to the same level as that of arbutin in control cells, although there was no suppression by plant cerebrosides and bovine brain cerebroside up-regulated melanin formation. None of the bovine brain cerebrosides examined had any effect on tyrosinase activity, but yeast cerebroside reduced the contents of tyrosinase. The results of the present study clearly showed that melanin formation is regulated by several different cerebrosides via tyrosinase. In addition, the findings presented here suggest that cerebrosides containing a 9-methyl type sphingoid base, such as yeast cerebroside, may be useful as skincare products for suppressing melanin formation.     

Developments in asymmetric hydrogenation from an industrial perspective

Examples of developments in asymmetric hydrogenation from various perspectives, in an effort to improve efficiency, are reported. Discussed in this Account are (1) the improved synthesis of BINAP ligands, (2) the design of SEGPHOS ligands for higher enantioselectivity, (3) a new protocol with fewer reaction steps to synthesize beta-aminoesters, and (4) a novel asymmetric hydrogenation mediated by a copper catalyst.     

Dopamine-induced endocytosis of Na+,K+-ATPase is initiated by phosphorylation of Ser-18 in the rat alpha subunit and Is responsible for the decreased activity in epithelial cells

Dopamine inhibits Na+,K+-ATPase activity in renal tubule cells. This inhibition is associated with phosphorylation and internalization of the alpha subunit, both events being protein kinase C-dependent. Studies of purified preparations, fusion proteins with site-directed mutagenesis, and heterologous expression systems have identified two major protein kinase C phosphorylation residues (Ser-11 and Ser-18) in the rat alpha1 subunit isoform. To identify the phosphorylation site(s) that mediates endocytosis of the subunit in response to dopamine, we have performed site-directed mutagenesis of these residues in the rat alpha1 subunit and expressed the mutated forms in a renal epithelial cell line. Dopamine inhibited Na+,K+-ATPase activity and increased alpha subunit phosphorylation and clathrin-dependent endocytosis into endosomes in cells expressing the wild type alpha1 subunit or the S11A alpha1 mutant, and both effects were blocked by protein kinase C inhibition. In contrast, dopamine did not elicit any of these effects in cells expressing the S18A alpha1 mutant. While Ser-18 phosphorylation is necessary for endocytosis, it does not affect per se the enzymatic activity: preventing endocytosis with wortmannin or LY294009 blocked the inhibitory effect of dopamine on Na+,K+-ATPase activity, although it did not alter the increased alpha subunit phosphorylation induced by this agonist. We conclude that dopamine-induced inhibition of Na+, K+-ATPase activity in rat renal tubule cells requires endocytosis of the alpha subunit into defined intracellular compartments and that phosphorylation of Ser-18 is essential for this process.     

Magnetic field analysis of a 70‐MW‐class superconducting generator by the 3D finite element method

The three‐dimensional magnetic field and eddy current distribution of the 70‐MW‐class superconducting generator was calculated by a finite element method. The condition for the exciting armature coil was calculated by the jω‐method. In the magnetic flux distribution of the armature winding bore, the value obtained by analysis had good agreement with the measurement. An analysis that let the rotor move by the synchronizing speed was also done. The armature voltage for the nonload condition and the armature current for the three‐phase short‐circuit condition obtained by calculations had good agreement with the measurements. The validity of the analytical model for three‐dimensional magnetic field analysis of superconducting generators was confirmed from these results. In addition, the synchronous reactances were calculated using these results with eddy current in the facing. It was found that the facing had the effect of decreasing synchronous reactance by about 5%. © 2000 Scripta Technica, Electr Eng Jpn, 134(2): 53–60, 2001     

Measurement of the damping coefficient of an electric power system by use of a superconducting magnet energy storage system

In this paper, a new application of superconducting magnetic energy storage (SMES) for diagnosis of power systems is proposed. Basic experiments for measurement of damping coefficient of power systems by use of SMES are carried out in an experimental system with a small generator, artificial transmission lines, and a small SMES. The SMES produces small power disturbances in the power system without affecting its operating conditions. The small power oscillations in the power system due to continuous power disturbances generated by SMES are observed. The relations among the damping coefficient, the power disturbances, and the power change of SMES are discussed for a one-machine infinite-bus system. The damping coefficients of the power system are obtained by investigating the oscillations due to the sinusoidal power changes of the SMES. The possibility of estimation of the steady-state power system stability by monitoring the damping coefficients of an operating power system by the use of SMES can be shown experimentally. © 1997 Scripta Technica, Inc. Electr Eng Jpn, 119(3): 40–48, 1997     

Beta tricalcium phosphate ceramics with controlled crystal orientation fabricated by application of external magnetic field during the slip casting process

Beta tricalcium phosphate (β-TCP) is a resorbable bioceramic that has hitherto been utilized in the medical field. Since it crystallizes in the anisotropic hexagonal system, properties such as chemical and physical ones are expected to depend on its crystal axis direction and/or on its crystal plane (anisotropy). Control of crystal orientation is thus important when used in polycrystalline form. Meanwhile, application of a strong magnetic field has been found to be a promising technique to control crystal orientation of anisotropic shape or structured crystals. In this work, we attempted to fabricate β-TCP ceramics with controlled crystal orientation by applying an external magnetic field during the slip casting process and subsequently sintering them at 1050 °C, below the β–α transition temperature. Application of a vertical magnetic field increased intensities of planes perpendicular to c-plane on the top surface, while a horizontal one with simultaneous mechanical mold rotation decreased it. These results indicated that crystal orientation of β-TCP ceramics were successfully controlled by the external magnetic field and together that the magnetic susceptibility of β-TCP is χ_c⊥ > χ_c//.