Synthesis and Self-Organization of Fluorene-Conjugated Bisimidazolylporphyrin and Its Optical Properties

A conjugated-bisimidazolylporphyrin bridged by bis(ethynylfluorene) was synthesized and organized into linear polymer through self-coordination having mean molecular weights, M_w and M_n, of ~2.1 × 10⁵ Da and ~1.6 × 10⁵ Da, respectively. A large two-photon absorption cross section value of 3.4 × 10⁵ GM (per dimer unit) was observed. This value was comparable to that of the previously reported self-assembled linear polymer consisting of butadiyne-bridged imidazolylporphyrins. The two-photon absorption properties could be controlled by tuning the wavelength and absorption intensity of the one-photon absorption.     

Intestinal absorption and biological effects of orally administered amorphous silica particles

Although amorphous silica nanoparticles are widely used in the production of food products (e.g., as anticaking agents), there is little information available about their absorption and biological effects after oral exposure. Here, we examined the in vitro intestinal absorption and in vivo biological effects in mice of orally administered amorphous silica particles with diameters of 70, 300, and 1,000 nm (nSP70, mSP300, and mSP1000, respectively) and of nSP70 that had been surface-modified with carboxyl or amine groups (nSP70-C and nSP70-N, respectively). Analysis of intestinal absorption by means of the everted gut sac method combined with an inductively coupled plasma optical emission spectrometer showed that the intestinal absorption of nSP70-C was significantly greater than that of nSP70. The absorption of nSP70-N tended to be greater than that of nSP70; however, the results were not statistically significant. Our results indicate that silica nanoparticles can be absorbed through the intestine and that particle diameter and surface properties are major determinants of the degree of absorption. We also examined the biological effects of the silica particles after 28-day oral exposure in mice. Hematological, histopathological, and biochemical analyses showed no significant differences between control mice and mice treated with the silica particles, suggesting that the silica nanoparticles evaluated in this study are safe for use in food production.     

Kinetics of Enthalpy Relaxation at the Glass Transition in Ternary Tellurite Glasses

The kinetics of enthalpy relaxation (recovery) at the glass transition in x K₂O·(20− x )MgO·80TeO₂ glasses has been examined from heat capacity measurements using differential scanning calorimetry to clarify the features of the structural relaxation in ternary TeO₂-based glasses. Ternary glasses such as 10K₂O·10MgO·80TeO₂ show high thermal resistance against crystallization compared with binary glasses. The degree of fragility m estimated from the activation energy for viscous flow E _η and the glass transition temperature T _g is m = 55–62, indicating a fragile character in TeO₂-based glasses. Large heat capacity changes of 43.1–48.2 J·mol⁻¹·K⁻¹ are also observed at the glass transition. The activation energy for enthalpy relaxation Δ H is evaluated from the cooling rate dependence of the limiting fictive temperature, and values of Δ H = 897–1268 kJ·mol⁻¹ are obtained. Negative deviation from additivity in Δ H is also observed. Values of the Kovacs–Aklonis–Huchinson–Ramos (KAHR) parameter θ estimated from Δ H and T _g are 0.33–0.42 K⁻¹. It has been proposed that ternary glasses have more homogeneous and constrained glass structure compared with binary glasses.     

Preparation method for supported metal catalysts using w/o microemulsion: Study on immobilization conditions of metal particles by hydrolysis of alkoxide

It was previously found that the silica-supported rhodium catalyst prepared using water-in-oil microemulsion had rhodium particles partly, or wholly, embedded in silica. In this work, consequently, we investigated the effect of hydrolysis conditions of tetraethylorthosilicate, employed as the source of silica, on the atomic ratio of surface rhodium in contact with the gas phase, to total surface rhodium of nanoparticles. This ratio is denoted as R in this paper. R became higher when the catalyst was prepared under the following hydrolysis conditions: a shorter hydrolysis time and a smaller amount of tetraethylorthosilicate. On the other hand, R showed the minimum value when the water content in the preparation solution was 33 vol%. From these results, it is demonstrated that it was important to form silica as early as possible in hydrolysis of TEOS in order to increase R values. In addition, the effect of R on the catalytic behavior in CO hydrogenation was investigated. At R values below 30%, the turnover frequencies increased with a decrease in R.     

Enantioselective addition Of diketene to aldehydes promoted by chiral schiff base—titanium alkoxide complex. Application to asymmetric synthesis of potential inhibitors of HMG coenzyme reductase

Highly enantioselective addition of diketene to aldehydes was achieved by using novel Schiff base—titanium alkoxide complexes. Up to 92% ee of 5-hydroxy-3-oxoesters was obtained. This procedure provides an efficient method for the asymmetric synthesis of potential inhibitors of HMG coenzyme reductase.     

Fabrication of optics by use of plasma chemical vaporization machining with a pipe electrode

We figure optical surfaces by plasma chemical vaporization machining (CVM) with a pipe electrode, in which an rf plasma generated at the electrode tip under approximately atmospheric pressure moves over the surfaces. We propose a shaping method in which the movement of plasma on the surfaces can be determined. Flat and aspheric surfaces are successfully figured with the desired peak-to-valley shape accuracy of 0.1 microm. The root-mean-square roughness of the resultant surfaces is at the subnanometer level. These results confirm that the plasma CVM and the shaping method have the capability to fabricate optics with high accuracy.     

Positioning device for outdoor mobile robots using optical sensors and lasers

We propose a novel method for positioning a mobile robot in an outdoor environment using lasers and optical sensors. Position estimation via a noncontact optical method is useful because the information from the wheel odometer and the global positioning system in a mobile robot is unreliable in some situations. Contact optical sensors such as computer mouse are designed to be in contact with a surface and do not function well in strong ambient light conditions. To mitigate the challenges of an outdoor environment, we developed an optical device with a bandpass filter and a pipe to restrict solar light and to detect translation. The use of two devices enables sensing of the mobile robot’s position, including posture. Furthermore, employing a collimated laser beam allows measurements against a surface to be invariable with the distance to the surface. In this paper, we describe motion estimation, device configurations, and several tests for performance evaluation. We also present the experimental positioning results from a vehicle equipped with our optical device on an outdoor path. Finally, we discuss an improvement in postural accuracy by combining an optical device with precise gyroscopes.     

Molecular valve consisting of poly(acrylic acid) gel

A molecular valve, consisting of poly(acrylic acid) gel-coated Au mesh, was developed based on volume change of the gel in response to cation concentration. The valve closed when concentration of cations such as H⁺, Na⁺, K⁺, Ca²⁺, Cu²⁺, or Al³⁺ was low, whereas opened upon increase in its concentration. The valve re-closed when water was flowed. The concentration where the valve opens was found to increase in the order of Al³⁺, Ca²⁺, and Na⁺ (2 × 10⁻⁴, 5 × 10⁻⁴, and 6 × 10⁻³ M, respectively). The response to Cu²⁺ ion showed similar behaviour, but the opening concentration was ca. 2 × 10⁻⁴ M, which is lower than that of Ca²⁺ ion. The valve appeared to close over the pH range from 3 to 12, whereas to open below and above it. The fastest response time to open the valve (less than 1 min) was obtained for a solution of pH 1–2. The valve showed repeatability at least 25 cycles upon successive loading of a solution of pH 2 and water. Effects of anions and pressure were also studied.     

A multilevel PWM strategy suitable for high‐voltage motor direct drive systems with consideration of the adverse effect of dead time

Recently, high‐voltage motor direct drive systems have been put to practical use, and various multilevel PWM strategies have also been proposed. This paper describes a multilevel PWM strategy [our group calls it the Carrier Phase Selection Method (CPS)] that has the lowest line voltage harmonic distortion in order to prevent the degradation of high‐voltage motor winding insulations. This method takes the adverse effect of dead time into consideration, and it controls the shift direction of a carrier phase. Therefore, a favorable output waveform without instantaneous voltage surges is achieved even if the line voltage level changes. Moreover, the switching transitions across all switching devices are well‐balanced, so the utilization of inverter unit cells is equalized. This is an important factor when designing the entire system. Based on simulation and experimental results, it is shown that this CPS method is particularly effective in high‐voltage motor direct drive systems. © 2008 Wiley Periodicals, Inc. Electr Eng Jpn, 165(2): 77–88, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/eej.20474