First synthesis of bidentate NHC-Pd complexes with anthracene and xanthene skeletons

We synthesized a series of new bidentate NHC (N-heterocyclic carbene) precursors with anthracene and xanthene skeletons. The corresponding NHC-Pd complexes were prepared from these precursors. The catalytic activity of these Pd complexes was examined.     

Evaluation of critical current based on a new transition concept

The critical current of high-temperature superconductor (HTS) tapes depends on temperature, magnetic field, and flux angle against the tape. Analyzing the performance of an HTS coil relies on the critical current equation, which has these dependencies. To date, the critical current equation has been obtained by fitting the measured data. However, this fitting method requires the time-consuming and laborious work of measuring the tapes. In this study, based on a new transition concept in applying a magnetic field, we show how to obtain the critical current equation, while keeping the temperature constant. From the wave function of the Cooper pair which distributes along a magnetic flux quantum, a wave function at the transition state is obtained; this yields the wave functions with perpendicular and parallel magnetic components against the tape. Combining these wave functions yields the conclusive critical current density equation. To confirm the accuracy of this equation, used Bi-2223/Ag tapes, it was compared with the measured critical current under various magnetic fields and flux angles; it was found that they agree well. The parameters of this equation can be obtained by measuring the perpendicular/parallel critical magnetic field component. This equation does not require fitting the measured data, therefore, it can be employed with any Bi-2223/Ag tape.     

Dimer effect on fractional polycondensation of poly(p‐oxybenzoyl)

Selective preparation of poly(p‐oxybenzoyl) (POB) crystals was examined from the viewpoint of a dimer effect on fractional polycondensation. Four different copolymerization systems were chosen as the combinations of p‐acetoxybenzoic acid (p‐ABA), m‐acetoxybenzoic acid (m‐ABA), and their dimers. The crystals obtained from the copolymerization of the dimer of p‐ABA (p‐ABAD) and m‐ABA contained only 3.1 mol % of m‐oxybenzoyl moiety even at high content of m‐oxybenzoyl moiety in feed (χ_f) of 40 mol %. p‐Oxybenzoyl homo‐oligomers were more rapidly formed from p‐ABAD in the solution than from p‐ABA, and they were crystallized to form the crystals with segregating co‐oligomers. While co‐oligomers containing more m‐oxybenzoyl moiety were formed in the solution, afterward they were unable to be phase‐separated because of higher miscibility. The further polycondensation proceeded in the precipitated crystal, and finally the POB crystal was selectively formed. Lower polymerization temperature and concentration enhanced the fractionability, and the POB crystals containing less than 1 mol % m‐oxybenzoyl moiety were prepared at χ_f of 30 mol %, 270 °C, and a concentration of 0.5%. The dimer effect on the fractional polycondensation was clearly observed. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1598–1606, 2008     

Enantioselective Friedel–Crafts reactions of ethenetricarboxylates and substituted pyrroles and furans and intramolecular reaction of benzene derivatives

Compared to enantioselective Friedel–Crafts reactions of indoles, reactions of alkylidene malonates with monocyclic aromatic compounds generally proceed with low enantioselectivity. The Friedel–Crafts reactions of ethenetricarboxylates 1 and monocyclic heteroaromatic compounds, such as substituted pyrroles and furans were investigated. The reaction of 1 with 2,4-dimethylpyrrole in the presence of a chiral bisoxazoline–copper(II) complex (10 mol %) in tetrahydrofuran at room temperature gave alkylated products in up to 72% ee. The reaction of 1 with 2-substituted furans gave alkylated products in 46–62% ee. The absolute stereochemistry of the furan Friedel–Crafts product 7e was determined by transformation to the known 2,3-dimethylbutyric acid. The intramolecular reaction of benzene derivatives gave cyclized products up to 56% ee.     

Direct importance estimation for covariate shift adaptation

A situation where training and test samples follow different input distributions is called covariate shift. Under covariate shift, standard learning methods such as maximum likelihood estimation are no longer consistent—weighted variants according to the ratio of test and training input densities are consistent. Therefore, accurately estimating the density ratio, called the importance, is one of the key issues in covariate shift adaptation. A naive approach to this task is to first estimate training and test input densities separately and then estimate the importance by taking the ratio of the estimated densities. However, this naive approach tends to perform poorly since density estimation is a hard task particularly in high dimensional cases. In this paper, we propose a direct importance estimation method that does not involve density estimation. Our method is equipped with a natural cross validation procedure and hence tuning parameters such as the kernel width can be objectively optimized. Furthermore, we give rigorous mathematical proofs for the convergence of the proposed algorithm. Simulations illustrate the usefulness of our approach.     

On the Iwasawa invariants of certain non-cyclotomic ℤ2-extensions

Let k be an imaginary quadratic field in which the prime 2 splits. We consider the Iwasawa invariants of a certain non-cyclotomic ℤ₂-extension of k and give some sufficient conditions for the vanishing of λ- and μ-invariants.     

二氧化钛负载的镍氧化态对乙腈气相加氢的影响

采用浸渍法制备了二氧化钛负载镍催化剂. 通过控制还原温度(200-400 ℃), 在TiO₂上得到不同氧化态的镍颗粒. 结果发现, 乙腈气相加氢反应受镍氧化态的影响, 300 ℃下还原的催化剂表现出最高的乙腈转化活性, 100 ℃时将乙腈完全转化. 产物产率受到Ni/TiO₂催化剂酸性的影响, 而催化剂的酸性不仅受到TiO₂载体的影响, 还受到负载物Ni 颗粒性质的影响. 随着催化剂还原温度升高, 金属态镍逐渐出现在催化剂表面, 降低了催化剂的酸性强度, 使三乙胺的最大产率升高(从34%升高到48%左右). 研究还发现在Ni/TiO₂催化乙腈加氢反应中, 三乙胺是初始产物. Ni 的状态不仅影响乙腈的转化, 还影响产物的脱附. 提出了乙腈加氢的第一步反应机理.     

Design theory and experiment of acousto-optical tunable filter by use of flexural waves applied to thin optical fiber

Spectral response of acoustically induced microbending through thin optical fiber is discussed from mode-coupling of core and cladding modes. The thin fiber is analyzed in three-layered structure (core-cladding-air) to gain insights into acousto-optic modulation. We explained the dependence of core and/or cladding diameters on acoustic source parameters from numerical calculations. According to the calculations, we successfully fabricated all-optical tunable filter using this thin fiber that yields an efficient mode-coupling at flexural wave frequencies less than 1MHz. To increase the acousto-optic effect, we used a specially designed thin optical fiber (80 μm of cladding diameter) in the section where flexural wave is produced, and spliced both ends of the thin fiber to the tapered 125 μm fibers. The frequency and voltage tuning of fabricated filter is also confirmed by changing the driven frequency and applied voltage of the PZT, respectively. This result suggests a possibility of fiber-optic device application as all-optical tunable filter at 1.55 μm.     

Clinical outcome of a novel photodynamic therapy technique using acridine orange for synovial sarcomas

Synovial sarcoma (SS) is one of common malignant soft-tissue tumors and is encountered most commonly in children and young adults. It frequently involves or invades major neurovascular structures and bones, and its local recurrence rate after simple resection has been reported to be as high as up to 80%. Because major nerves and vessels, as well as an adequate amount of bone, must be preserved to restore excellent limb function in cases of SS, a surgical technique entailing a low risk of local recurrence is needed. Based on the findings of recent experimental studies conducted by us using a mouse osteosarcoma model, we developed a novel therapeutic technique for SS, consisting of reduction surgery followed by photodynamic therapy using acridine orange (AO-PDT), with or without X-ray irradiation at 5 Gy. A preliminary study revealed that low-dose X-rays also excite AO like photons. After an initial study on cell cultures, this novel technique was applied to six cases of SS. A follow-up of the subjects to determine the clinical outcome revealed that none of the cases treated by AO-PDT, including the four cases treated by additional 5 Gy irradiation and the two cases not receiving any radiation, showed any evidence of recurrence or local/systemic complications during the follow-up period of 19-51 months after the surgery. Therefore, we believe that AO-PDT with 5 Gy irradiation may be an excellent novel therapeutic modality with reduction surgery to salvage excellent limb function in SS involving major nerves and vessels or bones.     

Surface-fluorinated graphite anode materials for Li-ion batteries

Surface modification of graphite powder has been performed by chemical fluorination using elemental fluorine at 200 °C and 300 °C. This process leads to an increase of the BET surface area due to partial CC bond breaking. Surface analyses performed by secondary ions mass spectrometry have shown that the H + O content at the surface of graphite is significantly decreased by this fluorination treatment. Fluorinated graphite powders have been tested as negative electrodes in Li-ion battery, chronopotentiometry measurements have shown that the fluorinated graphite exhibits better electrochemical performances than raw graphite powder notably due to an increase of the surface area which allows the storage of a higher amount of lithium into the host lattice. In addition, impedance measurements performed in a delithiated state have shown a significant decrease of the total cell resistance, i.e. a decrease of both the charge transfer resistance and the resistance related to the solid electrolyte interface (SEI) layer.