Language：English   Publishing type：Research paper (scientific journal)  

© 2018 American Chemical Society. [Cu(terpy)]2+ complexes encapsulated into Na-Y zeolite ([Cu(terpy)]2+@Y) were prepared, and their catalytic activities for the oxidation of sulfides using hydrogen peroxide were investigated. Several spectroscopic results, as well as elemental analysis, demonstrated the formation of [Cu(terpy)]2+ complexes in supercages of Y-zeolite. [Cu(terpy)]2+@Y exhibited high selectivity for the oxidation of thioanisole into methylphenylsulfoxide when H2O2 was used. The kinetic study of this oxidation at the catalyst [Cu(terpy)]2+@Y suggests that the reaction of [Cu(terpy)]2+ species with H2O2 is the rate-determining step. The oxidation of thioanisole, benzene, and 2-phenylethylamine using [[Cu(terpy)]2+@Y]∗, which was prepared from the reaction between [Cu(terpy)]2+@Y and H2O2, quantitatively proceeded to methylphenylsulfoxide, phenol, and 2-amino-1-phenylethanol, respectively. The reaction of [Cu(terpy)]2+@Y and H2O2 was found to yield thermally stable but active CuII-OOH species in [Cu(terpy)]2+@Y.

DOI： 10.1021/acscatal.7b04092

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Catalytic activity of iron complex-encapsulated zeolite catalyst ([Fe(bpy)(3)](2+)@Y) for oxidation of benzene increased with increasing the amount of water added to acetonitrile. Maximum value of catalytic activity was obtained when the volume ratio of the solvents was equal (CH3CN:H2O = 1:1). After reaction at 24 h, the turnover number of [Fe(bpy)(3)](2+)@Y was higher than that of [Fe(bpy)(3)](ClO4)(2) as a homogeneous catalyst.

DOI： 10.1246/cl.150479

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Language：Japanese   Publishing type：Research paper (scientific journal)  

DOI： 10.20731/zeoraito.32.3.80

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Fe-bipyridine complexes encapsulated into Na-Y ([Fe(bpy)(3)](2+)@Y) were prepared and their catalytic activities for oxidation of cyclohexene with hydrogen peroxide in CH3CN and H2O solvents were investigated. The prepared [Fe(bpy)(3)](2+)@Y was characterized by several methods and it was found that slightly distorted or compressed [Fe(bpy)(3)](2+) ions were formed within supercages of Y-type zeolite. [Fe(bpy)(3)](2+)@Y catalyst exhibited both higher activity and higher selectivity to 2-cyclohexen-1-ol in water solvent than another Fe catalysts. In addition, the selective hydroxylation of cyclohexene to 2-cyclohexen-1-ol with molecular oxygen was successfully achieved for [Fe(bpy)(3)](2+)@Y catalyst. (C) 2014 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cattod.2014.07.038

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

The selective hydroxylation of cyclohexene to 2-cyclohexen-1-ol with hydrogen peroxide in water was successfully achieved using [Fe(bpy)(3)](2+) complexes encapsulated into Y-type zeolite.

DOI： 10.1246/cl.2012.713

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

In order to understand the effect of an oxygen-containing Ligand on the physico-chemical properties and reactivities of hydrogenperoxocopper complexes, new copper(II) complexes with the N3O-type tripodal ligand bearing pivalamido groups, N,N-bis(6-pivalamido-2-pyridylmethyl)glycine (Hbpga), and N,N-bis(6-pivalamido-2-pyridylmethyl)-beta-alanine (Hbpaa), have been designed and synthesized. Copper(II) complexes without any external ligand and those with a monodentate ligand, such as azido and chloro, have been prepared and characterized with the aid of electronic absorption and ESR spectroscopic, cyclic voltammetric, and X-ray structure analytical methods. The redox potential values of the Cu(II) complexes, when they were compared with the Cu(II) complex of bis(6-pivalamido-2-pyridylmethyl)(2-pyridylmethyl)amine (bppa), reported previously, shifted toward the negative side upon the introduction of a carboxylate group in the place of one pyridine of bppa. Reactions of [Cu(bpga)]ClO4 (1a) and [Cu(bpaa)]PF6 (2a) with hydrogen peroxide in the presence of triethylamine in both MeCN and MeOH solutions gave mononuclear copper(II) complexes with hydrogenperoxide(1-), Cu-bpga-OOH (1d) and Cu-bpaa-OOH (2d) systems, respectively. The intense absorption bands, assignable to LMCT (HOO- --> Cu(II)) and d-d bands, and ESR and resonance Raman spectra have revealed that they form trigonal bipyramidal copper complexes with OOH- in an end-on fashion. The thermal stabilities of 1d and 2d have also been studied by following the reduction rate of the LMCT bands at 283 K. Those of copper(II) complexes with hydrogenperoxide(1-) have been reduced in the order 1d > 2d > [Cu(bppa)(OOH)](+) (3d), all of which are rather stable compared with that of Cu(II)-tpa-OOH (tpa = tris(2-pyridylmethyl)amine). These findings indicate that the hydrogenperoxocopper(II) complexes are activated by introducing carboxylate coordination, although they are stabilized by hydrogen-bonding interactions.

DOI： 10.1246/bcsj.78.116

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：NATL INST MATERIALS SCIENCE  

In this review, basic studies on the binding and activation of dioxygen species by copper complexes with originally designed ligands are described as the initial step for development of environment-friendly oxidation catalyst. In order to examine the stability/reactivity of such a mononuclear copper(II) complex, some copper complexes with hydroperoxide ion have been constructed using the ligands that have been prepared on the basis of the active center structures of metalloenzymes, and the effects of (i) hydrogen bond, (ii) hydrophobic sphere, (iii) coordination structure around metal, and (iv) coordinating atoms have been investigated systematically, from the point of view of synthetic, spectroscopic, structural, kinetic, and theoretical chemistries. It has also been found out that the decomposition rate constants and the O-O bond strengths of hydroperoxo copper(II) complexes are strongly correlated. (c) 2004 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.stam.2004.06.004

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

The effects of hydrogen bonding and hydrophobic field on the thermal stabilities of Cu(II)-OOH complexes have been studied using tripodal tetradentate ligands with their functional groups on the basis of UV-vis, ESR, ESI-mass, and resonance Raman spectroscopies.

DOI： 10.1246/cl.2004.1556

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A novel structural model, [Fe(bpga)(N-3)(OCH3)] (1) (BPGA: bis(6-pivalamido-2-pyridylmethyl)(carboxy-methyl)amine), for an active site of Fe-containing SOD enzyme with N-3(-) has been accurately designed and prepared, which has been characterized by X-ray structure analysis and UV-vis, ESR, and IR spectroscopies. Reaction of 1 with acid/base in methanol has shown that the superoxide-accessible site is the N-3(-)-coordination site in the equatorial plane.

DOI： 10.1021/ic034962t

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

In order to clarify the effect of hydrogen bonding on the stabilities of (mu-peroxo)dicopper complexes with a trans-mu-1,2-peroxo form, novel copper complexes with intramolecular hydrogen bonding interaction sites have been synthesized, and their spectroscopic properties and thermal stabilities studied. The selected tripodal tetradentate ligands were tris(2-pyridylmethyl)amine (TPA) derivatives bearing pivalamido and amino groups at the 6-position of the pyridine ring in TPA, {[6-(pivalamido)pyrid-2-yl]methyl}bis(pyrid-2-ylmethyl)amine (MPPA) and [(6-aminopyrid-2-yl)methyl]bis(pyrid-2-ylmethyl)amine (MAPA). The single-crystal X-ray structure of a monomeric Cu-II complex with N-3(-) namely [Cu(mppa)N-3]ClO4 (1a), revealed an interligand hydrogen bonding interaction between the substituent NH group of MPPA and the azide nitrogen atom in the axial position. The Cu-I complexes of MPPA and MAPA were immediately oxygenated with dioxygen in acetone solution at -78 degreesC to give the p-peroxo dinuclear copper(II) complexes [{Cu(mppa)}(2)(O-2)](2+) (1b) and [{Cu(mapa)}(2)(O-2)](2+) (2b). These complexes exhibited two kinds of characteristic absorption bands (pi*(sigma)-->d(sigma), pi*(v)-->d(sigma)) originating from the ligand-metal charge transfer (LMCT) Of O-2(2-) to Cu. Affected by the hydrogen bonding interaction, the pi*(sigma)-->d(sigma) CT band shifted significantly to a higher energy region and the pi*(v)-->d(sigma) CT absorbance decreased due to stabilization of the pi*(sigma) orbital and restriction of the Cu-O bond rotation. The thermal stabilities of the (mu-peroxo)dicopper(II) complexes were estimated from their decomposition rates which decreased in the order, 2b approximate to [{Cu(tpa)}(2)(O-2)](2+) (3b) > 1b much greater than [{Cu(6-metpa)}(2)(O-2)](2+) (4b) (6-MeTPA = [(6-methylpyrid-2-yl)methyl]bis(pyrid-2-ylmethyl)amine). The above findings indicate that the interligand hydrogen bonding interaction, although overcome to some extent by the adverse effect of the steric bulk of the NH group, is inclined to stabilize (mu-peroxo)dicopper(II) complexes. (C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003.

DOI： 10.1002/ejic.200300178

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A novel copper(II)-OOH complex with functional ligand that can form a hydrogen bond with the distal oxygen of hydroperoxide has been designed and prepared as a structural/functional model of dopamine beta-hydroxylases, whose spectroscopic characterization and decomposition rates have indicated that the hydroperoxide is activated through the hydrogen-bonding interaction with the distal oxygen.

DOI： 10.1021/ic035080x

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Publishing type：Research paper (scientific journal)   Publisher：MDPI AG  

Catalytic alkane hydroxylation activities of the iron complex encapsulated into the micropore of the Y-type zeolite and mesoporous zeolites, the latter of which were obtained by the partial removal of aluminum and alkaline treatment, have been explored by using H2O2 as the oxidant. The iron complex with tris(pyridylmethyl)amine (=TPA) encapsulated into the micropore of the genuine Y-type zeolite was a more stable and effective cyclohexane hydroxylating heterogeneous catalyst compared to the corresponding copper analogue as well as the non-encapsulated homogeneous Fe-TPA complex. The chemical modification of the zeolite supports with the organic groups led to changing the catalytic activity depending on the size and the hydrophobic or hydrophilic nature of the added organic groups. When the content of water in the solvent was increased, the activity of the hydrophilic longer chain-modified catalyst was improved compared to that applied on the reaction with the non-aqueous solvent. The hydrophobic fluoroalkyl modifier located near the entrance of the micropore hindered the access of the substrate and aqueous H2O2 to the encapsulated iron complex site in the genuine Y-type zeolite. On the other hand, the hydrophobic modification effectively improved the activity of the catalyst with the zeolite support having higher amounts of mesopores. The synergistic effect of the wider bore diameters and the hydrophobic nature derived from the fluoroalkyl chains led to the concentration of the hydrocarbon substrate near the active iron complex.

DOI： 10.3390/molecules30040966

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Publishing type：Research paper (scientific journal)   Publisher：Japan Petroleum Institute  

DOI： 10.1627/jpi.67.119

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Ceramic Society of Japan  

The tinmetal mixed hydroxides CaSn(OH)6, MnSn(OH)6, CoSn(OH)6, and ZnSn(OH)6, with cubic morphologies, were prepared using a coprecipitation method; they were subsequently transformed into the corresponding tinmetal mixed oxides by calcination at 600900 °C. The crystalline structures and the morphologies of the various samples at each calcination step (just prepared, dried at 110 °C, and calcined at 600 and 900 °C) were systematically evaluated by X-ray diffractometry, scanning electron microscopy, transmission electron microscopy, and X-ray absorption fine structure analyses. The cubic shapes of the CaSn(OH)6 and ZnSn(OH)6 nanoparticles were maintained after calcination of them at 600 and 900 °C, while those of MnSn(OH)6 and CoSn(OH)6 ones were not maintained after calcination of them.

DOI： 10.2109/jcersj2.21170

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：Frontiers Media SA  

SOFCs fed with dry H₂ and CH₄ fuels were examined using 20 wt% Ni/SDC and 0.2 wt% BaO-added 20 wt% Ni/SDC [Ni(BaO)/SDC] anodes. The i–v characteristics of the cells in H₂ and CH₄ resulted in a higher output produced by CH₄ fuel compared to that produced by H₂ fuel in both anodes. In both fuels, better anode characteristics were obtained for Ni(BaO)/SDC. Consequently, the anodic performance was in the order of Ni(BaO)/SDC in CH₄ > Ni/SDC in CH₄ > Ni(BaO)/SDC in H₂ > Ni/SDC in H₂. A significant carbon deposition was observed in the Ni/SDC anode in CH₄, but the carbon deposition observed in Ni(BaO)/SDC was less. From the DC electrical resistance measurement of the anode films, a remarkable decrease in resistance was observed in Ni/SDC due to the carbon deposition after CH₄ exposure. The resistance of Ni(BaO)/SDC was higher than that of Ni/SDC and did not change even after CH₄ exposure because of the less carbon deposit. The high dispersibility of Ni particles was confirmed in both anodes and was particularly remarkable in Ni(BaO)/SDC. The highest anodic performance in Ni(BaO)/SDC was attributed to the high Ni dispersibility which might promote CH₄ decomposition by producing less carbon deposit. It was speculated that the higher cell output in CH₄ than that in H₂ is due to the locally high concentration of H₂ and/or CO gas on the anode surface by the promotion of CH₄ decomposition.

DOI： 10.3389/fenrg.2021.652239

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Authorship：Lead author   Language：Japanese   Publishing type：Research paper (scientific journal)  

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© 2018 Elsevier B.V. The Ag-loaded perovskite-type oxide catalysts (Ag/LaFeO3-CN and Ag/LaFeO3-imp) were prepared using two different methods, and their catalytic activities for carbon combustion were examined. Ag loading was observed to exhibit a positive effect on the catalytic activity of carbon combustion for an Ag/LaFeO3-CN catalyst that was prepared by the calcination of an Ag-loaded heteronuclear metal cyano-complex precursor. However, Ag loading was not observed to be significantly effective in case of Ag/LaFeO3-imp that was prepared by a general impregnation method. Such a noticeable enhancement in the activity of an Ag/LaFeO3-CN catalyst was assumed to originate from both the high dispersion of Ag that was loaded on LaFeO3 and from the formation of reactive oxygen species between metallic Ag species and the perovskite-type oxide.

DOI： 10.1016/j.cattod.2018.08.019

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Language：English   Publishing type：Research paper (international conference proceedings)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCI LTD  

This study aimed to investigate a cerium triethanolamine complex precursor for the self-propagating high temperature synthesis (SHS) of highly dispersed ceria-supported noble metal catalysts. The cerium complex precursor (Ce-TEA) was prepared by mixing cerium nitrate and triethanolamine and analyzed its decomposition by the thermogravimetry and differential thermal analysis. It was found that, in air, Ce-TEA undergoes a thermal runaway at approximately 250 degrees C. This result suggested the possibility of inducing a self-sustained decomposition process at room temperature. In addition, the precursor can easily coordinate with metal noble nitrates in an aqueous solution. As a result, preparation of ceria-supported noble metal catalyst can be achieved by local ignition of the resulting noble metal doped cerium precursor. This novel approach can be used to yield Pd/CeO2 catalyst with various Pd loading in a single step without further annealing. XRD and XPS results of the prepared catalyst suggest that palladium is highly dispersed in its ionic state on the ceria support.

DOI： 10.1016/j.ceramint.2017.07.208

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCI LTD  

The effect of oxygen diffusion on the thermal decomposition kinetics of La[Fe(CN)6].5H(2)O has been explored. In particular, the critical conditions under which LaFeO3 can be synthesized via solid-state combustion of this cyano complex precursor were analytically and numerically investigated. Thermal analysis experiments as well as simulations showed that the oxygen diffusion enhancement facilitates the formation of a self-propagating combustion front during the decomposition of La[Fe(CN)(6)].5H(2)O. As a consequence, the sample undergoes local overheating that raises its temperature by several hundreds of degrees. This enables the production of LaFeO3 perovskite-type oxide with a minimum contribution of external heat resources. Although the self propagating high-temperature method has already proven to be successful for the synthesis of perovskite-type oxides from cyano complex precursors under oxygen atmosphere, we will show that under the appropriate settings, air can be used instead. Moreover, the temperature of the front is related to the ease of oxygen diffusion. Therefore, the surface area and the crystal size of LaFeO3 perovskite-type powders obtained via solid state combustion have been controlled by controlling the gas flow rate at which the sample has been exposed during the treatment.

DOI： 10.1016/j.ceramint.2016.11.134

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Treatment of dialkylbenzylsilanes (1) with trityl tetrakis(pentafluorophenyOborate (TPFPB) afforded the corresponding silylium ions in equilibrium with their intra-or intermolecular 2r-complexes, which underwent dehydrogenative annulation with various alkenes to form 1,2,3,4tetrahydro-2-silanaphthalenes (4) in up to 82% isolated yield. Sterically bulkier substituents on the silicon atom tended to increase the yield of cyclic products 4. The annulation products retained the stereochemistry in cases of the reactions using internal alkenes. The use of diisopropyl(1-naphthyl)silane (2) instead of 1 also resulted in annulation to obtain the 2,3-dihydro-1-sila-1H-phenalene derivatives 6. Electrophilic aromatic substitution at the 8position was predominant, despite the two potentially reactive positions on the naphthyl group. The steric hindrance of the naphthyl group prevented addition of the cis-alkene to the silylium ion, which would considerably decrease yields of the desired products from 2 compared to those from 1.

DOI： 10.1021/acs.joc.6b00793

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

A Zn-Sn precursor with cubic-shaped particles was successfully prepared by a simple coprecipitation method to obtain Zn-Sn mixed oxide (ZTO) catalysts. The resulting ZTO catalyst maintained the cubic shape even after calcination at 900 degrees C. The catalytic activity for the cyanosilylation of benzaldehyde with trimethylsilyl cyanide increased with increasing calcination temperature, and reached the maximum value at 600 degrees C. The ZTO catalyst calcined at 600 degrees C exhibited higher catalytic activity than the other solid acid catalysts, SiO2-Al2O3 and Amberlyst 15 DRY.

DOI： 10.1246/cl.160320

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Language：English   Publishing type：Research paper (scientific journal)  

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Language：Japanese   Publishing type：Research paper (scientific journal)  

CiNii Books

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Perovskite-type oxide, LaFeO3, was prepared from coordination polymer precursor, La[Fe(CN)(6)]center dot 5H(2)O by calcination with the different two systems. In a muffle furnace system, the perovskite-type oxide was given by calcination at >500 degrees C. The specific surface area of LaFeO3 powder calcined at 500 degrees C for 24 h was 18m(2).g(-1), which was the largest among single phase perovskite-type oxides calcined in a muffle furnace. In a gas-flow system, the perovskite-type oxide was given by calcination at significantly low temperature (>250 degrees C). The specific surface area of LaFeO3 powder calcined at 300 degrees C for 1 h in a gas-flow system was dependent on O-2 partial pressure. (C)2016 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.15198

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：MYU, SCIENTIFIC PUBLISHING DIVISION  

Temperature-programmed reduction measurement combined with resistance measurement (TPR&R) was performed to investigate the reduction behavior of the samples containing the semiconductor materials, SnO2 and CuO/SnO2. The four reduction peaks were observed in the H-2-TPR profile of SnO2, being assigned to the reductions of surface adsorbed oxygen species, surface lattice oxygen, amorphous SnO2 and bulk SnO2. On the other hand, the H-2-TPR profile of CuO/SnO2 was more complicated than that of SnO2. The TPR&R measurement enabled definite assignments of the six reduction peaks of CuO/SnO2: the reductions of (I) Cu2+ to Cu+ in highly dispersed copper oxide, (II) bulk CuO to Cu, (III) Cu+ to Cu in highly dispersed copper oxide, (IV) SnO2 lattice oxygen interacting with highly dispersed copper oxide, (V) amorphous SnO2, and (VI) bulk SnO2.

DOI： 10.18494/SAM.2016.1281

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER  

The perovskite-type oxide catalyst, SmFeO3, prepared by decomposition method of heteronuclear cyano complex precursor (CN method) was applied to liquid-phase organic reaction, cyanosilylation of benzaldehyde with TMSCN. The maximum catalytic activity per catalyst weight was achieved at 800 A degrees C of calcination temperature in CN method and it was found that the catalytic activity was strongly related to the crystallinity of SmFeO3 catalyst. The catalytic reaction performed in the presence of pyridine and 2,6-di-tert-butylpyridine suggests that the catalytically active sites are the Bronsted acid sites formed on the SmFeO3 catalyst. The catalytic activity of SmFeO3 catalyst prepared by CN method was much higher than those of acid catalysts: SiO2-Al2O3 and Amberlyst.

DOI： 10.1007/s11164-015-1980-y

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

The decomposition of La[Fe(CN)(6)]center dot 5H(2)O and La[Co(CN)(6)]center dot 5H(2)O under different atmospheres has been analyzed by thermogravimetry (TG) and differential thermal analysis (DTA). In addition, the decomposition temperature at different sample locations was monitored for sample masses around 2 g of La [Fe(CN)(6)]center dot 5H(2)O and La[Co(CN)(6)]center dot 5H(2)O, when they were calcined for 1 h at temperatures ranging from 200 to 400 degrees C in a controlled gas-flow system. Results showed that, the large enough of the cyano complex precursors undergo combustion when they are decomposed under oxygen atmosphere. X-ray diffraction results revealed that perovskite-type oxides crystallize due to the overheating of the process. As a result, it has been possible to produce LaFeO3 and LaCoO3 perovskite-type oxide powders by SHS under oxygen atmosphere using La[Fe(CN)(6)]center dot 5H(2)O and La[Co(CN)(6)]center dot 5H(2)O as a precursor. The effect of the ignition temperature has been investigated. The specific surface area of the perovskite-type oxides produced via SHS using heteronuclearcyano metal complex as a precursor is significantly higher than that of other LaMO3 produced using the same technique but obtained from other type of precursors. (C) 2015 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jallcom.2015.07.246

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Bilayer Ni-YSZ anode films for SOFCs were prepared by electrophoretic deposition (EPD). The thickness of each layer of the bilayer anode films, which consist of 50 wt% Ni-YSZ as the active layer and 70 wt% Ni-YSZ as the current collecting layer (50Ni-YSZ/70Ni-YSZ), were controlled by the deposition time of the EPD process. For the monolayer anodes, 70Ni-YSZ showed a better performance than 50Ni-YSZ. The bilayer film, 50Ni-YSZ/70Ni-YSZ, showed an even better performance than the 70Ni-YSZ monolayer film. Probably, 50Ni-YSZ anode has more reaction sites compared to 70Ni-YSZ; on the other hand, 70Ni-YSZ has higher porosity to be a gas diffusion (or current collecting) layer. The anodic performance of the bilayer film significantly depended on the film thickness of the 50Ni-YSZ layer, and 3 mu m was found to be the optimized thickness as the active layer, which suggests that the charge transfer reaction site extended up to a 3-mu m thickness from the anode/electrolyte interface. (C) 2015 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.123.235

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：Electrochemical Society Inc.  

Bimetallic Ni&lt
inf&gt
1-x&lt
/inf&gt
Fe&lt
inf&gt
x&lt
/inf&gt
/SDC powders containing 20wt% Ni-Fe were prepared and their anodic properties for SOFC were evaluated. The impedance spectra of the Ni&lt
inf&gt
1-x&lt
/inf&gt
Fe&lt
inf&gt
x&lt
/inf&gt
/SDC anodes at 800°C consisted of the ohmic component, R&lt
inf&gt
ohmic&lt
/inf&gt
, and depressed arcs, R&lt
inf&gt
HF&lt
/inf&gt
and R&lt
inf&gt
LF&lt
/inf&gt
. The R&lt
inf&gt
ohmic&lt
/inf&gt
component was due to the solid electrolyte layer, (ScO&lt
inf&gt
1.5&lt
/inf&gt
)&lt
inf&gt
0.18&lt
/inf&gt
(CeO&lt
inf&gt
2&lt
/inf&gt
)&lt
inf&gt
0.01&lt
/inf&gt
(ZrO&lt
inf&gt
2&lt
/inf&gt
)&lt
inf&gt
0.81&lt
/inf&gt
. The R&lt
inf&gt
HF&lt
/inf&gt
component was significantly reduced by the Fe addition, but apparent dependence was not observed for the R&lt
inf&gt
LF&lt
/inf&gt
component. The x=0.5 composition possessed the small R&lt
inf&gt
HF&lt
/inf&gt
and R&lt
inf&gt
LF&lt
/inf&gt
values. Accordingly, the single cell performance at 800°C was the maximum at x=0.5, and that was in the order of x=0.5 ≈ 0.2 &gt
0.8 ≈ 0 &gt
1.0. The mean crystallite size of Ni-Fe alloy increased approximately in this order. Therefore, we concluded that Fe addition to Ni decreases the particle size of Ni-Fe alloy, resulting in the enhancement of the catalytic activity of Ni&lt
inf&gt
1-x&lt
/inf&gt
Fe&lt
inf&gt
x&lt
/inf&gt
/SDC anode.

DOI： 10.1149/06801.1427ecst

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

Ni-impregnated SDC powders were prepared as a SOFC anode material. Surface area of the SDC powders was regulated with pre-calcination temperature and it was ranging from 12 to 93 m(2)/g. The averaged Ni particle size on SDC was fairly affected with surface area of the SDC supports. The smallest Ni particle size obtained in this study was 48 nm when the surface area of SDC was 27 m(2)/g. By further increasing the surface area of SDC to 93 m(2)/g, Ni particle size was adversely enlarged. The maximum power density increased with decreasing the averaged Ni particle size of Ni/SDC anode. The maximum power densities were 39.5 mWcm(-2) for dry H-2 and 106.5 mWcm(-2) for dry CH4. (C) 2014 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.ssi.2014.02.012

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：Materials Research Society  

Both Ni and alkaline earth metal oxide (MO: CaO, SrO, and BaO)-impregnated SDC powders were prepared as an SOFC anode material. The averaged Ni particle size on SDC was affected by the kind of alkaline earth metal oxide added. The addition of SrO and BaO to Ni/SDC anode enhanced power densities of both H2-SOFC and CH4-SOFC and the addition of CaO lowered them. The maximum power density increased with decreasing the averaged Ni particle size of Ni-MO/SDC anode.

DOI： 10.1557/opl.2014.815

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CERAMIC SOC JAPAN-NIPPON SERAMIKKUSU KYOKAI  

Two kinds of heterometal coordination polymer precursors, {Sm[M(ox)(3)]center dot nH(2)O}, (M = Fe and Co), were prepared by the reaction of K-3[M(ox)(3)]center dot 3H(2)O with Sm(NO3)(3)center dot nH(2)O in methanol solvent. These compounds were found to have oxalato-bridged network structure. On the other hand, the desired heterometal coordination polymer precursors could not be obtained by the present preparation method using water solvent. The thermal decomposition behaviors of these d-f heterometal coordination polymer precursors were investigated under air atmosphere. The perovskite-type oxides, SmMO3 (M = Fe and Co), were found to form in the temperature range of >600 degrees C. The specific surface area of SmFeO3 powder increased with decreasing calcination temperature of Fe-containing heterometal coordination polymer precursor. (C)2013 The Ceramic Society of Japan. All rights reserved.

DOI： 10.2109/jcersj2.121.84

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Language：Japanese   Publishing type：Research paper (scientific journal)   Publisher：JAPAN PETROLEUM INST  

Metal-supported active carbon adsorbents were applied to remove the small amount of H2S contained in biogas CH4. H2S adsorption experiments using column type-equipment demonstrated that copper-supported active carbon exhibited high H2S adsorption ability. From the practical point of view, the width and the rate of the adsorption layer were estimated using copper-supported active carbons. Assuming that the metal ion was initially coordinated with oxygen atoms in H2O molecules, the energy change in substituting a H2O molecule by a H2S molecule was calculated using a calculation program for the ab initio molecular orbital method (Gaussian 09). The results of these energy calculations suggest that Cu-0 and Cu+ species have the highest adsorption affinity with H2S among various metal and metal ions, in agreement with the present experimental results.

DOI： 10.1627/jpi.55.371

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The influence of A-site lanthanoids in the perovskite-type oxide catalysts, LnFe(x)Co(1-x)O(3) (Ln = La, Pr, Sm, Gd, Dy, Ho, Er, and Yb), prepared by the thermal decomposition of cyano complexes, Ln[FexCo1-x(CN)(6)]center dot nH(2)O, on the catalytic activity of CO oxidation was investigated. Using XRD, N-2 adsorption, SEM, XPS, and H-2-temperature programmed reduction (TPR) techniques, it was found that A-site lanthanoid ions in perovskite-type oxide LnFeO(3) affect the formation temperature of single phase, the crystalline structure, and the size of perovskite-type oxide particles. The catalytic activity of LnCoO(3) was improved by the replacement of Co ion with Fe ion regardless of the kind of A-site lanthanoid ion. A-site lanthanoids in perovskite-type oxide also affect the reducibility of B-site Co ion in LnFe(0.5)Co(0.5)O(3), leading to the change in the catalytic property. TPR results of LnFe(0.5)Co(0.5)O(3) suggest that the reducibility of Co ion is related to the distortion of perovskite structure. (C) 2011 Elsevier B. V. All rights reserved.

DOI： 10.1016/j.cattod.2011.09.023

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Language：Japanese   Publishing type：Research paper (scientific journal)  

CiNii Books

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Language：Japanese   Publisher：The Japan Petroleum Institute  

DOI： 10.11523/sekiyu.2012f.0_113

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER  

The carbon oxidation over copper ion-exchanged zeolites (Cu-MFI, Cu-MOR, Cu-FAU, and Cu-BEA) pretreated at 700 A degrees C was investigated. The catalytic activities of Cu-MFI, Cu-MOR, and Cu-FAU pretreated at 700 A degrees C were higher for carbon oxidation in NO + O(2) atmosphere than that of Cu-BEA. The TEM results demonstrated that Cu fine particles were formed on the external surface of Cu-MFI, Cu-MOR, and Cu-FAU, showing high activity. In addition, it was suggested that the coexisting NO plays an important role in enhancing the catalytic activity of Cu-MFI for carbon oxidation.

DOI： 10.1007/s11164-011-0381-0

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The thermal decomposition reaction of crystalline heteronuclear cyano complex precursor to crystalline perovskite-type oxide catalyst was investigated. From X-ray single crystal analysis and XRD, FT-IR, TG-DTA, SEM, and BET measurements, the thermal decomposition process of Sm[Fe(CN)(6)]center dot 4H(2)O precursor was elucidated. It was found that the specific surface area of SmFeO3 decreased monotonously with increasing calcination temperature of Sm[Fe(CN)(6)]center dot 4H(2)O, while the highest catalytic activity for CO oxidation was achieved for Sm[Fe(CN)(6)]center dot 4H(2)O calcined at 600 degrees C. The size of Sm[Fe(CN)(6)]center dot 4H(2)O precursor depended on the molar concentration of starting materials, Sm(NO3)(3)center dot 6H(2)O and K3Fe(CN)(6), in aqueous solution (C-s); the size of Sm[Fe(CN)(6)]center dot 4H(2)O decreased with decreasing C-s. The decrease in particle size of cyano complex was found to result in the increase in specific surface area of perovksite-type oxide obtained after calcination. (C) 2011 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.cattod.2011.04.048

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：PERGAMON-ELSEVIER SCIENCE LTD  

The photocatalytic reaction in the partial oxidation of alpha-methylstyrene (alpha-MS) to acetophenone (AP) was investigated for TiO(2) supported on H-ZSM-5 (H-MFI), H-mordenite (H-MOR), and H-Y-type (H-FAU) zeolites. XRD results demonstrated that the anatase was the stable phase of TiO(2) supported on zeolites. Photocatalytic activities of supported catalysts decreased in the following order: TiO(2)/H-MFI "TiO(2)/H-MOR > (TiO(2)) > TiO(2)/H-FAU" (blank). TiO(2)/H-MFI catalyst exhibited the best performance for photocatalytic oxidation of alpha-MS to AP. The maximal activity was obtained by 25 wt% TiO(2)/H-ZSM-5. The addition of water to the reaction solvent resulted in significantly lowering the photocatalytic activity for TiO(2)/H-ZSM-5 catalyst, although its activity for TiO(2) and TiO(2) + H-ZSM-5 mechanical mixture was little influenced by the amount of water added to reaction solvent. (C) 2009 Elsevier Ltd. All rights reserved.

DOI： 10.1016/j.electacta.2009.11.091

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：SPRINGER/PLENUM PUBLISHERS  

Pt catalysts supported on Al(2)O(3) beads prepared by a sputter deposition method showed the higher surface concentration of Pt than impregnated Pt catalysts. The catalytic activities of the oxidation of acetylene carbon black over the sputtered Pt catalysts were higher than those over the impregnated Pt catalysts with the same Pt content.

DOI： 10.1007/s11244-010-9500-1

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE BV  

The carbon oxidation was investigated over copper ion-exchanged MR zeolite (Cu-MFI) as a function of pretreatment temperature. Cu-MR pretreated at 700 degrees C exhibited high activity for carbon oxidation in NO + O(2) atmosphere. The activity of Cu-MFI pretreated at 700 degrees C increased with increasing the amount of copper ion exchanged. XRD and ESR measurements suggest that the CuO fine particles as an active site for carbon oxidation were formed on the surface of MR zeolite by pretreatment at 700 degrees C. (C) 2010 Elsevier By. All rights reserved.

DOI： 10.1016/j.catcom.2010.02.025

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

CaO catalysts supported on several metal oxides and zeolites were investigated for transesterification of triolein with methanol. Zeolite-supported CaO catalysts showed high catalytic activity for transesterification compared to the metal oxide-supported CaO catalysts; among the zeolites tested in this work, mordenite exhibited the best support. The catalytic activity of mordenite-supported CaO catalyst depended on both the amount of CaO loading and the calcination temperature for catalyst precursor.

DOI： 10.1246/cl.2010.198

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Language：English   Publishing type：Research paper (international conference proceedings)  

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：ELECTROCHEMICAL SOC INC  

The anodic performances of Ni/CeO2-Sm2O3(Ni/SDC) modified by the addition of alkaline earth metal oxides (MgO, CaO, SrO, and BaO) were investigated for direct oxidation of CH4 in solid oxide fuel cells (SOFCs). Although the initial power density of cell with Ni/SDC anode modified by the addition of CaO (Ni-CaO/SDC) was slightly lower than that of cell with Ni/SDC, the former anode exhibited an excellent stability compared to the latter one. After continuous operation of SOFC for 24 h, no or less amount of carbon deposition was observed over Ni-CaO/SDC.

DOI： 10.1149/1.3205764

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A new mu-eta(2):eta(2)-peroxo dicopper(II) complex, [Cu-2(II)(alpha SP)(2)(mu-eta(2):eta(2)-O-2) (Bz(.))]SbF6 (alpha Sp = alpha-isosparteine, Bz, = benzoate) was synthesized by oxygenation of [Cu-1(alpha Sp)(CH3CN)]SbF6 with Bz(.) at -80 degrees C in acetone. X-ray crystallographic analysis of the dark blue crystal revealed that the "bridged butterfly core" is formed by bridging Bz(.) bound in the axial position. The weaker sigma-electron donation of aSp causes the axial coordination of Bz(.) to stabilize the butterfly-type mu-eta(2):eta(2)-peroxo dicopper(II) species as an intermediate of stepwise O-2-activation to bis(mu-oxo) dicopper(III) species.

DOI： 10.1021/ja804201z

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A novel dialuminum-substituted silicotungstate TBA(3)H[gamma-SiW(10)O(36){Al(OH(2))}(2)(mu-OH)(2)]center dot 4H(2)O (1, TBA = tetra-n-butylammonium) was synthesized by the reaction of the potassium salt of [gamma-SiW(10)O(36)](8-)(SiW(10)) with 2 equiv of Al(NO(3))(3) in an acidic aqueous medium. It was confirmed by the X-ray crystallographic analysis that compound 1 was a monomer of the gamma-Keggin dialuminum-substituted silicotungstate with the {Al(2)(mu-OH)(2)} diamond core. The cluster framework of 1 maintained the gamma-Keggin structure in the solution states. The reaction of 1 with pyridine yielded TBA(3)[(C(5)H(5)N)H][gamma-SiW(10)O(36){Al(OH(2))}(2)(mu-OH)(2)]center dot 2H(2)O (2), and the molecular structure was successfully determined by the X-ray crystallographic analysis. In compound 2, two of three pyridine molecules coordinated to the axial positions of aluminum centers and one of them existed as a pyridinium cation, showing that compound 1 has two Lewis acid sites and one Bronsted acid site. Compound 1 showed high catalytic activity for the intramolecular cyclization of citronellal derivatives such as (+)-citronellal (3) and 3-methylcitronellal (4) without formation of byproduct resulting from etherification and dehydration. For the 1-catalyzed cyclization of 3, the diastereoselectivity toward (-)-isopulegol (3a) reached ca. 90% and the value was the highest level among those with reported systems so far. The reaction rate for the 1-catalyzed cyclization of 3 decreased by the addition of pyridine, and the cyclization hardly proceeded in the presence of 2 equiv of pyridine with respect to 1. On the other hand, the reaction rate and diastereoselectivity to 3a in the presence of 2,6-lutidine were almost the same as those in the absence. Therefore, the present cyclization is mainly promoted by the Lewis acid sites (aluminum centers) in 1. DFT calculations showed that the formation of the transition state to produce 3a is sterically and electronically more favorable than the other three transition states for the present 1-catalyzed cyclization of 3.

DOI： 10.1021/ja8014154

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ACADEMIC PRESS INC ELSEVIER SCIENCE  

The di-copper-substituted gamma-Keggin silicotungstate with bis-mu-1,1-azido ligands TBA(4)[gamma-H2SiW10O36Cu2(mu-1,1-N-3)(2)] (1, TBA = tetra-n-butylammonium) was synthesized in an aqueous medium. The crystal structure of the anion part of 1 was a monomer of the basal-basal end-on diazido-bridged di-copper-substituted gamma-Keggin silicotungstate. The NMR and CSI-MS spectra of 1 in organic solvents, such as acetonitrile, benzonitrile, and 1,2-dichloroethane, showed that complex 1 was present as a monomer of the di-copper-substituted gamma-Keggin silicotungstate. Complex 1 could act as on effective homogeneous catalyst for the oxidative homocoupling of various types of alkynes, including aromatic, aliphatic, and heteroatom-containing ones. The reaction possibly proceeds as follows: First, the ligand exchange proceeds between the azido groups in 1 and alkynyl groups to form the corresponding diyne with the reduced copper(I) species via the di-copper(II)-alkynyl intermediate, then the reduced species is reoxidized by molecular oxygen, and the oxidized species reacts with an alkyne to regenerate the alkynyl intermediate. (C) 2008 Elsevier Inc. All rights reserved.

DOI： 10.1016/j.jcat.2008.06.004

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The di- and tetranuclear metal sandwich-type silicotungstates Of (gamma-SiW(10)O(36))(2){Zr(H(2)O)}(2)(mu-OH)(2)]center dot 18H(2)O (Zr2, monoclinic, C2/c (No. 15), p = 25.3315(8) angstrom, b = 22.6699(7) angstrom, c = 18.5533(6) angstrom, beta = 123.9000(12)degrees, V = 8843.3(5) angstrom(3), Z= 4), Cslo[(y-SiW(10)O(36))2[Hf(H(2)O)}(2) (mu-OH)(2)]center dot 17H(2)O (Hf2, monoclinic, space group C2/c (No. 15), a = 25.3847(16) angstrom, b = 22.6121(14) angstrom, c = 18.8703(11) angstrom, beta = 124.046(3)degrees, V= 8974.9(9) angstrom(3), Z= 4), CS(B)[(gamma-Siw(10)O(36))(2)(Zr(H(2)O)(4)(mu-O)(mu-OH)6]-26H(2)O (Zr4, tetragonal, P4(1)2(1)2 (No. 92), a = 12.67370(10) angstrom, c= 61.6213(8) angstrom, V= 9897.78(17) angstrom 3, Z = 4), and CS(8)[(gamma-SiW(10)O(36))(2){Hf(H(2)O))(4)(mu(4)-O)(mu-OH)(6)]-23H(2)O (HM, tetragonal, P4(1)2(1)2 (No. 92), a = 12.68130(10) angstrom, c= 61.5483(9) degrees, V= 9897.91(18) angstrom(3), Z= 4) were obtained as single crystals suitable for X-ray crystallographic analyses by the reaction of a dilacunary gamma-Keggin silicotungstate gamma-SiW(10)O(36) with ZrOCl(2) center dot 8H(2)O or HfOCl(2) center dot 8H(2)O. These dimeric polyoxometalates consisted Of two gamma-SiW(10)O(36)- units sandwiching metal-oxygen clusters such as [M(2)(mu-OH)(6)](6+) and [M(4)(mu-O)(mu-OH)(6)](8+) (M = Zr or Hf). The dinuclear zirconium and hafnium complexes Zr2 and Hf(2) were isostructural. The equatorially placed two metal atoms in Zr2 and Hf(2) were linked by two mu-OH ligands and each metal was bound to four oxygen atoms of two gamma-SiW(10)O(36) units. The tertanuclear zirconium and hafnium complexes Zr4 and HM were isostructural and consisted of the adamantanoid cages with a tetracoordinated oxygen atom in the middle, [M(4)(mu-O)(mu-OH)(6)](8+) (M = Zr or Hf). Each metal atom in Zr4 and HM was linked by three mu-OH ligands and bound to two oxygen atoms of the gamma-SiW(10)O(36) unit. The tetra-nuclear zirconium and hafnium complexes showed catalytic activity for the intramolecular cyclization of (+)-citronellal to isopulegols without formation of byproducts resulting from etherification and dehydration. A lacunary silicotungstate gamma-SiW(10)O(34)(H(2)O)(2)](4-). was inactive, and the isomer ratio of isopulegols in the presence of MOCl(2) - 8H(2)O (M = Zr or Hf) were much different from that in the presence of tetranuclear complexes, suggesting that the [M(4)(mu-O)(mu-OH)(6)](8+) core incorporated into the POM frameworks acts as an active site for the present cyclization. On the other hand, the reaction hardly proceeded in the presence of dinuclear zirconium and hafnium complexes under the same conditions. The much less activity is possibly explained by the steric repulsion from the POM frameworks in the dinuclear complexes.

DOI： 10.1021/ja078313i

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

A novel ruthenium-containing silicotungstate of [(CH3)(2)NH2](8)K2H2[(gamma-SiW10O36)(2)Ru4Cl4O2(OH)(4)]center dot 23H(2)O (1) was obtained as a single crystal suitable for X-ray crystallographic analysis by the reaction of a divacant lacunary gamma-Keggin silicotungstate K-8[gamma-SiW10O36] with K-2[RuCl5(OH2)]. The unprecedented dimeric silicotungstate consisted of two [gamma-SiW10O36](8-) units sandwiching an adamantanoid ruthenium-oxygen cluster core [Ru4Cl4O2(OH)(4)](4+).

DOI： 10.1246/cl.2008.328

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-BLACKWELL  

DOI： 10.1002/anie.200705126

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

Hydrogen atom abstraction reactions have been implicated in oxygenation reactions catalyzed by copper monooxygenases such as peptidylglycine alpha-hydroxylating monooxygenase (PHM) and dopamine beta-monooxygenase (D beta M). We have investigated mononuclear copper(I) and copper(II) complexes with bis[(6-neopentylamino-2-pyridyl) methyl][(2-pyridyl) methyl] amine (BNPA) as functional models for these enzymes. The reaction of [Cu-II(bnpa)](2+) with H2O2 affords a quasi-stable mononuclear copper(II)-hydroperoxo complex, [Cu-II(bnpa)(OOH)](+) (4) which is stabilized by hydrophobic interactions and hydrogen bonds in the vicinity of the copper(II) ion. On the other hand, the reaction of [Cu-I(bnpa)](+) (1) with O-2 generates a trans-mu-1,2-peroxo dicopper(II) complex [Cu-2(II)(bnpa)(2)(O-2(2-))](2+) (2). Interestingly, the same reactions carried out in the presence of exogenous substrates such as TEMPO-H, produce a mononuclear copper(II)-hydroperoxo complex 4. Under these conditions, the H-atom abstraction reaction proceeds via the mononuclear copper(II)-superoxo intermediate [Cu-II(bnpa)(O-2(-))](+) (3), as con. rmed from indirect observations using a spin trap reagent. Reactions with several substrates having different bond dissociation energies (BDE) indicate that, under our experimental conditions the H-atom abstraction reaction proceeds for substrates with a weak X-H bond (BDE < 72.6 kcal mol(-1)). These investigations indicate that the copper(II)-hydroperoxo complex is a useful tool for elucidation of H-atom abstraction reaction mechanisms for exogenous substrates. The useful functionality of the complex has been achieved via careful control of experimental conditions and the choice of appropriate ligands for the complex.

DOI： 10.1039/b712572k

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

In order to gain an understanding of the role of the sulfenyl group of nitrile hydratase (NHase), a new Co(III) complex with a sulfenyl-type ligand (L-c=o:N-2(SO)(2)), Na[Co-III (L-c=o:N-2(SO)(2))(tBuNC)(2)] (2), was synthesized. The compound includes two amide groups, two sulfenate sulfurs in the equatorial plane, and two tBuNC molecules in the axial positions. Characterization of the compound was performed by UV-vis spectroscopic, IR spectral, thermogravimetric (TG), and X-ray structure analytical methods. The results are discussed in the context of Co(III) complexes containing the corresponding sulfur-type (L-c=o:N2S2) (1) and sulfinyl-type ligands (L-c=o:N-2(SO2)(2)) (3). Complex 2 crystallized with the formula Na[Co-III(L-c=o:N-2(SO)(2))(tBuNC)(2)]center dot urea-2H(2)O center dot 0.5EtOH. The X-ray structure revealed that the Co(III) complex has an octahedral geometry with Co-S = av. 2.221 (A) over circle, Co-N = av. 1.998 (A) over circle, and Co-C = av. 1.87 (A) over circle. The sulfenyl oxygen and amidate carbonyl oxygen are linked to urea, water, EtOH, and Na+ and participate in a hydrogen-bond and an electrostatic interaction. IR and TG measurements demonstrated that the coordination strength of tBuNC to the Cc atom increases as follows: 1 < 2 < 3. Complex 2 has almost the same stability as 3 in all solutions tested, although 1 exhibits a release of axial ligands in nonaqueous solutions. DFT calculations for 1, 2, and 3 demonstrated that Milliken atomic charges of the Co(III) centers are +1.466, +1.536, and +1.542, respectively, indicating that the extent of oxidation of the sulfur atoms increases the Lewis acidity of the Co(III) centers. Interestingly, the solution-state IR spectrum of 2 exhibits a solvent-dependent S-O stretching frequency. The frequency decreases with an increase in the electrophilicity (acceptor number) of the solvent. This solvent dependence was not observed for 3, which has a sulfinate (SO2) group, suggesting that the sulfenyl oxygen atom has nucleophilic character and promotes strong binding of the tBuNC molecule to lower the reaction barrier. These findings may suggest that the sulfenate oxygen in native NHase acts as a base (proton acceptor) and contributes to the activation of a water molecule and/or nitrile molecule.

DOI： 10.1021/ic701107x

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A novel dinuclear zirconium sandwich-type silicotungstate cluster Of [(gamma-SiW10O36)(2)Zr-2(mu-OH)(2)](10-) (1) was synthesized by the reaction of a divacant lacunary gamma-Keggin silicotungstate [gamma-SiW10O36](8-) with ZrOCl2 center dot 8H(2)O. The anion consisted Of two [gamma-SiW10O36](8-) units sandwiching a diamond Zr-2(mu-OH)(2) core, and each zirconium atom in 1 was six-coordinated to two mu-0H ligands and four oxygen atoms Of two [gamma-SiW10O36](8-) units. The Zr-2(mu-OH)(2) core in 1 reacted with methanol to give the corresponding monomethoxo derivative [(gamma-SiW10O36)(2)Zr-2(mu-OH)(mu-OCH3)](10-) (2).

DOI： 10.1021/ic701488s

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

Reaction of hydroxozinc(II) complex bearing amino group with CO2 gave carbarnate product, whose generation and reaction mechanism have been studied structurally and spectroscopically as a structural/functional model of biotin-dependent carboxylase.

DOI： 10.1246/cl.2007.842

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

The reaction of the dinuclear peroxotungstate, [(n-C4H9)(4)N](2)[{WO(O-2)(2)}(2)(mu-O)] (II), with H2O2 gives the novel mu-eta(1):eta(1)-peroxo-bridging dinuclear tungsten species, [(n-C4H9)(4)N](2)[{WO(O-2)(2)}(2)(mu-O-2)] (I), which has been characterized by X-ray crystallography, elemental analysis, IR, Raman, UV-vis, and W-183 NMR. Only I is active for the epoxidation of cyclic, internal, and terminal olefins, whereas II is inactive for each. The low X-SO (X-SO = (nucleophilic oxidation)/(total oxidation)) value of I (0.18 +/- 0.02) in comparison with that of II (0.39 +/- 0.01) for the stoichiometric oxidation of thianthrene 5-oxide, which is a mechanistic probe for determining the electronic character of an oxidant, reveals that I is more electrophilic than II. On the basis of the kinetic and spectroscopic results, the catalytic epoxidation proceeds by the reaction of I with an olefin to form II and the corresponding epoxide followed by the regeneration of I by the reaction of II with H2O2.

DOI： 10.1021/ic0701211

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ELSEVIER SCIENCE SA  

A novel (mu(3)-oxo)tetraruthenium cluster (2) was synthesized in an isolated yield of 73% by the reaction of a zerovalent ruthenium complex, Ru(eta(6)-cot)(eta(2)-dmfm)(2) (1) [Cot = 1,3,5-cyclooctatriene, dmfm = dimethyl fumarate], with water under reflux in 1,4-dioxane for 6 h. The structure and the X-ray characterization of this novel complex 2 as well as a possible formation mechanism of 2 are disclosed. (c) 2006 Elsevier B.V. All rights reserved.

DOI： 10.1016/j.jorganchem.2006.08.062

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

In an attempt to understand the unique active site structure of nitrile hydratase, four Co-III complexes with square-planar N2S2- or N-2(SO2)(2)-type donor sets, Na[Co-III(L:N2S2)] (1-Na), PPh4[Co-III(L:N2S2)] (1-PPh4), PPh4[COIII(L:N2S2)(tBuNC)(2)] (2), and PPh4[Co-III{L:N-2(SO2)(2)}(tBuNC)(2)] (3) were synthesized and characterized on the basis of electronic absorption spectroscopy, IR spectroscopy, cyclic voltammetry, and X-ray structural analysis. Both of the crystal structures of complexes 1-Na and 1-PPh4 revealed a square planar structure with N2S2 donating atoms, and 2 exhibited an octahedral structure coordinated with two tert-butylisocyanide (tBuNC) molecules at the axial sites of complex 1-PPh4. Complex 3, which showed an octahedral structure with sulfinate sulfur atoms equatorially coordinated to the center, was synthesized by the treatment of 2 with a suitable oxidant. The reduction potential values from Co-III to Co-II for complex 3 in solution demonstrated a larger positive shift when compared with those of complexes 1-PPh4 and 2, which indicates that the oxygenation of the sulfur atoms increased the Lewis acidity of the Co-III center. Interestingly, the coordination equilibrium, the C=O stretching frequency, and the redox potential for 1-PPh4 were all closely related to the acceptor number (AN) of the solvents. Furthermore, the coordination of monodentate tBuNC to the axial position of 1-PPh4 was dependent on the solvents used. These findings indicate that an electrophilic interaction between the carbonyl oxygen atoms and the solvent molecules control the Lewis acidity of the metal ion. On the other hand, such a solvent dependence was not detected in the S=O stretching frequency of sulfinates 3. We have concluded that the increase in the redox potential/ Lewis acidity of the metal center is a result of the oxygenation of sulfur, and that this increase is controlled by the interaction of the amidate carbonyl oxygen with the secondary coordination sphere. As demonstrated in previous mutation studies, this study suggests that the interaction of the nitrile hydratase active site with the functional groups from the peptide backbone is essential for the catalytic activity of the complex. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006).

DOI： 10.1002/ejic.200600507

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Language：English   Publishing type：Research paper (international conference proceedings)   Publisher：TRANS TECH PUBLICATIONS LTD  

A disodium tetrakis(phthalimide) palladium(H) complex, [Na2Pd(phthal)(4)] (1), was synthesized by reaction of four phthalimide molecules with Pd(OAC)(2) in the presence of Et3N. The above and below axial sites of the I'd coordination plane formed the spaces suitable for capturing Na+ ions, which were coordinated with the four imidato oxygen atoms. The complex 1 was linked through the Na+ ions bridged by the water molecules, building an infinite chain structure along the crystallographic a axis. The four phthalimidato moieties contacted in the four orthogonal directions together through their pi-pi stacking interaction. Such a self-assembly of molecule 1 constructed nanopores with a pore size of ca. 3 x 4 angstrom in the crystals.

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A mononuclear copper(II)-hydroperoxo species has been generated by the reaction of Cu(I)-H(2)BPPA complex with dioxygen, which illustrates the enzymatic reaction process of the Cu-B site in the D beta M and PHM.

DOI： 10.1039/b609673e

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Language：Japanese   Publishing type：Research paper (scientific journal)  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Enantiopure organoruthenium aqua complexes, Ru(dppe)(dmfm)(2)(H2O) (1) [dmfm = dimethyl fumarate] and Ru(QUINAP)(dmfm)(2)(H2O) (2) [QUINAP = 1-(2-diphenylphosphino-1-naphthyl)isoquinoline-1, were prepared and the absolute structures were determined by X-ray crystallography. In the crystals of these complexes, the water molecule is captured in the chiral coordination environment assisted by two different hydrogen bonds; that is, a chiral center is generated on the coordinated oxygen of water. The behavior of the coordinated water in 1 and 2 was monitored by variable-temperature H-1 NMR measurement. At lower than -60 to -70 degrees C, the nonequivalency of the geminal protons in the coordinated water molecule was observed even in solution. On the basis of the VT NMR data and DFT study, the behavior of the coordinated water was discussed. Complex 1 reacts with ammonia to give Ru(dppe)(dmfm)(2)(NH3) (4), which is the first example of the isolated mononuclear Ru(0) ammonia complex. Complex 4 was reversibly converted into 1 by the reaction with water.

DOI： 10.1021/om050664n

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Language：English  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

A novel distorted square-pyramidal N2S3-type Co(III) complex with a vacant site was synthesized as an active center model of nitrile hydratases (NHases) and characterized by UV-vis and (HNMR)-H-1 spectroscopic and X-ray analyses. The electronic absorption spectra were characteristic of a five-coordinate structure in organic solvents such as acetonitrile, while the complex in an aqueous solution gave different spectrum characteristic of a six-coordinate octahedron. These results suggest that the coordination of a water molecule is a key for the hydration of nitrile compound in the NHases.

DOI： 10.1246/cl.2005.18

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：WILEY-V C H VERLAG GMBH  

DOI： 10.1002/anie.200501157

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

Ruthenium(II/III) complexes with tripodal tris(pyridylmethyl)amine ligands bearing one, two, or three pivalamide groups (MPPA, BPPA, TPPA: amide-series ligands) or neopentylamine ones (MNPA, BNPA, TNPA: amine-series ligands) at the 6-position of the pyridine ring have been synthesized and structurally characterized. The X-ray structure analyses of the single crystals of these complexes reveal that they complete an octahedral geometry with the tripodal ligand and some monodentate ligands. The amide-series ligands prefer to form a Ru(II) complex, while the amine-series ones give a Ru(III) complex. In the presence of PhIO oxidant, the catalytic activities for epoxidation of olefins, hydroxylation of alkane, and dehydrogenation of alcohol have been investigated using the six ruthenium complexes [Ru-II(tppa)Cl-2] (1), [Ru-III(tnpa)Cl-2]PF6 (2), [Ru-II(bppa)Cl]PF6 (3), [Ru-III(bnpa)Cl-2]PF6 (4), [Ru-II(mppa)Cl]PF6 (5), and [Ru-III(mnpa)Cl-2]PF6 (6). Among them, the amide-series complexes, 1, 3, and 5, showed a higher epoxidation activity in comparison with the amine-series ones, 2, 4, and 6. On the other hand, the latter showed a higher reactivity for hydroxylation, allylic oxidation, and C=C bond cleavage reactions compared with the former. Such a complementary reactivity is interpreted by the character of the ruthenium-oxo species involving electronically equivalent formulas, Ru(V)=O and Ru(IV)-O-..

DOI： 10.1021/ic0494399

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：AMER CHEMICAL SOC  

A series of the copper(II) complexes with tripodal tetradentate tris(pyridyl 2-methyl)amine-based ligands possessing the hydrogen-bonding 6-aminopyridine units (tapa, three amino groups; bapa, two amino groups; mapa, one amino group) have been synthesized, and their copper(II) complexes with a small molecule such as dioxygen and azide have been studied spectroscopically and structurally. The reaction of their Cu(II) complexes with NaN3 have given the mononuclear copper complexes with azide in an end-on mode, [Cu(tapa)(N-3)]ClO4 (1a), [Cu(bapa)(N-3)]ClO4 (2a), [Cu(mapa)(N-3)]ClO4 (3a), and [Cu(tpa)(N-3)]ClO4 (4a) (tpa, no amino group). The crystal structures have revealed that the coordination geometries around the metal centers are almost a trigonal-bipyramidal rather than a square-planar except for la with an intermediate between them. The UV-vis and ESR spectral data indicate that the increase of NH2 groups of ligands causes the structural change from trigonal-bipyramidal to square-pyramidal geometry, which is regulated by a combination of steric repulsion and hydrogen bond. The steric repulsion of amino groups with the azide nitrogen gives rise to elongation of the Cu-N-py bonds, which leads to the positive shift of the redox potentials of the complexes. The hydrogen bonds between the coordinated azide and amino nitrogens (2.84-3.05 Angstrom) contribute clearly to the fixation of azide. The Cu(l) complexes with bapa and mapa ligands have been obtained as a precipitate, although that with tapa was not isolated. The reactions of the Cu(I) complexes with dioxygen in MeOH at -75 degreesC have given the trans-mu-1,2 peroxo dinuclear Cu(II) complexes formulated as [{(tapa)Cu}(2)(O-2)](2+) (1c), [{(bapa)Cu}(2)(O-2)](2+) (2c), and [{(mapa)Cu}(2)(O-2)](2+) (3c), whose characterizations were confirmed by UV-vis, ESR, and resonance Raman spectroscopies. UV-vis spectra of 1c, 2c, and 3c exhibited intense bands assignable to pi*(O-2(2-))-to-d(Cu) charge transfer (CT) transitions at lambda(max)/nm (epsilon/M(-1)cm(-1)) = 449 (4620), 474 (6860), and 500 (9680), respectively. The series of the peroxo, adducts generated was ESR silent. The resonance Raman spectra exhibited the enhanced features assignable to two stretching vibrations v(O-16-O-16/O-18-O-18)/cm(-1) and v(Cu-O-16/Cu-O-18)/cm(-1) at 853/807 (1c), 858/812 (2c), 847/800 (3c), and at 547/522 (2c), 544/518 (3c), respectively. The thermal stability of the peroxo-copper species has increased with increase in the number of the hydrogen-bonding interactions between the peroxide and amino groups.

DOI： 10.1021/ic0496572

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Language：Japanese   Publishing type：Research paper (scientific journal)  

CiNii Books

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：ROYAL SOC CHEMISTRY  

A novel hydroperoxo-copper(II) complex with a square-planar geometry has been prepared, which has exhibited a higher selectivity and catalytic reactivity for dimethyl sulfide, in contrast to that with a trigonal-bipyramidal one.

DOI： 10.1039/b308073k

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Language：English   Publisher：ELSEVIER SCIENCE INC  

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Language：English   Publisher：ELSEVIER SCIENCE INC  

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Language：English   Publishing type：Research paper (scientific journal)   Publisher：CHEMICAL SOC JAPAN  

A novel Zn(II)-OH complex surrounded with hydrogen bonding and hydrophobic interaction groups has been prepared as a structural/functional model of carbonic anhydrases, and characterized by X-ray structure analysis and ESIMS and H-1- and C-13-NMR spectroscopies. The complex has been found to exhibit a reversible binding of CO2.

DOI： 10.1246/cl.2003.406

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Language：English   Publisher：ELSEVIER SCIENCE INC  

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Venue：首都大学東京南大沢キャンパス（東京都八王子市）  

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Venue：岩手大学（岩手県盛岡市）  

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Venue：香川大学幸町キャンパス（香川県高松市）  

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Venue：首都大学東京南大沢キャンパス（東京都八王子市）  

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Venue：首都大学東京南大沢キャンパス（東京都八王子市）  

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Venue：首都大学東京南大沢キャンパス（東京都八王子市）  

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Venue：Sapporo  

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Venue：Beijing (China)  

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Venue：Beijing (China)  

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Venue：広島大学東広島キャンパス（広島県東広島市）  

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