Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 79 , Issue 8
Showing 1-22 articles out of 22 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2004
  • Tatsumi Ishihara
    2006 Volume 79 Issue 8 Pages 1155-1166
    Published: 2006
    Released: August 07, 2006
    JOURNALS FREE ACCESS
    Solid Oxide Fuel Cell (SOFC) show great promise as new power generators with high efficiency. Decreasing the operating temperature is critically required for the further development of SOFC. This review introduces that oxide ion conductivity in the perovskite oxide of LaGaO3, which was found by our group. LaGaO3 doped with La and Mg exhibits the high oxide ion conductivity over a wide PO2 range; the value is higher than that of Y2O3-stabilized ZrO2 by an order of magnitude. When LaGaO3-based oxide was used as the electrolyte of SOFC, the power density could be improved greatly, in particular over the low-temperature range. In this study, the power generating property of LSGM using a thin film of LaGaO3 is also introduced. The maximum power density of the cell using LaGaO3-based oxide is as high as 0.6 W cm−2 at 773 K. This suggests that SOFC could be operable at temperature lower than 773 K.
The Chemical Society of Japan Award for Young Chemists for 2004
  • Soichiro Yoshimoto
    2006 Volume 79 Issue 8 Pages 1167-1190
    Published: 2006
    Released: August 07, 2006
    JOURNALS FREE ACCESS
    In this research, molecular assembly and function of aromatic thiols, porphyrins, phthalocyanines, and fullerenes on gold single crystal surfaces was studied by electrochemical methods and scanning tunneling microscopy (STM). Surface functions of promoter molecules such as pyridinethiols, pyrimidinethiols, and benzenethiol for cytochrome c electrochemistry were characterized by electrochemical techniques. Adlayer structures of those molecules were investigated by in situ STM, and molecular orientations for each molecule on the Au surfaces were clarified at molecular level. Adlayers of porphyrins and phthalocyanines for electrocatalytic reduction of dioxygen were examined to elucidate the relationship between activity and adlayer structure. Stable two-dimensional arrays of cobalt porphyrins indicated two-electron reduction of O2 to H2O2, whereas two-step four-electron reduction of O2 to H2O occurred because of highly mobile porphyrinatoiron molecules on the surface. Furthermore, well-defined adlayers of crown-substituted phthalocyanine for host–guest interface and binary array consisting of porphyrin and phthalocyanine for the design of supramolecular nanoarchitectures were clearly visualized by STM. Finally, a unique approach for controlling molecular orientation was found by the formation of supramolecular assemblies consisting of porphyrin and fullerene. The electrochemical redox reaction of carbonyl and ferrocene moieties was promoted by using the simple method for the construction of a 1:1 supramolecular assembled film consisting of C60 derivative and octaethylporphyrinatometal on Au single crystal surfaces.
BCSJ Award Article
  • Tapan Kumar Saha, Yutaka Yoshikawa, Hiroyuki Yasui, Hiromu Sakurai
    2006 Volume 79 Issue 8 Pages 1191-1200
    Published: 2006
    Released: August 07, 2006
    JOURNALS FREE ACCESS
    We prepared and characterized [meso-tetrakis(4-sulfonatophenyl)porphyrinato]oxovanadate(IV)(4−), [VO(tpps)], and its in vitro insulin-mimetic activity, metallokinetic features in the blood of healthy rats, and in vivo hypoglycemic effect in streptozotocin (STZ)-induced diabetic mice (STZ mice) were investigated. The results were compared with those of previously proposed insulin-mimetic [meso-tetrakis(1-methylpyridinium-4-yl)porphyrinato]oxovanadium(IV)(4+), [VO(tmpyp)], and vanadium(IV) oxide sulfate. The in vitro insulin-mimetic activity, the retention time and bioavailability of [VO(tpps)] in blood were considerably better than those of [VO(tmpyp)] and vanadium(IV) oxide sulfate. [VO(tpps)] caused a significant hypoglycemic effect in STZ mice within 8 h following a single oral administration of the complex at 15 mg V/kg of body mass without ascorbate; this effect was sustained for at least 60 h. [VO(tpps)] normalized the hyperglycemia of STZ mice within 2 days when administered orally at 4–10 mg V/kg of body mass for 18 days. Vanadium, as determined by instrumental neutron activation analysis, was distributed in the tissues examined in the following decreasing order: bones, kidneys, liver, lungs, spleen, heart, pancreas, muscles, fatty pads, and brain. The improvement in diabetes was supported by oral glucose tolerance test, HbA1c level and blood pressure. Based on the above results, [VO(tpps)] is an orally active oxovanadium(IV)–porphyrin complex for treating type 1 diabetic animals.
Articles
  • Yasunori Yoshioka, Hideaki Sano, Masaki Mitani
    2006 Volume 79 Issue 8 Pages 1201-1210
    Published: 2006
    Released: August 07, 2006
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    Geometries and electronic structures of the quintet and septet states of the [Mn(P)(O2)] (P: porphinato) anion were theoretically investigated. Four local minimum geometries with two side-on additions of O2 to MnP, 1 (5B2) and 3 (7A2), and two end-on additions of O2, 2 (5A″) and 4 (5A′), were found. One of the side-on forms, 1, corresponds to that observed by X-ray crystallographic study. 3 is a septet state with higher spin than the quintet states of 1, 2, and 4. Each of the two end-on forms has the corresponding transition state with the side-on geometry. Energy differences among 1, 2, and 3 are less than 1 kcal mol−1. The electronic structures of four local minimum states were essentially different. 1 has an electronic structure presented as [MnIII(O22−)]. 2 has antiferromagnetically coupled diradical character presented by the formal chemical formula of [MnII•(O2•−)]. 3 has ferromagnetically coupled diradical character. 4 is presented by [MnII(O2)].
  • Takuya Hasegawa, Masaru Sugita, Kohei Takatani, Hirotaka Matsuura, Tom ...
    2006 Volume 79 Issue 8 Pages 1211-1214
    Published: 2006
    Released: August 07, 2006
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    Assay of alkaline phosphatase (ALP) in salmon egg cell cytoplasm was performed by size exclusion chromatography (SEC) with fluorescence detection of enzymatic activity and element-selective detection of zinc by ICP-MS, where 4-methylumbelliferyl phosphate (4-MUP) was used as the substrate for the enzymatic reaction of ALP. Two peaks were observed at retention times of ca. 21 and 27 min in the fluorescence-detected SEC chromatogram for salmon egg cell cytoplasm diluted 10-fold with 0.1 M Tris-HNO3 buffer solution, corresponding to the molecular weights (MWs) of ≥300 and 100 kDa, respectively. On the other hand, in the 66Zn-detected chromatogram for the same sample, a broad peak with a shoulder on the side of longer retention time was observed at ca. 21 min (MW≥300 kDa). When salmon egg cell cytoplasm was diluted 10-fold with pure water or 0.01 M Tris-HNO3 buffer solution, precipitation occurred. The supernatant obtained after filtration produced only one clear peak at a retention time of ca. 27 min in the fluorescence-detected chromatogram, at which the peak corresponding to zinc was also observed in the Zn-detected chromatogram. Therefore, the peak near 27 min was assigned to hydrophilic ALP in the salmon egg cell cytoplasm. Furthermore, the concentration of hydrophilic ALP (MW ca. 100 kDa) in the salmon egg cell cytoplasm was about 350 ng g−1, which was determined as an E. coli ALP-equivalent concentration by fluorescence intensity measurements.
  • Masashi Hojo, Tadaharu Ueda, Chihiro Daike, Fumiko Takezaki, Yumi Furu ...
    2006 Volume 79 Issue 8 Pages 1215-1222
    Published: 2006
    Released: August 07, 2006
    JOURNALS FREE ACCESS
    In reverse micelle systems, a large enhancement of the oxidation ability of dilute nitric acid was discovered, and its oxidation mechanism was explored. The Br ion in the surfactant, CTAB, was oxidized to Br2 (or Br3) in the CHCl3/CTAB/H2O reverse micelle system with W = 1.0–4.0 by diluted nitric acid (0.25–2.5 mol dm−3 in 1.0 vol % H2O portion) at 15–40 °C where CTAB stands for cetyltrimethylammonium bromide, and the W value is the ratio of [H2O]/[surfactant]. At higher concentrations of nitric acid and temperatures, faster reactions occurred. Otherwise, long reaction times were needed, e.g., 10 h for 1.0 mol dm−3 HNO3 at 25 °C. Light or ambient oxygen did not appear to affect the reaction. The ratio of produced Br2 or (Br3) to the initial amount of HNO3 indicated the following reaction scheme: 2HNO3 + 2Br → Br2 + NO2 + NO3 + H2O. The nitroyl ion (or nitronium ion), NO2+, was proposed as the intermediate active species. The addition of HClO4 as a proton source caused the complete reduction of N(V) as follows: NO3 + 6H+ + 5e → 1/2N2 + 3H2O. The hydrogen-bonding structure of H2O in the CTAB or CTAC (cetyltrimethylammonium chloride) micelle system was found to be distorted, compared to that in bulk water, by the 1H NMR chemical shift of H2O. The change in 1H NMR chemical shift also demonstrated the consumption of protons during the oxidation of Br, but not of Cl, by dilute HNO3.
  • Hidenori Tannai, Kiyoshi Tsuge, Yoichi Sasaki
    2006 Volume 79 Issue 8 Pages 1223-1230
    Published: 2006
    Released: August 07, 2006
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    Mononuclear and dinuclear Pd(II) complexes with mercapto-1,3,4-thiadiazolate were prepared by reacting [Pd(OH)(terpy)](PF6) with 2-amino-5-mercapto-1,3,4-thiadiazole (Hamct) and 2,5-dimercapto-1,3,4-thiadiazole (H2dmct). The reaction of [Pd(OH)(terpy)](PF6) and [Pt(Hdmct)(terpy)](PF6) resulted in the formation of the Pd(II)–Pt(II) heterometallic complex [{Pd(terpy)}(μ-dmct-S,S′){Pt(terpy)}](PF6)2, which showed that dmct2− can be utilized to prepare rationally heterometallic systems. Crystal structure analysis of the complexes showed that the ligands coordinate to the Pd(II) and Pt(II) centers by their mercapto groups in a κ1S coordination mode. The electronic spectra, redox properties, and molecular orbitals of the palladium complexes have been compared to those of Pt(II) congeners that we reported previously. The properties of a Pd(II)–Pt(II) mixed metal complex were elucidated based on the properties of each metal center.
  • Emi Sato, Kiyoshi Matsumoto, Hiroshi Okochi, Manabu Igawa
    2006 Volume 79 Issue 8 Pages 1231-1233
    Published: 2006
    Released: August 07, 2006
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    Hydrophobic volatile organic compounds (VOCs) are usually found in rainwater with higher concentrations than the values determined from Henry’s law partitioning. Laboratory experiments demonstrated that dissolved organic compounds, such as humic acids, act as cosolvents to solubilize the VOCs. Wet removal by rainfall is a significant sink of trace VOCs.
  • Yuki Matsunaga, Kiyoshi Fujisawa, Nagina Amir, Yoshitaro Miyashita, Ke ...
    2006 Volume 79 Issue 8 Pages 1234-1236
    Published: 2006
    Released: August 07, 2006
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    A systematic study on the effects of different metals and halogenide ions was carried out by using [MX2(sp)] (M = Zn and Cd; X = Cl, Br, and I; sp = (−)-sparteine). The complexes have been characterized by X-ray crystallography, and far-IR and Raman spectroscopy.
  • Yosuke Konno, Nobuyuki Matsushita
    2006 Volume 79 Issue 8 Pages 1237-1239
    Published: 2006
    Released: August 07, 2006
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    A platinum complex with a non-innocent ligand, [PtII(L)2] (1), where L is o-semibenzoquinonediimine monoanion, has two polymorphs. In one polymorph, molecules related by translation are arranged in the same orientation along the c axis, while in the other, molecules related by a c-glide plane are aligned alternately in different orientation.
  • Mitsutaka Kudoh, Susumu Sudoh, Shigeyoshi Katagiri, Tomoo Nakazawa, Ma ...
    2006 Volume 79 Issue 8 Pages 1240-1247
    Published: 2006
    Released: August 07, 2006
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    The precise X-ray structures of furo[3,4-d]tropone (2), 2,4-dimethyl-8H-3-oxaheptalen-8-one (5), and 4,5-benzotropone (6) were determined. Their tropone rings show definite bond alternation and nearly planar conformation, though slightly boat-shaped like polycyclic tropone. The ground-state dipole moments of 2, 5, and 6, and also 8H-3-oxaheptalen-8-one (3) and 2-methyl-8H-3-oxaheptalen-8-one (4) were measured in benzene at 25 °C. Analyses of the ground-state dipole moments by means of ab initio calculations demonstrate that the polar structures of 2 and 6 having an annulated aromatic ring are based on the local dipoles of penta-1,4-dien-3-one and the induced dipole of the annulated ring, whereas those of 3 and 5 are based not only on the local dipoles but also on the partial intramolecular CT interaction from the olefinic oxepin ring to the pentadienone moiety. According to the McRae equation, the dipole moments of the two lowest excited states of 2, 3, 5, and 6 were evaluated by using the frequency shifts of the absorption maxima in a number of polar and nonpolar solvents. They are all oriented in the same direction as that of the ground state, but are greater in magnitude.
  • Masanori Morinaga, Masahiro Taniguchi, Tsuyoshi Sonogi, Gou Watanabe, ...
    2006 Volume 79 Issue 8 Pages 1248-1254
    Published: 2006
    Released: August 07, 2006
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    New chiral host compounds have been prepared from L-tryptophan and 3-aroylpropionic acids. These hosts show broad inclusion and sorption abilities toward solvent and racemic molecules, and are characterized by X-ray crystallographic analysis, which clarify the one-dimensional channel structures of the hosts, the helical arrangements of the guests, and the occurrence of weak interactions such as C–H···O and C–H···Cl between the hosts and the guests. The TG and DTA data show the high cohesion of the hosts, and the PXRD patterns indicate that the crystal structures of the hosts remain ordered after removal of the guest molecules. These hosts have potential usefulness in the optical resolution of racemic guest molecules such as s-butyl chloride and 4-methylcyclohexene.
  • Hidenori Aoki, Teruaki Mukaiyama
    2006 Volume 79 Issue 8 Pages 1255-1264
    Published: 2006
    Released: August 07, 2006
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    An alkylation reaction of alcohols with alkyl N-(methylsulfonyl)diphenylphosphinimidates proceeded smoothly in the presence of a catalytic amount of trimethylsilyl triflate (Me3SiOTf) in DME at room temperature and the corresponding ethers were afforded in good to high yields. An alkyl N-(methylsulfonyl)diphenylphosphinimidate can be prepared easily from an alkyl diphenylphosphinite and methanesulfonyl azide, and is isolated without tedious operation. Moreover, it is easy to handle and can be stored for several months at room temperature because of its air- and moisture-resistant character. Also, one-pot tertiary alkylations of alcohols by using t-alkyl diphenylphosphinites and diphenoxyphosphoryl azide proceeded efficiently in the presence of a catalytic amount of Me3SiOTf in cyclohexane/CH2Cl2 at 0 °C or −10 °C, and gave the corresponding tertiary alkyl ethers in good yields. By following these methods, various ethers having alkali-sensitive functional groups can be prepared easily.
  • Yasushi Yanagimoto, Yutaka Takaguchi, Sadao Tsuboi, Masahiro Ichihara, ...
    2006 Volume 79 Issue 8 Pages 1265-1270
    Published: 2006
    Released: August 07, 2006
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    Novel tetra-substituted anthracene derivatives were synthesized, and their liquid crystallinities were characterized by using polarizing optical microscopy, DSC, and XRD. Although photodimerization of the anthracene derivatives proceed quantitatively upon irradiation with high-pressure mercury lamp in chloroform, the photoirradiation of the mesophases of these derivatives did not yield the corresponding photodimers. XRD analysis of the mesophases showed unusual stacking of anthracene moieties, which have insufficient orbital overlap. Structural analysis is consistent with the photoreactivity.
  • Hiroto Yasui, Toshihiro Nishikawa, Hideki Yorimitsu, Koichiro Oshima
    2006 Volume 79 Issue 8 Pages 1271-1274
    Published: 2006
    Released: August 07, 2006
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    Cobalt salts such as cobalt(II) chloride catalyze allylzincation reactions of 1-aryl-1-alkynes. The allylzincations proceed in a syn fashion to form 2-allyl-1-aryl-1-alkenylzinc species. Other internal alkynes such as 6-dodecyne or 2-nonyn-1-ol are much less reactive than 1-aryl-1-alkynes.
  • Yoshinori Sato, Hidehiko Fujisawa, Teruaki Mukaiyama
    2006 Volume 79 Issue 8 Pages 1275-1287
    Published: 2006
    Released: August 07, 2006
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    Lewis base-catalyzed [2,3]-Wittig rearrangement of silyl enolates generated from α-allyloxy carbonyl compounds is described. The [2,3]-Wittig rearrangement of silyl enolates generated from α-allyloxy ketones proceeded smoothly by using a Lewis base catalyst, such as lithio or sodio 2-pyrrolidone, in DMF at room temperature without an accompanying [3,3]-Claisen rearrangement. The nature of the catalyst determines the pathway to proceed either by [2,3]-Wittig or [3,3]-Claisen rearrangement. In addition [2,3]-Wittig rearrangement of silyl enolates generated from α-allyloxy esters was tried. It was found that ammonium carboxylates, such as 4-methoxybenzoate, effectively promoted the reaction to afford the [2,3]-Wittig rearrangement product in good yield. This is the first example of the Lewis base-catalyzed [2,3]-Wittig rearrangement of silyl enolates generated from α-allyloxy carbonyl compounds.
  • Sota Sato, Tomoko Fujino, Hiroyuki Isobe, Eiichi Nakamura
    2006 Volume 79 Issue 8 Pages 1288-1292
    Published: 2006
    Released: August 07, 2006
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    Diels–Alder reactions of a cyclopentadienone acetal with aromatic heterocycles, such as pyrrole or indole, took place with the latter acting as a 2π dienophile. The reaction gave a polycyclic heterocycle in good yield regioselectively. Analysis of the frontier molecular orbitals showed that inverse electron demand interactions control the regioselectivity.
  • Gaku Yamamoto, Yuriko Kobayashi, Kasumi Ono, Emiko Yano, Mao Minoura, ...
    2006 Volume 79 Issue 8 Pages 1293-1299
    Published: 2006
    Released: August 07, 2006
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    9-Triptycylallene (1) was synthesized by LiAlH4 reduction of 1-(9-triptycyl)-2-propynyl methanesulfonate (7), and three 3-substituted derivatives of 1 were also obtained by reacting compound 7 with appropriate metal reagents. LiAlH4 reduction of 1,3-di(9-triptycyl)-2-propynyl methanesulfonate (10) gave 1,3-di(9-triptycyl)propyne (12). The molecular structures of some of the allenes and of the propyne were determined by X-ray crystallography. As well, the allenes and some of the related compounds were characterized by NMR spectroscopy.
  • Tianyan Zhou, Yifan Wang, Xinming Li, Qiang Zhang, Tianhu Li
    2006 Volume 79 Issue 8 Pages 1300-1302
    Published: 2006
    Released: August 07, 2006
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    A fluorescein-labeled circular G-quadruplex was readily synthesized chemically using a linear G-rich precursor. Hydrolysis tests and fluorescence spectroscopic examination confirmed that the product in our investigation has a circular backbone and possesses a fluorescein moiety.
  • Takeshi Itakura, Ryo Sasai, Hideaki Itoh
    2006 Volume 79 Issue 8 Pages 1303-1307
    Published: 2006
    Released: August 07, 2006
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    A new treatment method for wastewater containing concentrated fluoride and fluoroborate ions by hydrothermal treatment were developed. The treatment is an earth-mimetic method to produce natural minerals by hydrothermal treatment with Ca(OH)2 as a mineralizer. Results of various analyses of the precipitate indicated that the recovered minerals were Ca2B2O5·H2O (parasibirskite) and CaF2 (fluorite). By optimizing the conditions, it was possible to recover more than 98 percent of the boron and 99.9 percent of the fluorine from model wastewater samples containing fluoride (7000 mg L−1) and fluoroborate (8000 mg L−1) ions. Moreover, in the case of fluoroborate ions, the present treatment simultaneously caused the decomposition of the fluoroborate ion, the formation of each minerals, and the preventation of redissolution of parasibirskite. Therefore, the present hydrothermal mineralization treatment with the Ca(OH)2 mineralizer is an effective technique to recover boron and fluorine from wastewater.
  • Nalinakumari Preethi, Hiromi Shinohara, Hiroyuki Nishide
    2006 Volume 79 Issue 8 Pages 1308-1311
    Published: 2006
    Released: August 07, 2006
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    The pore surface of a porous glass membrane was modified with phthalocyanato- and tetraphenylporphyrinato-1-(benzylimidazole)cobalt(II) complexes, which specifically and reversibly binds molecular oxygen from air. The lower oxygen-binding affinity enhanced surface oxygen diffusion which improved permeability (3.0 × 10−11 kmol m s−1 m−2 kPa−1) and (oxygen/nitrogen) permselectivity (10).
  • Peijun Cai, Yuhua Zhang, Li Feng
    2006 Volume 79 Issue 8 Pages 1312-1313
    Published: 2006
    Released: August 07, 2006
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    Hollow carbon spheres with in diameter ranging from 50 to 150 nm have been successfully synthesized by the decomposition of poly(tetrafluoroethylene) ([CF2CF2]n, PTFE) at 550 °C using NaN3 as a defluorination reagent. The formation mechanism of hollow carbon spheres is also proposed. The present study provides a promising route to decompose other plastics that are difficult to degrade in the environment.
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