Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 63 , Issue 9
Showing 1-50 articles out of 57 articles from the selected issue
  • Hidetomo Noda, Shoichiro Ikeda, Yoshiyuki Oda, Kazumoto Imai, Masunobu ...
    1990 Volume 63 Issue 9 Pages 2459-2462
    Published: 1990
    Released: June 05, 2006
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    The electrochemical reduction of carbon dioxide at various metallic electrodes was carried out potentiostatically at 298 K in aqueous potassium hydrogen carbonate solution in order to make clear the electrocatalysis of metals in reduction of CO2. It was found that metals used as electrodes are classified into four groups according to their main products from CO2, i. e., metallic In, Sn, Hg, and Pb are selective for the production of formic acid; metallic Ag and Au are selective for the formation of carbon monoxide; metallic copper has the highest electrocatalytic activities in formation of hydrocarbons, aldehydes, and alcohols; and metallic Al, Ga, Group a, and Group VIII elements except Pd have scarce electrocatalytic activity in reduction of CO2. Effects of the reduction potential on products from CO2 were also examined in detail for Zn, In, and Au electrodes which have some interesting properties.
  • Yoshihiro Shigemasa, Osamu Yamasaki, Hitoshi Sashiwa, Hiroyuki Saimoto
    1990 Volume 63 Issue 9 Pages 2463-2467
    Published: 1990
    Released: June 05, 2006
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    The effects of voltage, electrolytes, monosaccharides, and pH on the transportation of monosaccharides by electrodialysis were investigated. Transportation was strongly affected by the formation of monosaccharide-borate esters. It was possible to separate saccharides using an electrodialysis technique.
  • Nobuaki Kanamaru
    1990 Volume 63 Issue 9 Pages 2468-2474
    Published: 1990
    Released: June 05, 2006
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    Fluorescence depolarization after R branch excitation of 000 1B1 pyrimidine was interpreted by utilizing ΔJ=0 and/or ±1 coupling schemes within a singlet manifold through triplet rovibronic levels where spin-orbit, vibration-rotation, and hyperfine interaction terms are involved. These schemes are suggested to be useful interpreting the intermediate-case phenomena observed in this kind of molecules.
  • Tsuneo Fujii, Akira Ishii, Hiroshi Satozono, Satoshi Suzuki, Michel Ch ...
    1990 Volume 63 Issue 9 Pages 2475-2480
    Published: 1990
    Released: June 05, 2006
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    The fluorescence, fluorescence excitation, and time-resolved fluorescence spectra of pyrene molecules adsorbed on calcinated (773 K) Vycor glass (average pore diameter, 40 Å) have been investigated as a function of the amount of adsorbed pyrene. The results of the analyses of these spectra and multi-component decays of fluorescence suggest that there are three fluorescent species with different decay times on the surface of Vycor glass. Their lifetimes are determined to be 303–355, 100–145, and 19–48 ns. These decay components are reasonably assigned to the emissions of monomeric, dimeric, and excimer-like species in the order of decreasing the lifetimes. A 26600 cm−1 peak appearing at the first stage of the time-resolved fluorescence spectra is assingned to the 0–0 hand of dimeric pyrene based on the results reported by Yamazaki et al. in the Langmuir-Blodgett monolayer.
  • Kazuaki Harata
    1990 Volume 63 Issue 9 Pages 2481-2486
    Published: 1990
    Released: June 05, 2006
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    Crystal structures of hexakis(2,6-di-O-methyl)-α-cyclodextrin complexes with 1-propanol and iodine were determined by X-ray analysis. Crystals of both complexes are isomorphous and the space group is P21 with cell dimensions: a=14.136(2), b=10.680(1), c=21.479(2) Å, and β=106.00(1)° for the 1-propanol complex and a=14.124(2), b=10.667(2), c=21.443(3) Å, and β=106.29(1)° for the iodine complex. The structures were solved by the R-map method combined with the rigid-body least-squares technique and refined by the block-diagonal least-squares method to the R-value of 0.058 for the 1-propanol complex and 0.094 for the iodine complex. The host molecules are arranged in a herring-bone fashion to form a typical cage-type packing structure. Both guest molecules are included within the “cage” which is created by the block of both ends of the annular host cavity by adjacent molecules. The 1-propanol molecule is in van der Waals contact with the inside wall of the host cavity, whereas the iodine molecule forms a charge-transfer complex with an O(3)H hydroxyl group of the adjacent host.
  • Yoshimi Sueishi, Seiji Furui, Yukinobu Matsumoto, Shunzo Yamamoto, Nor ...
    1990 Volume 63 Issue 9 Pages 2487-2493
    Published: 1990
    Released: June 05, 2006
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    Di-t-butyl diperoxyoxalate (DBPO) was allowed to decompose at 40 °C in benzene and xylenes, and transient radicals were trapped by some nitroso compounds. By means of an ESR simulation technique, the trapped radicals were assigned. In benzene, t-butoxyl radicals were trapped. Exceptionally, when 1,3,5-tri-t-butyl-2-nitrosobenzene(1) was used, methoxyl radicals were trapped first, but the ESR signals changed with time and methyl radicals were finally trapped. In xylenes, monomethylbenzyl radicals were exclusively trapped by 1 and 2,4,6-trimethyl-l-nitrosobenzene(2). The hyperfine coupling constant (hfcc) of β-hydrogens exhibited a negative temperature dependence for adducts formed between 1 and benzyl radicals(1-BZ), while for adducts formed between 2 and benzyl radicals(2-BZ), a positive one.
  • Tai-ichi Shibuya, Susumu Narita
    1990 Volume 63 Issue 9 Pages 2494-2497
    Published: 1990
    Released: June 05, 2006
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    The previously proposed scheme of parametrized equations of motion for the π→π* transitions of linear polyenes [Bull. Chem Soc. Jpn., 62, 701 (1989)] has been simplified in the treatment of the σ–π electron correlations. The simplified schemes seem to give results as accurate as the original one for the low-lying excited states.
  • Jun-ichi Aihara, Hiroshi Ichikawa, Hiroaki Tokiwa, Yasuaki Okumura
    1990 Volume 63 Issue 9 Pages 2498-2503
    Published: 1990
    Released: June 05, 2006
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    β-Carboline anhydro-bases generally have a large positive topological resonance energy although they apparently disobey the rule of topological charge stabilization (TCS rule). π-Electron densities and molecular geometries calculated at the STO-3G+ level support the view that the dipolar aromatic structure contributes appreciably to the stability of β-carboline anhydro-bases. However, these molecules are still worse in energy than the isomeric β-carbolines. Protonated anhydro-bases or β-carbolinium ions conform to the TCS rule. All biogenic β-carboline anhydro-bases must be protonated in living organisms.
  • Ayyakkannu Manivannan, Kazuhito Hashimoto, Tadayoshi Sakata, Akira Fuj ...
    1990 Volume 63 Issue 9 Pages 2504-2510
    Published: 1990
    Released: June 05, 2006
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    Electroluminescence (EL) due to band-band transition was observed for n-InP single crystal electrodes in solutions containing current doubling reagents like peroxodisulfate and various redox electrolytes. The mechanism for the EL emission in relation to surface properties of n-InP crystals in these electrolytes is presented. The cathodic decomposition process of n-InP electrodes involved in various electrolytes especially in peroxodisulfate medium has been analyzed from the EL emission as a function of electrode potential under steady state as well as pulsed conditions. The intensity of the EL signal depends on the electron density at the interface which is controlled by the potential and on the chemical composition of the electrode surface. Moreover, a hydrogen evolution reaction reduces the EL efficiency at higher cathodic potentials. Though the potential has no effect on the shape of the EL spectra, a significant change in EL intesity was observed. In all the electrolytes used the InP electrodes seem to decompose during cathodic polarization to form indium metal. The change in the surface composition plays an important role in the relation between potential and the EL intensity. Moreover, during pulsed polarization the EL behavior is different from the steady state conditions and also depends on the concentration of the electrolyte species.
  • Satoshi Kawata, Hiroshi Yokoi, Masamoto Iwaizumi
    1990 Volume 63 Issue 9 Pages 2511-2515
    Published: 1990
    Released: June 05, 2006
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    Dimer formation of the title complex in toluene and benzene mixed solvents has been demonstrated by the EPR spectroscopy. The dimer structure and the spin-exchange energy have been examined by spectral simulation for ΔMs=2 transitions and the temperature dependence of their spectral intensities, respectively. It has been found that the structure and the magnetism are similar to those of the inversion pair of bis(benzoylacetonato)oxovanadium(IV) in a crystal which is known to show dimeric interactions in its EPR spectra. The formation constant of the dimer, K, for 2 [monomer] \ ightleftharpoons dimer has been determined by analyzing the concentration dependence of the dimer and the monomer EPR signals, indicating that K is remarkably solvent-dependent.
  • Jianhua Liu, Yoshitaka Masuda, Eiichi Sekido
    1990 Volume 63 Issue 9 Pages 2516-2520
    Published: 1990
    Released: June 05, 2006
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    The first ionic association constants between five macrocyclic Schiff base metal(II) complexes (cation and perchlorate or thiocyanate anion) were determined by conductometric measurements in methanol at 25 °C by using a modified Onsager limiting equation, according to Fuoss and Edelson method. The limiting equivalent conductivities of the chelate cations of these complexes were calculated. These results were used to evaluate the performance of coated-wire perchlorate ion-selective electrodes (PCWE) based on these complexes.
  • Koji Yamada, Hiroshi Kawaguchi, Takashi Matsui, Tsutomu Okuda, Sumio I ...
    1990 Volume 63 Issue 9 Pages 2521-2525
    Published: 1990
    Released: June 05, 2006
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    A series of solid solutions, CH3NH3Sn1−xPbxBr3 (x=0–1), having cubic perovskite structures was obtained by solid-state reactions. The 119Sn Mössbauer spectra for x<0.4, however, indicated that the tin environment was considerably distorted from a regular octahedron at 110 K. On the other hand, a single Lorentzian spectrum having a large isomer shift was observed for x>0.7, suggesting the presence of a regular SnBr6 octahedra in the perovskite CH3NH3PbBr3 matrix. The high electrical conductivity of the perovskite CsSnBr3 drastically decreased upon the replacement of the cation by CH3NH3 and the central metal by Pb. This behavior suggests that both the infinite linear chain (–Br–Sn(Pb)–Br–) and its bond length have significant importance regarding electrical conductivity.
  • Shiro Shimada, Ryusaburo Furuichit
    1990 Volume 63 Issue 9 Pages 2526-2530
    Published: 1990
    Released: June 05, 2006
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    A new apparatus for simultaneous measurements of acoustic emission (AE) and differential thermal analysis (DTA) is described. Two fused silica cells are used as the sample and reference holders and a fused silica rod, fixed at the bottom of the sample holder, acts as the waveguide for AE signals emitted in the sample. A 140 KHz resonance frequency sensor is attached at the end of the rod to detect the AE signals which are converted by an AE tester to three parameters, the wave form, the event count rate, and the cumulative count. The technique has been successfully utilized to study the dehydration, phase transition, and decomposition of NaN3, KNO3, KClO4, CaCrO4·0.1H2O, and MgCl2· 6H2O, for which the interesting results are reported.
  • Teruo Kurihara, Sumio Ishikawa, Tetsuo Nozoe, Jun-ichi Aihara
    1990 Volume 63 Issue 9 Pages 2531-3539
    Published: 1990
    Released: June 05, 2006
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    The fundamental skeleton of the tropones possessing a unique heptagonal structure is predicted to be aromatic with positive resonance energies and conforming to the topological charge stabilization rule (TCS rule). Similarly, naturally occurring tropolones also nicely fit the theory that conformity to the TCS rule gives a stable molecular system. Thus, many of the troponoids so far synthesized and those occurring in nature are energetically very stable molecules as well as being synthetically very accessible. The TCS rule applies very well to the formation mechanism of heterocycle-fused tropones. It is very likely that there are various reaction paths in nature which are compatible with the TCS rule for the formatin of tropylium compounds having annulated heterocycles.
  • Satoshi Moriyama, Takayuki Karakasa, Shinichi Motoki
    1990 Volume 63 Issue 9 Pages 2540-2548
    Published: 1990
    Released: June 05, 2006
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    5,6-Dihydro-2-phenyl-3-thiobenzoyl-2H-naphtho[1,2-b]thiin (8a) and the related dienic thioketones were synthesized in 3 steps starting from 2-(phenylthio)methylenetetralin-1-thione with chalcone, 4′-chrolochalcone, 4′-methoxychalcone, 2-cinnamoylthiophen, 2-cinnamoylfuran, 1-phenyl-2-buten-1-one, and acrylophenone respetively. Similarly, 3-thiobenzoyl-2,6-diphenyl-2H-thiin (8i) was synthesized from 1-phenyl-3-phenylthio-2-propene-1-thione. All of these dienic thioketones were found to exist in stable monomeric form. The conjugated dienic thioketone (8a) reacted as α,β-unsaturated thioketone with 2-norbornene, 2,5-norbornadiene, diethyl azodicarboxylate, diphenyl fumarate, N-phenyl- and N-(p-tolyl)maleimides, 2-chloroacrylonitrile, methyl methacrylate, acrylonitrile, and styrene to give the corresponding [4+2]cycloadducts. The thioketone (8i) also reacted with 2-norbornene to give the corresponding cycloadduct. The reaction provides a useful method for the syntheses of various sulfur-containing heterocycles.
  • Masashi Kijima, Kiyokatsu Miyamori, Tomoko Nakamura, Takeo Sato
    1990 Volume 63 Issue 9 Pages 2549-2554
    Published: 1990
    Released: June 05, 2006
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    The reactivity of photoactivated organocobaloxime was investigated by the reaction of thiol. Alkyl(pyridine)cobaloxime and ethyl mercaptoacetate were irradiated with a tungsten lamp under anaerobic conditions in an organic solvent to give ethyl alkylthioacetate, diethyl 2,2′-dithioacetate, and ethoxycarbonylmethylthiocobaloxime. Mechanistic investigations were carried out to determine the reaction course. Sulfide was assumed to be produced via a homolytic substitution between alkylcobaloxime and disulfide formed during the reaction. Disulfide was formed from thiol catalytically in the presence of cobaloxime under anaerobic conditions. Homolytic methyl-transfer scarcely occurred from methylcobaloxime into thiol.
  • Yoshio Tamura, Hiroo Takizawa, Gaku Yamamoto, Michinori Oki, Shigeru M ...
    1990 Volume 63 Issue 9 Pages 2555-2563
    Published: 1990
    Released: June 05, 2006
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    Changing the substituent at the 4-position of 9-chloromethyl-1-methoxytriptycene shows that the nitro group increases the sc conformation whereas the methoxyl group favors the ap conformation in a relative sense, as judged from the 1H NMR spectra at low temperatures. Examination of rotational barriers, solvent effects, and thermodynamic parameters has not been able to distinguish three possibilities, O···CH2Cl interactions, head-to-tail arrangement of two dipoles, and van der Waals repulsions as a main cause for the observed population change. X-Ray crystallographic analyses of the title compound and related ones suggest that in the crystalline state the 1-methoxyl group in the title compound takes an anomalous conformation in which the group is nonplanar with the benzeno bridge. This feature was not observed in 1,4-dimethoxy-9-methyltriptycene. This structural feature is attibuted to the presence of O···CH2Cl interactions in the title compound and eliminates the van der Waals repulsion and the head-to-tail arrangement of two dipoles from being the main cause that favors the ap form.
  • Shigeru Futamura, Ken-ichiro Fujimoto, Yoshio Kamiya
    1990 Volume 63 Issue 9 Pages 2564-2568
    Published: 1990
    Released: June 05, 2006
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    The Fe-catalyzed hydrogenolysis of trans-stilbene was carried out in aromatic hydrocarbon solvents at 380 °C. α-Fe and pyrrhotite catalyze bimolecular hydrogen transfer from hydroaromatic hydrocarbons to trans-stilbene and hydroaromatic hydrocarbon-mediated hydrogenolysis of trans-stilbene by molecular hydrogen at 380 °C. This catalyzed hydrogen transfer proceeds by radical mechanism. The product distribution is affected by the catalyst species. Pyrrhotite catalyzes the hydrogenation of trans-stilbene more effectively than α-Fe. Both the iron catalysts are inactive toward the cleavage of carbon to carbon single bond in bibenzyl.
  • Hidehiko Tanaka, Eiji Kimoto
    1990 Volume 63 Issue 9 Pages 2569-2572
    Published: 1990
    Released: June 05, 2006
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    The addition of sodium hydroxide to an ethanolic dehydro-L-ascorbic acid solution produced a yellowish precipitate which was enriched by a reductant possessing absorption maxima at 345 and 225 nm. This reductant was purified by DEAE-Sepharose column chromatography and Cellulofine-gel chromatography; on the basis of physicochemical analyses it was deduced to be the 2,3-enediol form of 2,3-diketo-L-gulono-δ-lactone (2,3,6-trihydroxy-4-oxo-2-hexen-5-olide). The process, derived from dehydro-L-ascorbic acid, involved a hydrolytic cleavage of a 5-membered γ-lactone ring, conversion to the 2,3-enediol form and rearrangement to 6-membered δ-lactone. The marked bathochromic shift of the absorption maximum of this reductant from that of ascorbic acid (265 nm) could be due to an extended conjugation among the enediol group and two carbonyl groups on both sides.
  • Kazuaki Ito, Yukie Noro, Katsuhiro Saito, Kensuke Takahashi
    1990 Volume 63 Issue 9 Pages 2573-2577
    Published: 1990
    Released: June 05, 2006
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    Thermal addition reactions of tropone and 8,8-dicyanoheptafulvene with a homoconjugated diene, dimethyl 3-cyanotricyclo[3.2.2.02,4]nona-6,8-diene-6,7-dicarboxylate derivative, proceeded stereoselectively to give endo-[4+2]-type cycloadducts, where the troponoids acted as 4 π components. Upon photo-irradiation the adducts afforded intramolecular [2+2]-type addition products to verify the endo-form of the adducts. Molecular orbital caluculations suggested that the stereoselectivity could be explained by secondary orbital interactions between the HOMO of the troponoid compounds and the LUMO of the tricyclic compound. A thermal reaction of the adducts gave three-membered ring opened products, which further proceeded through an intramolecular [2+2]-type reaction upon photo-irradiation.
  • Kyoko Nozaki, Koichiro Oshima, Kiitiro Utimoto
    1990 Volume 63 Issue 9 Pages 2578-2583
    Published: 1990
    Released: June 05, 2006
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    The reduction of dithiocarbonates or thiocarbonates by n-Bu3SnH–Et3B easily gives the corresponding hydrocarbons. The intermediate alkoxythiocarbonyl radical equivalents are trapped by properly located carbon–carbon multiple bonds. The dithiocarbonates derived from either homopropargylic or homoallylic alcohols produce tetrahydrofuranones upon treatment with n-Bu3SnH–Et3B. Application of this new method to the conversion of carbonyl compounds into olefins is also described.
  • Katsukiyo Miura, Koichiro Oshima, Kiitiro Utimoto
    1990 Volume 63 Issue 9 Pages 2584-2587
    Published: 1990
    Released: June 05, 2006
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    Proton abstraction from 3-trimethylsilylmethylthio-1-propene by butyllithium followed by treatment with iodomethane provided 1-methylthio-4-trimethylsilyl-1-butene. Meanwhile, 1-trimethylsilylmethylthio-2-butene afforded 3-methyl-4-methylthio-1-trimethylsilyl-1-butene upon successive treatment with butyllithium and iodomethane.
  • Makoto Hojo, Masahiro Hojo, Yoshihiko Inoue, Shigeo Tanimoto
    1990 Volume 63 Issue 9 Pages 2588-2592
    Published: 1990
    Released: June 05, 2006
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    Several α-keto esters and methyl N-p-tolylsulfonyl-2-aryl-2-iminoacetates were reduced to the corresponding α-hydroxy esters and methyl N-p-tolylsulfonyl-2-arylglycinates in high yields by a combination of aluminum(III) chloride and diphenylsilane under operating conditions in which diphenylsilane was added to the pre-formed substrate-aluminum(III) chloride complex in dichloromethane and the mixture stirred. The case of an exactly equivalent amount of aluminum(III) chloride as the substrate resulted in good results.
  • Kazuyuki Umemura, Haruo Matsuyama, Nobumasa Kamigata
    1990 Volume 63 Issue 9 Pages 2593-2600
    Published: 1990
    Released: June 05, 2006
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    The reactions of dialkylphenylsulfonium salts (1) with several nucleophiles such as phenols, amine, enolate ion, and thiolate ions, have been investigated. The relative reactivities of the alkyl groups of sulfonium salts for the phenolate ion (hard nucleophile) were as follows; Me:Et:i-Pr =1.0:1.34:3.44. In the alkylation of the p-toluenethiolate ion (soft nucleophile) with 1, the opposite reactivity (Me:Et:i-Pr=1.0:0.22:0.03) was found. When a sulfonium salt (1e) having an optically active (S)-s-butyl group was reacted with a phenolate ion, an optically active (R)-s-butyl phenyl ether was obtained with an inversion of the configuration at the chiral carbon atom. A reaction mechanism via a sulfurane intermediate is proposed for the alkylation of the phenolate ion with alkylsulfonium salts. The relative reactivities for the alkylation of several nucleophiles with dialkylphenylselenonium salts (12) were also investigated.
  • Hiromichi Yamazaki, Yasuhito Kanno, Yasushi Inoue
    1990 Volume 63 Issue 9 Pages 2601-2609
    Published: 1990
    Released: June 05, 2006
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    The affiinity for various cations and the thermal stability were studied on hydrous silicon–titanium(IV) oxide ion exchangers with various titanium contents. An exchanger with 52 mol% Ti shows a higher affinity for an alkali metal ion having a smaller hydrated radius but similar affinity, which depends little on the pH′s of solutions, for alkaline earth metal ions, except for Ba2+. In the sorption of transition metal ions, the formation of a covalent bond is a factor in determining the selectivity of the exchanger, along with the remote coulombic interaction. The composition dependence of the affinities for Cs+, Ba2+, Co2+, Eu3+, and UO22+ was explained in terms of the acid-base properties of the exchangers. The exchangers with 37 to 67 mol% Ti do not suffer from any drastic change in the surface area and in the crystallinity upon heating up to 540 °C, and are much more heat-resistant than the component simple hydrous metal oxides. The degree of the decrease in the exchange capacity upon heat treatment is larger in exchangers with a higher titanium content. The effect of a heat treatment on the acid-base property and the affinity for cations was also studied.
  • Jan Labuda, Kumiko Mafune, Yutaka Fukuda
    1990 Volume 63 Issue 9 Pages 2610-2614
    Published: 1990
    Released: June 05, 2006
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    Electrochemical and electronic spectral bahaviors of complexes [Cu(acac)(tmen)]ClO4 and [Cu2(taet)(tmen)2](ClO4)2, where acac=acetylacetonate ion, tmen=N,N,N′,N′-tetramethylethylenediamine, taet=1,1,2,2-tetraacetylethanediide ion, were investigated in six solvents by cyclic voltammetry, constant potential coulometry, and visible absorption spectroscopy. Copper(II) undergoes electrolytic reduction to copper(I) coupled with the complex decomposition. The values of reduction potential vs. \ ildeν max of the d-d absorption band show linear correlation in accordance with coordination ability of the solvent.
  • Toshio Nakamura, Yasuyuki Nakamura, Teruhito Kojima, Kosuke Izutsu
    1990 Volume 63 Issue 9 Pages 2615-2619
    Published: 1990
    Released: June 05, 2006
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    The voltammetric behavior of barium and lithium ions in acetonitrile (AN) was studied at polymer membrane ion-selective electrodes which showed Nernstian responses to those metal ions in AN, in order to elucidate the mechanism of their potentiometric responses. The membrane electrodes consisted of polyacrylamide coupled to such poly(oxyethylene) derivatives as tetraethylene glycol monododecyl ether, dibenzo-18-crown-6, and cryptand222B and coated on platinum or gold disk. The cyclic voltammograms for barium and lithium ions, recorded repeatedly after setting the electrodes at the rest potentials, showed a cathodic peak at −1.5±0.2 V vs. Ag/0.01 M Ag+ (AN). The cathodic peak current (icp) decreased markedly between the first and second scans, but reached a steady value after the third scan. The icp values after the third scan were diffusion controlled and considered to be due to a transfer of the metal ions from the solution into the membrane. The differences in icp between the first and the third scans were proportional to the potential scan rate and attributed to a transfer of the metal ions which had been accumulated at or near the surface of the membrane by combining with the functional groups of the polymer. The accumulation occurred rather slowly and saturated with time. Based on the fact that the response processes of the ion-selective electrodes were very much similar to the accumulation processes, the response mechanism of the ion-selective electrodes is discussed.
  • Kiyohiko Nakajima, Katsuhide Kojima, Masaaki Kojima, Junnosuke Fujita
    1990 Volume 63 Issue 9 Pages 2620-2630
    Published: 1990
    Released: June 05, 2006
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    Oxovanadium(V) complexes, VVO (Schiff base)Y (Y=ClO4, Cl, NO3), with quadridentate Schiff base ligands derived from optically active 1,2-diamines and salicylaldehyde or its derivatives were prepared by oxidizing the corresponding VIVO (Schiff base) with CeIV in acetonitrile followed by the addition of HY. The complexes were characterized by their 1H NMR, IR, UV-Vis, and circular dichroism spectra, and electrochemistry. Reversible reduction potentials (V5+/V4+) obtained by cyclic voltammetry for a series of oxovanadium(V) complexes with Schiff base ligands derived from 5-substituted salicylaldehydes showed a linear dependence on the Hammett parameter. Both the vanadium(IV) and the vanadium(V) complexes catalyze asymmetric oxidation of sulfides into the corresponding sulfoxides with organic hydroperoxides. The oxovanadium(IV) complex catalysts gave much better asymmetric induction than the oxovanadium(V) complex catalysts and in most cases the enantiomeric excess (ee) ranged between 20 and 40%. In the reaction of VIVO (Schiff base) with an organic hydroperoxide the complex is finally converted into the oxovanadium(V) species, and a dark brown intermediate is suggested to be the catalytically active species.
  • Yuzo Tamari, Hideaki Ogawa, Yuji Fukumoto, Haruo Tsuji, Yuzuru Kusaka
    1990 Volume 63 Issue 9 Pages 2631-2638
    Published: 1990
    Released: June 05, 2006
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    The selenium content of 188 samples (115 igneous rocks, 46 sedimentary rocks, and 27 sediments, including 38 rock-forming minerals and 25 rock reference materials) issued from the Geological Survey of Japan were determined. In these samples selenium was distributed over a wide range of concentrations, 0.1–19500 ng g−1. Especially, selenium was rich in alkali-feldspar (7.5–149 ng g−1) as well as in plagioclase (3.6–147 ng g−1), though not in mica (2.4–14.8 ng g−1) and quartz (0.6–6.4 ng g−1). Selenium, rich in feldspar, was easily dissolved as selenite with CO2-bubbling water. In a reservoir sediment-core (from the surface to 15-cm depth), selenite and much organically-complexed selenium were dissolved with 0.1 M hydrochloric acid and the subsequent 1 M sodium hydroxide solutions, respectively.
  • Mutsuo Kodama, Anung Budhi Mahatma, Toru Koike, Eiichi Kimura
    1990 Volume 63 Issue 9 Pages 2639-2645
    Published: 1990
    Released: June 05, 2006
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    Polyaza macrocycles carrying acetate groups, HAHA and PAPA, were found to form solely 1:1 ratio complexes with Eu(III), Gd(III), or Ho(III) ions. The PAPA complexes of the Eu(III), Gd(III), and Ho(III) ions and the HAHA complex of the Eu(III) ion in acetate buffer solutions containing an excess of the Eu(III), Gd(III), or Ho(III) ion produce anodic waves, which are kinetic in nature. They can be ascribed to the free macrocycles formed upon the dissociations of the complexes preceding electron-transfer steps at the electrode surface. From an experimental examination of the nature of these kinetic waves, the reaction mechanisms and rates for the dissociation reactions were determined. The dissociation reactions for the HAHA and PAPA complexes were found to proceed through (A) and (B), respectively. The (kd)o values for the Eu(III)-HAHA and -PAPA complexes were 5.1×10−1 and 3.9×10−2 (sec−1), respectively, and those for the Gd(III)- and Ho(III)-PAPA complexes, 4.04×10−2 and 1.2×10−2 (sec−1).
    (Remark: Graphics omitted.)
    The (kd) values for the Eu(III)-HAHA abd -PAPA complexes were 3.70×102 and 4.24×105 (mol−1dm3s−1) and those for the Gd(III)-and Ho(III)-PAPA complexes, 2.45×104 (mol−1dm3s−1).
  • Takeo Ohsaka, Yoshio Yamaguchi, Noboru Oyama
    1990 Volume 63 Issue 9 Pages 2646-2653
    Published: 1990
    Released: June 05, 2006
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    A new amperometric glucose sensor based on bilayer film coating has been fabricated and its sensor characteristics under a steady-state condition have been examined. The electrode substrate was coated with two kinds of polymer films in a bilayer state, i.e., first with the redox-active montmorillonite clay film into which [Ru(NH3)6]3+ complexes are incorporated electrostatically and they function as an electron shuttle which delivers electrons to redox-active sites in the clay film, and then with the enzyme film consisting of bovine serum albumin and glucose oxidase (GOx). The glucose concentration could be monitored by measuring the current for H2O2 reduction electrocatalyzed by the inner clay film where H2O2 was produced by the glucose–GOx enzyme reaction in the outer enzyme film. The mechanism of the overall electrode/enzyme reaction for this amperometric glucose sensor is represented as follows:
    (Remark: Graphics omitted.)
    where reactions 1,2,3, and 4 correspond to the glucose–glucose oxidase enzyme reaction, the hydrolysis reaction of D-glucono-δ-lactone, the electrocatalytic reduction of H2O2 by the montmorillonite clay containing [Ru(NH3)6]2+ and the electrode reaction of the [Ru(NH3)6]2+⁄3+ couple, respectively. The reproducible relationship between glucose concentration and sensor output was obtained. The sensitivity and the dynamic range were found to depend on the amount of GOx confined in the enzyme film and its thickness.
  • Hisayoshi Shiozaki, Hiroyuki Nakazumi, Yoshikazu Takamura, Teijiro Kit ...
    1990 Volume 63 Issue 9 Pages 2653-2658
    Published: 1990
    Released: June 05, 2006
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    An iterative numerical determination of the rate constants for both quenching of, kq, and reaction with, kr, singlet oxygen by dithiolato nickel complexes is developed. This numerical method gives accurate rate constants for a small number of kinetic runs. The substituent effects of these complexes on rate constants lead us to conclude that the complexes quench singlet oxygen by an energy-transfer mechanism. This numerical method developed for solution systems was applied to the estimation of the photofading rate of a cyanine dye on an epoxy resin plate.
  • Noboru Oyama, Takeo Ohsaka, Osamu Hatozaki, Yuko Kurasawa, Nobushige Y ...
    1990 Volume 63 Issue 9 Pages 2659-2664
    Published: 1990
    Released: June 05, 2006
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    The electrochemical calorimetry of the electrolysis of D2O has been carried out using a Pd cathode in an undivided, open cell fashion, together with measuring the total volume of the evolved gases. The excess heat production, observed using a Pd cathode pretreated by a special procedure, can not be explained as a result of the D2–O2 recombination alone. However, the present data certainly do not confirm “cold fusion”, because no evidence has yet been obtained for neutron, gamma-ray, tritium or helium production during our electrolysis of D2O with Pd cathodes.
  • Kazuya Uejoh, Makoto Shimokozono, Motohiko Koyanagi
    1990 Volume 63 Issue 9 Pages 2665-2671
    Published: 1990
    Released: June 05, 2006
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    Phosphorescence spectra of p-fluorobenzaldehyde have been observed in (i) the vapor phase at room temperature and in (ii) methylcyclohexane and (iii) methyl benzoate matrices at 4.2 K. From the vibrational analysis and deuteration effect it is established that the phosphorescent state is nπ* in cases i and ii while it is ππ* in case iii. A close similarity between the vapor phase emission spectra of p-fluorobenzaldehyde and benzaldehyde leads us to the conclusion that the substitution of the fluorine atom for the para hydrogen atom of benzaldehyde has little effect to the both triplet states. Several experimental data for low frequency vibrations in the excited 3nπ* state will be given by analyzing hot sequence bands of the vapor phosphorescence spectrum.
  • Kazuhiro Maruyama, Fumikazu Kobayashi, Atsuhiro Osuka
    1990 Volume 63 Issue 9 Pages 2672-2681
    Published: 1990
    Released: June 05, 2006
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    Reversible Schiff base condensation of bis(salicylaldehyde)-linked porphyrins and ethylenediamine under high dilution gave salen-capped porphyrins in high yields. Site selective insertion of nickel(II) into the salen and zinc(II) into the porphyrin gave the corresponding Ni–Zn heterobinuclear complexes. The geometrical relationship between the two metal centers was estimated by 1H NMR spectroscopy. The porphyrin π electronic state of these Ni-salen-capped Zn-porphyrins was perturbed by their Ni-salen cap, which was studied by 400 MHz 1H NMR, UV-Vis spectra, fluorescence, and cyclic voltammetry measurements.
  • Mutsuo Goto, Yuji Mikata, Atsuyoshi Ohno
    1990 Volume 63 Issue 9 Pages 2682-2686
    Published: 1990
    Released: June 05, 2006
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    Reduction of 1,4-benzoquinone and its various derivatives with 1-benzyl-1,4-dihydronicotinamide (BNAH) and its 4-deuteriated derivative was studied. The kinetic deuterium primary isotope effect (kHkD) for this reaction appears always larger than the isotopic ratio in the product, BNA+(YHYD; product isotope effect). In the absence of magnesium ion, YHYD increases as the substrate becomes less electron-demanding. In the presence of magnesium ion which accelerates the reaction, YHYD stays small whereas kHkD is not affected. The results reveal that the reaction proceeds with a multi-step mechanism in which the product-determining and rate-determining steps differ each other.
  • Teruaki Mukaiyama, Shigekazu Matsui, Koichi Homma, Sh\={u} Kobayashi
    1990 Volume 63 Issue 9 Pages 2687-2690
    Published: 1990
    Released: June 05, 2006
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    In the presence of a catalytic amount of trityl perchlorate, ethynyl vinyl ketone derivatives regioselectively react with silyl enol ethers to afford the corresponding Michael adducts in high yields. 2-Propynyl ether derivatives also react with silyl enol ethers in the presence of a catalytic amount of trityl perchlorate, to give the corresponding adducts in high yields. In the case of the reaction with 2-propynyl ether derivatives, regioselectivities were apparently different between two silylated nucleophiles, silyl enol ethers of ketones and ketene silyl acetals.
  • Hiroshi Hara, Ei-ichi Ito, Takunori Katou, Yoko Kitamura, Tetsuhito Ko ...
    1990 Volume 63 Issue 9 Pages 2691-2697
    Published: 1990
    Released: June 05, 2006
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    Precipitation chemistry within Japan has been assessed in order to judge both the magnitudes of the concentrations and the deposition of major ions: H+, NH4+, Ca2+, K+, Mg2+, Na+, SO42, NO3, and Cl. A data set was obtained through an acid precipitation survey by Japan Environment Agency at 14 stations from April 1984 to March 1986. The annual average pH at each site ranged from 4.5 to 5.1 with a mean value of 4.7. The free acidity was derived both from sulfuric and nitric acids; sulfuric acid was found to contribute to 67–83% of the free acidity. The acidity was apparently lower than that expected from SO42− and NO3 levels, mainly because alkaline species, such as NH3, and Ca2+ species neutralized a certain fraction of the original acidity. This neutralization would certify the fact that SO42− and NO3 deposition were comparable to, or smaller than those in eastern North America, but the Ca2+ and NH4+ deposition within Japan exceeded that within the U. S.
  • Shoji Harada, Teruhiko Doi, Takayuki Sano, Teruyo Yamashita (Isoda), H ...
    1990 Volume 63 Issue 9 Pages 2698-2700
    Published: 1990
    Released: June 05, 2006
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    The base dissociation of ammonia has been studied by an ultrasonic absorption method in both the absence and presence of SDS micelle in aqueous solution, and kinetic parameters were obtained. The micellar catalyzed reaction mechanism, including the interactions of ammonium ion with SDS micelles, are discussed.
  • Shiro Hatakeyama, Hajime Akimoto
    1990 Volume 63 Issue 9 Pages 2701-2703
    Published: 1990
    Released: June 05, 2006
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    Reactions of ozone with 1-methylcyclohexene and methylenecyclohexane were studied for the purpose of obtaining the reaction mechanism as a prototype of the reaction of ozone with pinenes. The similarity of the yields of corresponding gaseous products between 1-methylcyclohexene and α-pinene and between methylenecyclohexane and β-pinene indicates the similarity of the reaction mechanisms.
  • Koichi Tange, Kazuo Suzuki, Ken-ichi Sasaki, Yasushige Kuroda, Yuzo Yo ...
    1990 Volume 63 Issue 9 Pages 2704-2706
    Published: 1990
    Released: June 05, 2006
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    Spiral growth patterns were found on the crystals of (+)D-and (−)D-[Co(ox)(en)2]Cl·4H2O. The handedness of the spirals was statistically counted on each enantiomeric complex crystal. No stereoselectivity of the handedness suggests that the visible spirals do not arise from the molecular or crystal structural origin, but more macroscopic one.
  • Teiichiro Ogawa, Toshifumi Yoshidome, Hirofumi Kawazumi
    1990 Volume 63 Issue 9 Pages 2707-2709
    Published: 1990
    Released: June 05, 2006
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    The elecron energy-loss spectrum of dimethyl ether was measured at electron energies of 50, 20 and +2(residual energy) eV and at scattering angles of 0–90°. Six new bands were observed at about 6.4, 7.0, 7.5, 7.8, 8.2, 8.9 eV and assigned as the singlet-triplet and/or symmetry-forbidden transition.
  • Masaki Yamada, Yoshio Nakamura, Shigeyasu Kuroda, Ichiro Shimao
    1990 Volume 63 Issue 9 Pages 2710-2712
    Published: 1990
    Released: June 05, 2006
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    Though the chlorination of an N,N′-annelated phenanthrolinedione, 3,6,7,9-tetrahydro-5H-[1,4]diazepino[1,2,3,4-lmn][1,10]phenanthroline-3,9-dione, gave 2,9-dichloro-1,10-phenanthroline, another dione, 3,5,6,8-tetrahydropyrazino[1,2,3,4-lmn][1,10]phenanthroline-3,8-dione, did not. It demonstrated a simultanous introduction of two chlorine substituents to non-substituted 1,10-phenanthroline via only the former intermediate.
  • Kohichiroh Hinokuma, Kenji Sakamaki, Akira Fujishima
    1990 Volume 63 Issue 9 Pages 2713-2715
    Published: 1990
    Released: June 05, 2006
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    A scanning tunneling microscope (STM) under photoelectrochemical control was used to investigate an in situ dynamically light-induced morphological transformation at an n-MoS2 electrode surface in CH3CN by the addition of I ions. The anistropic photocorrosion rate around the “disk-like” cavities was extremely slow due to the effects of the added I ions when compared to the results achieved by adding only H2O.
  • E. Grech, L. Stefaniak, Isao Ando, Hiroaki Yoshimizu, Graham A. Webb, ...
    1990 Volume 63 Issue 9 Pages 2716-2717
    Published: 1990
    Released: June 05, 2006
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    13C and 15N NMR spectra are measured for 1,8-bis(dimethylamino)naphthalene and its complex with tetrazole in both solution and the solid state. On the basis of the solution and solid state 15N results, an equilibrium involving the half protonated form of the base in the solution of the complex salt was identified. On the other hand, it is found that the 13C results for the solutions are closely similar to those found for the solid state, and are rather insensitive to salt formation.
  • Kazumi Fujita, Chizuko Nakamura, Keizo Matsuda, Shunmei Mitsuzawa
    1990 Volume 63 Issue 9 Pages 2718-2720
    Published: 1990
    Released: June 05, 2006
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    The production of tin(II) oxide from tin(II) chloride and urea was found to depend on the concentration of urea. An amorphous compound was produced for a lower concentration of urea, 5SnO·2H2O was produced for a higher concentration of urea, and tin(II) oxide was produced for a middle-range concentration of urea.
  • Shuji Oishi, Minoru Hirao
    1990 Volume 63 Issue 9 Pages 2721-2723
    Published: 1990
    Released: June 05, 2006
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    Calcium tungstate crystals were grown from M2WO4 (M=Li, Na, and K) fluxes. Observations of the obtained CaWO4 crystals showed that a high-temperature solution of Na2WO4 was superior to both Li2WO4 and K2WO4 solutions. It was experimentally confirmed that the Na2WO4 flux chosen on the basis of the guiding principle was the most suitable.
  • Kazuo Ito, Yutaka Tamaura, Takashi Katsura
    1990 Volume 63 Issue 9 Pages 2724-2725
    Published: 1990
    Released: June 05, 2006
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    Stoichiometric Al-bearing ferrites[AlxFe3-xO4 (x=0.05–0.46)] are formed by a transformation reaction from γ-FeOOH in an aqueous suspension. The transformation reaction proceeds in a suspension containing γ-FeOOH, Fe(II) and Al ions without oxidation at 25°C and a pH of 9.5–11.0.
  • Taira Imamura, Akio Furusaki
    1990 Volume 63 Issue 9 Pages 2726-2727
    Published: 1990
    Released: June 05, 2006
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    The molecular structures of the title complexes have been determined by a single-crystal X-ray diffraction method. The crystals of MoO(tpp)NCS·CH2Cl2 (tpp= 5,10,15,20-tetraphenylporphyrinato) and MoO(tpp)F are triclinic and tetragonal respectively. An isothiocyanate ion is coordinated to the central molybdenum atom at an angle of 145° with the Mo–N(NCS) bond through the nitrogen atom. In both complexes, the molybdenum atoms are displaced toward oxo ligands from the 4N plane composed of pyrrole nitrogens.
  • Tatsuo Oshikawa, Mitsuji Yamashita
    1990 Volume 63 Issue 9 Pages 2728-2730
    Published: 1990
    Released: June 05, 2006
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    Optically active (S)-2-aminopropylphosphonic and (S)-2-amino-4-methylpentylphosphonic acids were synthesized from commercially available chiral α-amino acids [(S)-(+)-alanine and (S)-(+)-leucine] without racemization.
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