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| 1.
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土成, 昭弘 ; 保木井, 利之 ; 下林, 修 ; 金岡, 千嘉男
概要:
In a permeable MgO ceramic containing TiO_2 and Al_2O_3 as matrix MgO ・ Al_2O_3-2MgO・TiO_2 solid solutions were detected
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and no Al_2O_3・TiO_2 was observed. Therefore, the solid state reaction among MgO, TiO_2 and Al_2O_3 with excess MgO was studied at various firing temperatures. The formation mechanism of MgO・Al_2O_3-2MgO・TiO_2 solid solutions was studied from the results of interface reactions between MgO-TiO_2 and MgO-Al_2O_3. MgO・Al_2O_3-2MgO・TiO_2 solid solutions were detected at 1573-1673 K and increased with the firing temperature. 2MgO・TiO_2 was formed in the system MgO-TiO_2, but was not produced in the system MgO-TiO_2-Al_2O_3, because the amount of Mg diffusion at the interface of aggregate and matrix additives was not enough due to the large aggregate size of MgO. MgO・Al_2O_3 and 2MgO・TiO_2 formed at the interface between MgO-TiO_2 and MgO-Al_2O_3 decreased with the firing time at 1873 K. On the other hand, MgO・Al_2O_3-2MgO・TiO_2 solid solutions increased. Mg was recognized in the matrix without addition of MgO as a matrix. Al diffused in the layer of MgO-TiO_2, in opposition Ti diffused in the layer of MgO-Al_2O_3 by EPMA analysis. From the above results, the formation mechanism of a MgO・Al_2O_3-2MgO・TiO_2 solid solution was proposed; (1) Mg diffusion at the interface of MgO aggregate and matrix additives, (2) formation of MgO・TiO_2 and MgO・Al_2O_3, (3) formation of 2MgO・TiO_2 due to the reaction with MgO・TiO_2 and MgO, (4) reaction of the solid solution with MgO・Al_2O_3 and 2MgO・TiO_2. In the reactions between MgO・TiO2 and MgO-Al_2O_3 the product layer of MgO・Al_2O_3-2MgO・TiO_2 solid solution increased as the firing time increased. The diffusion coefficient of Mg was about 4.8×10^<-7>(cm^2/s), in a good agreement with that of Mg which was reported.
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| 2.
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Somei, Masanori ; Yamada, Fumio ; Yamazaki, Yoshihisa ; Shinkura, Akiko
概要:
We developed a novel synthesis of 2-aminoindan derivatives, having a 2-methyl-1-propenyl group at the 1-position and oxygen functional groups in the benzene ring, in 8 or 9 steps from vanillin.
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| 3.
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Murata, Yasue ; Kinoshita, Hideki ; Inomata, Katsuhiko
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The syntheses of 3,4-disubstituted 2-tosylpyrroles and 5-tosyl-1,5-dihydro-2H-pyrrol-2-ones were accomplished via 3,4-disubstituted 2-iodo-5-tosylpyrroles starting from ethyl 3,4-disubstituted 2-pyrrolecarboxylates.
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| 4.
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Somei, Masanori ; Hayashi, Hiroyuki ; Ohmoto, Shinobu
概要:
金沢大学大学院自然科学研究科生理活性物質科学<br />金沢大学薬学部<br />Indigo was converted to 2,2′-bisindole by the direct reduction with zinc in ace
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tic acid and acetic anhydride under argon or hydrogen atmosphere. Reduction with tin and iron afforded 3-acetoxy-2,2′-bisindole predominantly. Useful building blocks such as 1-acetyl-2,3-dihydro-, 3-acetoxy-3′-acetyl-, and 3-acetoxy-1,3′-diacetyl-2,2′-bisindoles were also produced depending on metal and reaction conditions.
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| 5.
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Suzuki, Masatatsu ; Sugisawa, Toshiharu ; Uehara, Akira
概要:
Two dinuclear cobalt(II,II) complexes, [Co2(tpdp)(CH3COO)](ClO4)2·0.5H2O (1) and [Co2(tmdp)(CH3COO)](ClO4)2·H2O (2), wer
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e prepared, where Htpdp and Htmdp are 1,3-bis[bis(2-pyridylmethyl)amino]-2-propanol and 1,5-bis[bis(2-pyridylmethyl)amino]-3-pentanol respectively. Their electronic spectral and magnetic data revealed that 1 and 2 are five-coordinate in the high-spin state, in the same manner as [Co2(bpmp)(CH3COO)]2+ (3) (Hbpmp=2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenol). The complexes reacted with molecular oxygen to form μ-peroxo complexes in dichloromethane and acetonitrile. The oxygen affinity of the complexes decreased in the order of 3>2>1. The relationships between the oxygen affinities and (1) the donor abilities of dinucleating ligands, (2) the energies of the charge-transfer bands (O22− to Co3+) of the μ-peroxo complexes, and (3) the redox potentials of the Co3+–O2−–Co3+/Co3+–O22−–Co3+ couple indicated that a steric effect arising from the dinucleating ligands contributes significantly to the oxygen affinities of the complexes.
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| 6.
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Ikeda, Masazumi ; Ohtani, Shinji ; Okada, Michiyo ; Minakuchi, Emi ; Sato, Tatsunori ; Ishibashi, Hiroyuki
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| 7.
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Somei, Masanori ; Kodama, Atsushi
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金沢大学大学院自然科学研究科生理活性物質科学<br />金沢大学薬学部
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| 8.
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Tsutiya, Ryokichi
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| 9.
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Tsutiya, Ryokichi
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| 10.
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Sumiyoshi, T. ; Kido, H. ; Sakamoto, H. ; Urasaki, K. ; Suzuki, K. ; Yamaguchi, N. ; Mori, Hirofumi ; Shiba, Kazuhiro ; Yokogawa, K. ; 柴, 和弘
概要:
金沢大学疾患モデル総合研究センター<br />An in vivo receptor binding technique was applied to evaluate the affinities of risperidone and h
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aloperidol for dopamine-D2 receptors (D2) and serotonin-5-HT2 receptors (5-HT2) in rat brain with [3H]YM-09151-2 and [3H]ketanserin as selective ligands. Radioactivities were obtained in the striatum, frontal cortex, and cerebellum of the rats treated with the ligands. Time course study of receptor occupancy at 25 to 250 min after single doses of the drugs (1 mg/kg, IP) showed higher 5-HT2 occupancy in the frontal cortex and lower D2 occupancy in the striatum by risperidone than by haloperidol. Dose-response analysis of receptor occupancy revealed risperidone demonstrated higher binding affinity for 5-HT2 than for D2, while the reverse was observed with haloperidol. It appeared that risperidone (1 mg/kg, IP), but not haloperidol (1 mg/kg, IP), demonstrated regional selectivity in D2 occupancy favouring frontal cortex more than the striatum. That risperidone displayed a higher ratio of 5-HT2 to D2 in occupancy than haloperidol is in agreement with the previous findings obtained in vitro. © 1994.
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| 11.
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Sugimoto, Hideki ; Nagayama, Toshihiko ; Maruyama, Sachihito ; Fujinami, Shuhei ; Yasuda, Yuichi ; Suzuki, Masatatsu ; Uehara, Akira
概要:
A new dinucleating ligand containing a sterically bulky imidazolyl group, Ph-Htidp (N,N,N′,N′-tetrakis[(1-methyl-4,5-dip
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henyl-2-imidazolyl)methyl]-1,3-diamino-2-propanol), and its μ-alkoxo-diiron(II) complexes [Fe2(Ph-tidp)(RCO2)](ClO4)2, (RCO2 = C6H5CO2 (1), C6F5CO2 (2), CF3CO2 (3), and C2H5CO2 (4)), were synthesized. The structure of complex 1 was determined by X-ray crystallography. Complex 1 crystallizes in the monoclinic space group P21/c with a = 13.464(2), b = 19.223(4), c = 31.358(4) Å, β = 92.84(2)°, and Z = 4. The complex has a doubly-bridged structure with μ-alkoxo of Ph-tidp and μ-benzoate; the two iron centers have a distorted five-coordinate structure with N3O2 donor set. All the complexes showed fairly good reversible oxygenation below −30 °C in CH2Cl2, which was monitored by UV-vis and NMR spectroscopies, and dioxygen up-take measurements. Introduction of 4,5-diphenyl substituents into 2-imidazolyl group stabilized the μ-peroxo diiron species against irreversible oxidation, just as introduction of 6-methyl substituent into 2-pyridyl group did. Phenyl substituents appear to weaken the electron donor ability of a dinucleating ligand to stabilize divalent oxidation state of iron and to form a hydrophobic cavity for a O2 binding site, which would suppress the irreversible oxidation and facilitate the reversible oxygenation. Dioxygen affinities of the Ph-tidp and Me4-tpdp diiron(II), and the tpdp and bpmp dicobalt(II) complexes were measured, [Fe2(Me4-tpdp)(RCO2)]2+ (RCO2 = C6H5CO2 and RCO2 = CF3CO2) and [Co2(L)(RCO2)]2+ (L = tpdp, RCO2 = CH3CO2, and L = bpmp, RCO2 = C6F5CO2, and CF3CO2), where Me4-tpdp, tpdp, and bpmp are N,N,N′,N′-tetrakis[(6-methyl-2-pyridyl)methyl]-1,3-diamino-2-propanolate, N,N,N′,N′-tetrakis(2-pyridylmethyl)-1,3-diamino-2-propanolate, and 2,6-bis[bis(2-pyridylmethyl)aminomethyl]-4-methylphenolate, respectively. Within a series of the Ph-tidp diiron(II) complexes, dioxygen affinity is well correlated with electron donor ability of bridging carboxylates (1 (C6H5CO2) > 2 (C6F5CO2) > 3 (CF3CO2)). In contrast to the above trend, dioxygen affinities of the Ph-tidp complexes are lower than those of the Me4-tpdp complexes, although electron donor abilities of the Me4-tpdp complexes are weaker than those of the Ph-tidp complexes. Significant enhancement of dioxygen affinity was observed for both iron and cobalt complexes with 2,6-bis(aminomethyl)phenolate bridging skeleton compared to the complexes with a 1,3-diamino-2-propanolate bridging one. Thermodynamic study suggested that the observed enhancement is mainly attributable to a favorable entropy effect along with a steric effect.
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| 12.
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Ihara, Yoshinori ; Satake, Yasuhiro ; Fujimoto, Yumi ; Senda, Hitoshi ; Suzuki, Masatatsu ; Uehara, Akira
概要:
The structures of two diaquabis(N,N-dialkylethylenediamine)nickel(II) chlorides ([Ni(H2O)2(diamine)2]Cl2·nH2O) were dete
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rmined by X-ray crystallographic studies, where diamine is N,N-dimethylethylenediamine(NN-dmen) or N,N-diethylethylenediamine (NN-deen). Both complexes are trans and crystallize in the monoclinic space group P21⁄n. The unit cell parameters of the NN-dmen complex, NiCl2C8N4O2H32, are a=7.531(1), b=13.092(1), c=9.591 Å, β=107.76(1)°, and Z=2, and those of the NN-deen complex, NiCl2C12N4O2H36, are a=9.154(1), b=8.692(1), c=12.395(2) Å, β=104.46(1)°, and Z=2. In trans-[Ni(H2O)2(NN-dmen)2]Cl2·2H2O and trans-[Ni(H2O)2(NN-deen)2]Cl2, the Ni–NMe2 and Ni–NEt2 bond distances (2.183 and 2.271 Å) are much longer than the Ni–NH2 distances (2.078 and 2.064 Å), forming tetragonally distorted octahedrons with four close in-plane neighbors(N2O2) and two remote axial ones(N2). It is apparent that this distortion originates from the steric requirement of N-substituted groups. Such a distortion significantly affects the electronic spectra of these complexes.
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| 13.
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Iwasa, Junko ; Miyoshi, Ken-ichi
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| 14.
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Ihara, Yoshinori ; Tsuchiya, Ryokichi
概要:
The following ten nickel(II) complexes with meso- or dl-1,2-diphenyl-1,2-ethanediamine (abbreviated as meso-stien and dl-stien, respectively) were prepared, and their thermal behavior was investigated in the
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solid phase: [Ni(meso-stien)2]X2 (X=Cl, Br, I, NO3, or ClO4), [Ni(dl-stien)2]X2 (X=I or ClO4), and [Ni(H2O)2(dl-stien)2]X2 (X=Cl, Br, or NO3). The square planar bis(dl-stien) complex chloride, bromide, and nitrate obtained by thermal dehydration of their respective octahedral diaqua complexes were found by various techniques to be transformed, upon further heating, to the octahedral diacido bis(dl-stien) complexes. The complexes containing dl-stien have a stronger tendency to show such structural transformations than those containing meso-stien. The reason for this difference is discussed.
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| 15.
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Murahashi, Tsuyoshi ; Kizu, Ryoichi ; Kakimoto, Hitoshi ; Toriba, Akira ; Hayakawa, Kazuichi
概要:
Diesel-engine exhaust and airborne particulates were collected in downtown and suburban areas and five mutagenic nitroarenes (2-nitrofluoranthene (NF), 1-, 2- and 4-nitropyrenes (NPs) and 6-nitrochrysene (NC) in benzene-ethanol extracts
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were determined by high-performance liquid chromatography with chemiluminescence detection. 1- and 4-NPs and 6-NC were found in diesel-engine exhaust particulates, however, 2-NF and 2-NP were not detected. On the other hand, all five nitroarenes were found in airborne particulates. Diurnal concentration patterns of 4-NP and 6-NC in the downtown area were similar to the pattern of 1-NP, but the patterns of 2-NF and 2-NP were different from the pattern of 1-NP. These results strongly suggested that 2-NF and 2-NP are formed in the atmosphere. Of the five nitroarenes, 2-NF had the largest suburban / downtown concentration ratio. 2- and 4-NPs and 6-NC all showed larger ratios than did 1-NP. These results showed that 2-NF and 2-NP were formed in the atmosphere, but that the secondary formation of 4-NP and 6-NC were not known. Taking mutagenic activity and the atmospheric concentration into consideration, the mutagenic contribution of 2-NF was estimated to be comparable with that of 1-NP in the downtown area, and more than that of 1-NP in the suburban area. This result suggested that the mutagenic contribution of the minor nitroarenes formed in urban air might not be negligible.
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| 16.
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Yoshimura, Osamu ; Ueda, Kazumasa ; Yamamoto, Yoshikazu
概要:
2-(2-Thiazolylazo)-4-methoxyphenol (TAMP) forms a brownish 2:1 complex with iron(ll) in the presence of ascorbic acid; t
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he complex has a characteristic absorption at 784 nm in chloroform. By utilizing this peculiar absorption, selective spectrophotometry determination of iron has been developed. The optimum pH for iron extraction lies between 5.0-9.3 and Beer's law holds up to 5.0 ng/ml of iron. Many type of ions are tolerable. The method was successfully applied to the determination of iron in river waters. The extraction constant of iron(ll) complex was log Kex=-2.50±0.12 and the extraction mechanism was kinetically investigated. The complexation rate was first-order with respect to iron(ll) and TAMP concentrations and independent of ascorbic acid concentration. From these results, the major extraction rate-determining step was concluded to be a 1:1 complexation reaction between iron(ll) and dissociated TAMP. Kinetic data and activation parameters for the first-order reaction were determined and discussed. © 1988, The Japan Society for Analytical Chemistry. All rights reserved.
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| 17.
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Kawashima, Hiroshi
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| 18.
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Sakurai, Ikuo ; Suzuki, Harumi ; Shimizu, Sakae ; Yamamoto, Yuzuru
概要:
It was found that Macrophoma commelinae (IFO 9570) had an ability to transform 5-acetyl-4-methoxy-6-methyl-2-pyrone (1) to 4-acetyl-3-methoxy-5-methylbenzoic acid (2). This biotransformation was investigated using 13C- and 14C-labeled
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compounds. It is likely that 2 is formed by condensation of the added 2-pyrone and a catabolic pyruvate.
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| 19.
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谷野, 淳
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| 20.
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Kodama, Akio
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| 21.
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Matsumoto, Takeo ; Banno, Shohei
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| 22.
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| 23.
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Senda, Kantaro
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| 24.
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Suzuki, Masatatsu ; Uehara, Akira
概要:
Reaction of copper(II) ion with hexacyanoferrate(II) ion, [Fe(CN)6]4−, in an aqueous solution containing such an amine a
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s en (1,2-ethanediamine), tn (1,3-propanediamine), dien (bis(2-aminoethyl)amine), or dpt (bis(3-aminopropyl)amine), gave two types of complexes: Double complex salts, [Cu(en or tn)2]2[Fe(CN)6]·nH2O(n=5–8), and cyanide-bridged complexes, [(Cu(dien or dpt))2(NC)2Fe(CN)4]·4H2O. The infrared spectra of the complexes in the νCN region revealed that the complexes, [(Cu(dien or dpt))2(NC)2Fe(CN)4]·4H2O, contain cyanide bridges, while in [Cu(en or tn)2]2[Fe(CN)6]·nH2O, no cyanide bridge is present. The thermal reactions of the complexes in the solid state were investigated by means of derivatography under dynamic conditions (D conditions). It was found that dehydration from [Cu(en)2Fe(CN)6]·nH2O resulted in formation of cyanide bridge in the apical position of square planer [Cu(en)2]2+. For [(Cu(dien or dpt))2(NC)2Fe(CN)4]·4H2O, dehydration resulted in the formation of additional cyanide bridges. All the complexes showed metal to metal (iron(II) to copper(II)) charge-transfer transitions (MMCT) in the near ultraviolet or visible region. The complexes, [Cu(en or tn)2]2[Fe(CN)6]·nH2O, exhibited the outer sphere iron(II) to copper(II) charge-transfer bands (OSMMCT) in the near ultra-violet region. [(Cu(dien or dpt))2(NC)2Fe(CN)4]·4H2O and the dehydrated complexes prepared by thermal reaction showed the inner-sphere iron(II) to copper(II) charge transfer bands (ISMMCT) in the visible region. A good correlation was observed between the energies of the MMCT and the d-d band maxima of copper(II) ions.
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| 25.
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Ngwe, Hla ; Kinoshita, Hideki ; Inomata, Katsuhiko
概要:
Diethyl 3,4-disubstituted 1,5-dihydro-5-oxo-2H-pyrrol-2-ylphosphonates were regioselectively prepared by acidic hydrolysis of diethyl 3,4-disubstituted 5-bromo-2-pyrrolylphosphonates. The resulting 1,5-dihydro-2H-pyrrol-2-ones
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readily underwent the coupling reaction with various aldehydes to afford the corresponding 1,5-dihydro-5-methylene-2H-pyrrol-2-ones including pyrromethenone derivatives in good yields. A series of these reactions was successfully applied to the synthesis of C/D-rings component of phycocyanobilin.
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| 26.
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Ihara, Yoshinori ; Sakino, Tomomi ; Ishikawa, Mieko ; Koyata, Takanori
概要:
The solid-phase thermal reactions of trans-diaquabis(diamine)nickel(II) complexes (trans-[Ni(diamine)2(H2O)2]X2) were in
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vestigated by means of TG/DTA and DSC, and high-temperature electronic spectrometry, where the diamine is an optically active diamine such as (1S,2S)-1,2-diphenyl-1,2-ethanediamine or (S)-4-methyl-1,2-pentanediamine, and X is Cl−, Br−, or NO3−. Several complexes were peculiarly transformed into cis-[NiX2(diamine)2] upon thermal deaquation-anation, and then isomerized to trans-[NiX2(diamine)2] upon further heating. The results were in contrast to the reactions of the complexes with the corresponding racemic diamines which underwent a simple deaquation-anation, retaining an original trans configuration. The differences must come from a slight difference in the conformation of diamine ligands between trans-[Ni(R-diamine)(S-diamine)(H2O)2]X2 which is obtained for the rac-diamines and trans-[Ni(R- or S-diamine)2(H2O)2]X2 which is obtained for the optically active diamines.
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| 27.
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Sumiyoshi, T. ; Kido, H. ; Sakamoto, H. ; Urasaki, K. ; Suzuki, K. ; Yamaguchi, N. ; Mori, Hirofumi ; Shiba, Kazuhiro ; 森, 厚文 ; 柴, 和弘
概要:
金沢大学疾患モデル総合研究センター<br />An in vivo receptor binding technique was applied to evaluate the affinities of clozapine (20 mg/
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kg), RMI-81582 (20 mg/kg), and haloperidol (1 mg/kg) for dopamine D1, D2 and serotonin 5-HT2 receptors in rat brain with [3H]-SCH23390, [3H]-YM-09151-2, and [3H]-ketanserin as selective ligands. The time course study of receptor occupancy at 25 to 250 min after intraperitoneal administration of the drugs showed higher 5-HT2 and lower D2 receptor occupancies of clozapine and RMI-81582 than those of haloperidol both in the striatum and frontal cortex. The 5-HT2/D2 ratios of receptor occupancy for clozapine and RMI-81582 were about 6 to 8 times higher than that for haloperidol. Stable occupancies of D1 receptors were observed only with RMI-81582 and clozapine, the former demonstrating the higher occupancy. These findings are in agreement with the previous findings obtained under in vitro conditions and may account for some part of the properties of atypical antipsychotic drugs. © 1994.
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| 28.
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Watanabe, Chikara
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| 29.
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Ihara, Yoshinori ; Wada, Akiko ; Fukuda, Yutaka ; Sone, Kozo
概要:
Nickel(II) complexes of 1,2-butanediamine(1,2-bn) and 3,3-dimethyl-1,2-butanediamine(dmbn), were prepared, and their the
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rmal behavior was investigated in solid phase. The original complexes were all violet, octahedral diaquabis(diamine) complexes([Ni(H2O)2(1,2-bn/dmbn)2]X2; X=Cl, Br, NO3, or ClO4). The 1,2-bn complexes with Cl− or Br− and the dmbn complex with NO3− showed a two-step thermochromism, violet→yellow→violet blue, upon heating. These steps correspond to structural changes to a square planar anhydride, and then to an octahedral dianiono complex. The complexes of both ligands with ClO4− underwent only thermal deaquation, changing into orange square planar anhydride. Other salts, the 1,2-bn complex with NO3− and the dmbn complexes with Cl− or Br−, were converted into octahedral dianiono complexes by thermal deaquation-anation which occurs in one step. The differences among the thermal reactivities of the complexes with different diamines can be understood on the basis of steric hindrance caused by the substituent groups on the diamine.
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| 30.
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Sakurai, Ikuo ; Shimizu, Sakae ; Yamamoto, Yuzuru
概要:
Three new metabolites, named macommelinal, macrophin and macrophic acid, were isolated from the culture broth of Macrophoma commelinae IFO 9570. Their structures were determined to be
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2-(4-methoxy-6-methyl-2-oxo-2H-pyran-5-yl)ethanal, 3-methyl-2-butenoic acid (E)-[5-hydroxymethyl-4-methoxy-6-(2-methoxycarbonylethenyl)-2-oxo-2H-pyran-3-ly]methyl ester and 3-(4-methoxy-3,5-dimethyl-2-oxo-2H-pyran-6-yl)-2-propenoic acid, respectively. 4 Acetyl-3-methoxy-5-methylbenzoic acid, now named macrophomic acid, was also isolated from a large-scale culture.The biosynthesis of the macommelin group, novel 5-substituted 2-pyrone metabolites, has been investigated by feeding experiments with [1-^<13>C]-, [1,2-^<13>C_2]- and [1-^<13>C, 2-^2H_3]acetate and [2-^<13>C]malonate. It was concluded that all these metabolites originated from a single straight tetraketide chain. Furthermore, the biogenetic mutual relationships of these metabolites including potential intermediates were estabished through incorporation experiments with ^<14>C-labeled compounds.
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| 31.
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Kayatani, Takayuki ; Hayashi, Yoshihito ; Suzuki, Masatatsu ; Inomata, Katsuhiko ; Uehara, Akira
概要:
A dicopper(II) complex with a novel unsymmetric dinucleating ligand, H2L-1, which can provide donor atom, coordination n
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umber, and geometric asymmetries at metal centers, [Cu2(L-1)(CH3COO)]ClO4·H2O·0.5NaClO4 (1), was synthesized, where H2L-1 is a racemic 1-bis(2-pyridylmethyl)amino-3-salicylideneaminopropan-2-ol. The ligand is a hybrid one of 1,3-bis[bis(2-pyridylmethyl)amino]propan-2-ol (Htpdp) and 1,3-bis(salicylideneamino)propan-2-ol (H3L-2). Crystal structure of 1 was determined by X-ray crystallography. Complex 1 crystallizes in monoclinic space group C2/c with a = 42.704(8), b = 12.689(6), c = 29.008(9) Å, β = 128.28(1)°, and Z = 16. The crystal structure showed that two stereoisomers (1a and 1b) are present in solid state. This is attributable to the presence of an enantiomeric pair of L-1. Dinuclear cations consist of one square-planar site with a NO3 donor set and one five-coordinate site with a N3O2 donor set, which are linked by an endogenous alkoxide bridge of L-1 and an exogenous acetate bridge. A powdered sample of 1 shows weak antiferromagnetic interaction (2.60 B.M./Cu2 at 300 and 1.81 B.M./Cu2 at 5 K). Cryomagnetic data is analyzed using two exchange coupling constants, J1 = −0.18 cm−1 and J2 = −9.05 cm−1. EHMO calculations revealed that the observed weak antiferromagnetic interaction(s) compared with that found for [Cu2(L-2)(CH3COO)] (3) (J = −85 cm−1) is reasonably interpreted in terms of the energy gap and the nature of HOMO and LUMO. Some other physicochemical properties of the complex are discussed in comparison with those of the parent complexes, [Cu2(tpdp)(CH3COO)]2+ (2) and [Cu2(L-2)(CH3COO)] (3).
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| 32.
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Fujii, Tozo ; Ohba, Masashi
概要:
8-Hydroxyprotoemetine [(-)-2f], an aldehyde of biogenetic interest, has been synthesized for the first time from the tri
…
cyclic ester (-)-5 through the intermediate (-)-6. Wolff-Kishner reduction of (-)-2f produced the 2-ethyl congener (-)-2g. As a result of these syntheses, the circular dichroism (CD) spectra of (-)-2f・HClO_4 and (-)-2g in 0.1 N aqueous HCl and in EtOH, together with those of the Alangium alkaloids ankorine (2d) and alancine (2e), are now availale.
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| 33.
論文 |
論文
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Ishibashi, Hiroyuki ; Higuchi, Masahiro ; Masuko, Hiromi ; Kodama, Kazuya ; Ikeda, Masazumi
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| 34.
論文 |
論文
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Somei, Masanori ; Kobayashi, Tetsuya
概要:
金沢大学大学院自然科学研究科生理活性物質科学<br />金沢大学薬学部
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| 35.
論文 |
論文
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Hishiki, Masanobu ; Suzuki, Masatatsu ; Uehara, Akira
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| 36.
論文 |
論文
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Nagata, Isamu
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| 37.
論文 |
論文
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Saaler, Sven
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| 38.
論文 |
論文
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Suhara, Masahiko ; Murata, Shigeo
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| 39.
論文 |
論文
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Kudo, K ; Hori, S
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| 40.
論文 |
論文
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Nakatani, T ; Nishibata, K
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| 41.
論文 |
論文
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Senda, Kantaroo
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| 42.
論文 |
論文
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Somei, Masanori ; Hayashi, Hiroyuki ; Izumi, Tohru ; Ohmoto, Shinobu
概要:
金沢大学大学院自然科学研究科生理活性物質科学<br />金沢大学薬学部
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| 43.
論文 |
論文
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| 44.
論文 |
論文
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加野, 軒作 ; 植竹, 厚子 ; 清水, 栄 ; 新田, 啓一 ; 山本, 譲
概要:
Metabolism of 6-methyl-2-thiouracil was studied in rats by using ^<14>C-labeled compound. Following the oral administration of 6-methyl-2-thiouracil [2-^<14>C] (490 mg/kg), the about 68% of the administered radioactivity was excreted in
…
urine, 27% in feces, and 1.2% in respiratory CO_2 within 72 hr. After oral ingestion of the radioactive compound, radioactive substances excreted in urine after 48 hr were 6-methyl-2-thiouracil, 6-methyl-uracil, 6-methyl-2-methylthiouracil, 6-methyl-4-oxo-pyrimidine, 2-amino-6-methyl-4-oxopyrimidine, and urea which were present in about 46.2,9.1,1.6,1.8,0.2,and 0.8% of total radioactivity in the urine, respectively. In in vitro tests using rat liver slices, radioactivity was also detected in 5,6-dihydro-6-methyluracil along with the above metabolites.
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| 45.
論文 |
論文
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Ialnazov, Dimiter
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| 46.
論文 |
論文
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Kobayashi, Nobuo ; Kumeda, Minoru ; Shimizu, Tatsuo
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| 47.
論文 |
論文
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桑原, 義晴
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| 48.
論文 |
論文
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倉田, 悟
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| 49.
論文 |
論文
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Nozu, Yoshitomo ; 野津, 良知
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| 50.
論文 |
論文
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Ito, Koji ; 伊藤, 浩司
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| 51.
論文 |
論文
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Ihara, Yoshinori
概要:
Nickel(II) complexes [Ni(phenen)2](ClO4)2 and [Ni(H2O)2(phenen)2]X2 (phenen=1-phenyl-1,2-ethanediamine, X=Cl, Br, or NO3
…
) were prepared, and their thermal behavior was investigated in the solid phase. The nitrate showed a thermochromism consisting of two steps, violet→yellow→violet, which corresponds to a structural change from an octahedral diaqua complex to a square planar anhydride, and then to the octahedral dinitrato complex, respectively. Both the chloride and bromide were converted into the octahedral dianiono complexes by thermal deaquation-anation, retaining their octahedral configuration. However, no change was observed in the perchlorate, which is invariably square planar.
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| 52.
論文 |
論文
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Fujii, Tozo ; Yoshifuji, Shigeyuki ; Ohba, Masashi
概要:
A highly stereoselective, efficient synthetic route to ethyl trans-5-ethyl-2-oxo-4-piperidineacetate (11a) from 1-benzyl-2,4-dioxo-5-ethylpiperidine (2) is described. The steps involved are
…
conversion of 2 into 1-benzyl-5-ethyl-2-oxo-1,2,5,6-tetrahydropyridine (6) through the lactam alcohol (5), the Michael condensation of 6 with diethyl malonate followed by alkaline hydrolysis, decarboxylation of the resulting trans-lactam dicarboxylic acid (8a) to the trans-lactam acid (9a), and debenzylation of 9a followed by esterification.
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| 53.
論文 |
論文
|
Hayashi, Hiroyuki ; Ohmoto, Shinobu ; Somei, Masanori
概要:
金沢大学大学院自然科学研究科生理活性物質科学<br />The first simple total syntheses of 6-cyano-5-methoxy- (1a) and -12-methylindolo[2,3-a]carba
…
zolc (1b) are attained from indigo (2) in only five and six steps, respectively. Preparations of 5-hydroxy- (13), 5-bromoindolo[2,3-a]carbazole (14), and a novel spiro compound (7) are also included.
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| 54.
論文 |
論文
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Kaneko, Chikara ; Fujii, Harue ; Kawai, Shinji ; Hashiba, Kazuhiko ; Karasawa, Yoshio ; Wakai, Masue ; Hayashi, Reiko ; Somei, Masanori
概要:
Irradiation (≥300 nm) of methyl 2-phenyl-3, 1-benzoxazepine-5-carboxylate in an alcohol afforded the Z-isomer of methyl
…
3-alkoxy-2-(2-benzamidophenyl)-acrylate as the major addition product. In contrast, thermal reaction of the oxazepine with a primary alcohol in the presence of triethylamine led to the exclusive formation of the corresponding E-isomer. The same kinds of Michael addition products were also obtained stereoselectively from 3, 1-benzoxazepines having an acetyl group at the 5-position under these conditions. The interrelation between the stereoisomers obtained from the oxazepine and an alcohol under these two conditions was established by photochemical equilibration, and the stereochemistry of the two isomers was determined by proton magnetic resonance spectroscopy. An explanation is proposed for the observed stereoselectivities in the two kinds (photochemical and thermal) of reactions.
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| 55.
論文 |
論文
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Kaneko, Chikara ; Naito, Toshihiko ; Hashiba, Marimi ; Fujii, Harue ; Somei, Masanori
概要:
Two alkaloids, 1-methyl-4-(3-methylbut-2-enyloxy)-2-quinolone (revenine : IIc) and 4-methoxy-1-methyl-2-quinolone (IIa), were synthesized by means of a photochemical rearrangement reaction of the corresponding
…
4-alkoxy-2-methylquinoline 1-oxide (Ic and Ia), which were conveniently prepared from 4-chloro-2-methylquinoline 1-oxide (XVII), which in turn is readily obtainable from 2-methylquinoline 1-oxide via the 4-nitrated compound (XVIII). The mechanism of the photo-rearrangement reaction of 4-alkoxy-2-methylquinoline 1-oxides (Ia-d) in methanol is discussed.
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| 56.
論文 |
論文
|
金沢大学考古学研究会
概要:
能美丘陵周辺遺跡分布図
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| 57.
論文 |
論文
|
Kinoshita, Hideki ; Tanaka, Shingo ; Nishimori, Natsu ; Dejima, Hiroshi ; Inomata, Katsuhiko
概要:
2-Hydroxymethyl-1-methylsulfonyl-3,4-disubstituted pyrroles and 2-hydroxymethyl-3,4-disubstituted pyrroles were effectively converted into the corresponding 2-(substituted methyl)pyrrole derivatives by the reaction with
…
various nucleophiles in the presence of base. These products were further transformed to the corresponding porphyrins regioselectively under almost neutral or basic conditions.
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| 58.
論文 |
論文
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Hayashi, Hiroyuki ; Suzuki, Yoshiaki ; Somei, Masanori
概要:
金沢大学大学院自然科学研究科生理活性物質科学<br />金沢大学薬学部<br />Starting from indigo, simple synthetic methods for 6-cyano-5-methoxy- 12-methyl
…
indolo[2,3-a]carbazole and novel 6-aminoindolo[2,3-a]thiazolo-[5,4- c]carbazoles are achieved using only conventional reagents.
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| 59.
論文 |
論文
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Ihara, Yoshinori ; Satake, Yasuhiro ; Suzuki, Masatatsu ; Uehara, Akira
概要:
The thermochemical changes in coordination structure of diaquabis(N,N- or N,N′,-dialkylethylenediamine)nickel(II) comple
…
xes ([Ni(H2O)2(diamine)2]X2·nH2O) were reinvestigated by means of TG-DTA and electronic spectroscopy at room and elevated temperatures, where diamine is N,N (or N,N′-dimethylethylenediamine (NN- or NN′-dmen) or N,N-(or N,N′)-diethylethylenediamine (NN- or NN′-deen); X is Cl−, Br−, I−, or NO3−; n is 0, 1, 2, or 3. The diaqua complexes prepared were all trans except for cis-[Ni(H2O)2(NN-dmen)2]I2. The trans complexes with the symmetric (N,N′-dialkylsubstituted) diamines brought about a deaquation-anation upon heating, retaining the original trans configuration, while those with the asymmetric (N,N-dialkylsubstituted) diamines transformed into the cis complexes. In the case of the NN-dmen complexes, cis-halogenoaqua species were isolated as a stable intermediate during the thermal reactions. The complex nitrates changed to trans-dinitrato or cis-mononitrato species depending upon the diamines. The effects of the N-substituents in the diamines and of the anions on the patterns of thermal reactions were also discussed.
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| 60.
論文 |
論文
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宮下, 英明
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| 61.
論文 |
論文
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Fujii, Tozo ; Ohba, Masashi ; Yoshifuji, Shigeyuki ; Akiyama, Shigeaki
概要:
In order to investigate the effect of an N-substituent on thermal cis-trans isomerization of the 5-ethyl-2-oxo-4-piperid
…
ineacetic acid system, the N-alkyl analogs (±)-1b, c and (±)-2b, c and the N-(2-arylethyl) analogs (-)-1f, g, i and (+)-2f, g, i were separately heated neat at 180℃, and the propress of their cis-trans isomerization reactions was followed by determining the isomer ratios in the reaction mixtures according to the previously reported C-13 nuclear magnetic resonance spectroscopic method. It has been found that in all cases the reaction comes to equilibrium within 28-130 min, when the cis and trans isomers exist in a ration of 1 : 2. These results together with those obtained previously with the analogs (±)-1a, d, e, (-)-1h, (±)-2a, d, e, and (+)-2h indicate that a higher and/or bulkier N-substituent tends to decrease the rate of cis-trans isomerization of the 5-ethyl-2-oxo-4-piperidineacetic acid system, which is a useful synthon for the synthesis of benzo-[a] quinolizidine-type Alangium alkaloids. Among the substrates used in the present equilibration study, (±)-1b, c and (±)-2b, c were prepared from the corresponding N-unsubstituted lactam esters (±)-3 and (±)-7 by the"lactim ether method."
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| 62.
論文 |
論文
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上野, 英雄
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| 63.
論文 |
論文
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Hirata, Megumu
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| 64.
論文 |
論文
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海野, 八尋
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| 65.
論文 |
論文
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Sarre, Friedrich
|
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| 66.
論文 |
論文
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水上, 哲次 ; 本多, 幸三郎
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| 67.
論文 |
論文
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北陸の植物の会
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| 68.
論文 |
論文
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今堀, 宏三 ; 瀬嵐, 哲夫 ; IMAHORI, K. ; SEARASI, T.
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| 69.
論文 |
論文
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蟹本, 信雄 ; KANIMOTO, N.
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| 70.
論文 |
論文
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Takahashi, Kohshin ; Terashima, Tetsuo ; Komura, Teruhisa ; Imanaga, Hiroto
概要:
The fluorescence of parent porphyrins in ZnPC2bpy+(n), (PC2bpy+(n), 5-[n-[2-[4-(4-pyridyl)pyridinio]ethoxyl]phenyl]-10,1
…
5,20-triphenylporphyrin bromide, n=2,3, and 4), and ZnPC8bpy+(3), (PC8bpy+(3), 5-[3-[8-[4-(4-pyridyl) pyridinio]octyloxy]phenyl]-10,15,20-triphenylporphyrin bromide), was effectively quenched in non-coordinating solvents, such as o-dichlorobenzene and dichloromethane, because the pyridyl group in bpy+ (ω-[4-(4-pyridyl)pyridinio]alkyl group) was coordinated to zinc in porphyrin. On the other hand, the fluorescence of parent porphyrins in ZnPC2bpy+(3), ZnPC2bpy+(4), and ZnPC8bpy+ (3) was partly quenched in such coordinating solvents as N,N-dimethylformamide and pyridine. However, only the fluorescence of the parent porphyrin in ZnPC2bpy+(2) was effectively quenched, even in coordinating solvents. The hydrophobic interaction between the porphyrin ring and bpy+ in ZnPC2bpy+(2) may be considerably large, for bpy+ in ZnPC2bpy+(2) is covalently linked to the ortho position of the phenyl group in ZnTPP, (TPP 5,10,15,20-tetraphenylporphyrin), by a short chain. The emission was effectively quenched by the photoinduced electron transfer from the porphyrin ring to bpy+, because the axial coordination or the hydrophobic interaction gave bpy+ access to the porphyrin ring.
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| 71.
論文 |
論文
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Somei, Masanori ; Ohnishi, Hiroyuki
概要:
The first synthesis of (±)-paniculidine B is achieved from 2-nitrotoluene in seven steps with an overall yield of 16%.
|
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| 72.
論文 |
論文
|
Kasahara, Yoshihito ; Miyawaki, Toshio ; Kato, Kimitaka ; Kanegane, Hirokazu ; Yachie, Akihiro ; Yokoi, Toru ; Taniguchi, Noboru
概要:
金沢大学大学院医学系研究科血管病態制御学<br />The present study was undertaken to elucidate different requirements for CD2-mediated activati
…
on of naive (CD45RO-) and memory (CD45RO+) CD4+ T cells. A mitogenic combination of anti-CD2 (anti-T112 and anti-T113) mAbs could effectively induce the proliferation of memory CD4+ T cells even in the absence of monocytes. In marked contrast, naive CD4+ T cells did not disclose any proliferative responses to antiCD2 mAbs, when monocytes were absent in culture. This differential responsiveness of naive and memory CD4+ T cells appeared to be related largely to a difference in IL-6 - producing ability between both populations. IL-6 among monocyte-derived cytokines could correct unresponsiveness of naive CD4+ T cells to anti-CD2 stimulation. Unlike naive CD4+ T cells, memory CD4+ T cells produced IL-6 by themselves, with its mRNA being expressed on anti-CD2 stimulation. Anti-IL-6R mAb significantly inhibited proliferation of memory CD4+ T cells seen in the anti-CD2-stimulated cultures without monocytes, indicating the involvement of their own production of IL-6 in CD2-mediated activation. The results suggest an essential role of IL-6 for triggering of CD4+ T cells via the CD2 molecule.
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| 73.
論文 |
論文
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Kasahara, Yoshihito ; Miyawaki, Toshio ; Kato, Kimitaka ; Kanegane, Hirokazu ; Yachie, Akihiro ; Yokoi, Tohru ; Taniguchi, Noboru
概要:
The present study was undertaken to elucidate different requirements for CD2-mediated activation of naive (CD45RO-) and memory (CD45RO+) CD4+ T cells. A mitogenic combination of anti-CD2 (anti-T112 and anti-T113) mAbs could
…
effectively induce the proliferation of memory CD4+ T cells even in the absence of monocytes. In marked contrast, naive CD4+ T cells did not disclose any proliferative responses to antiCD2 mAbs, when monocytes were absent in culture. This differential responsiveness of naive and memory CD4+ T cells appeared to be related largely to a difference in IL-6 - producing ability between both populations. IL-6 among monocyte-derived cytokines could correct unresponsiveness of naive CD4+ T cells to anti-CD2 stimulation. Unlike naive CD4+ T cells, memory CD4+ T cells produced IL-6 by themselves, with its mRNA being expressed on anti-CD2 stimulation. Anti-IL-6R mAb significantly inhibited proliferation of memory CD4+ T cells seen in the anti-CD2-stimulated cultures without monocytes, indicating the involvement of their own production of IL-6 in CD2-mediated activation. The results suggest an essential role of IL-6 for triggering of CD4+ T cells via the CD2 molecule.
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| 74.
論文 |
論文
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清水, 康一
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| 75.
論文 |
論文
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Sugawara, Masayuki
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| 76.
論文 |
論文
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Wada, Akira
|
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| 77.
論文 |
論文
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Ihara, Yoshinori ; Tsuchiya, Ryokichi
概要:
Thermal reactions of the complexes, [Ni(abi)4]X2·nH2O (abi, 2-aminobenzimidazole; X, Cl, Br, I, NO3, ClO4, or 1/2SO4; n,
…
3 for chloride and bromide, 1 for nitrate, and 0 for others) were investigated. Distinct color changes from orange to green were observed in the three complexes of chloride, bromide, and nitrate upon heating. It was found from the changes in absorption and far-IR spectra and magnetic susceptibilities under the thermal reactions that the complexes undergo transformation from square planar to tetragonally distorted octahedral structures, involving an increase in the coordination number from four to six. No such transformation could be found in the corresponding iodide, perchlorate, and sulfate. The effect of the introduced amino group on the structural conversion reactions of the abi complexes is discussed as compared with the corresponding benzimidazole complexes, [Ni(bimd)4]X2, which underwent transformation from square planar to octahedral structure upon heating when X is I or NO3.
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| 78.
論文 |
論文
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村上, 清敏
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| 79.
論文 |
論文
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Otsuka, Iwao
|
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| 80.
論文 |
論文
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上田, 正行
概要:
本学文学部・教授
|
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| 81.
論文 |
論文
|
Ito, K. R. ; Tamura, Hiroshi
概要:
We investigate critical temperature of the classical O(N) spin model in two dimensions. We show that if N is large and there is a phase transition in the system, the critical inverse temperature gc obeys the bound gc(N)> const. N log N.
|
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| 82.
論文 |
論文
|
Takahashi, Kotaro ; Takani, Masako ; Wada, Yoshikazu
概要:
金沢大学大学院自然科学研究科分子作用学<br />金沢大学薬学部<br />The structure of a new alkaline degration product of 1-dihydrousnic acid was eluci
…
dated as 5-acety-1,2,3,3a,7,7a-hexahydro-2,6-dihydroxy-1,2,3a-trimethyl-4-oxo-4H-inden-3,3-dicarboxylic acid (I) by chemical and spectral studies, together with X-ray analysis. The mechanism of formation of I from 1-dihydrousnic acid is discussed.
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|
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| 83.
論文 |
論文
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Fujii, Tozo ; Ohba, Masashi
|
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| 84.
論文 |
論文
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Shiraishi, Yukimasa
|
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| 85.
論文 |
論文
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Tsutsumi, Kitomi
概要:
金沢大学理学部
|
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| 86.
論文 |
論文
|
Fujimoto, Hirotaka
|
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| 87.
論文 |
論文
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Kazama, Hideyuki ; Fujinami, Shuhei ; Sado, Akira
|
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| 88.
論文 |
論文
|
Kono, Yoshiteru ; Hibi, Takeshi ; Kubo, Masayuki ; Michigami, Osamu ; Shibuya, Kyoji ; Sunami, Motoaki ; Suzuki, Keijiro ; Furuse, Nobuhiro
|
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| 89.
論文 |
論文
|
Umebachi, Yoshishige ; Aburano, Yasuhiro
|
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| 90.
論文 |
論文
|
Yoshii, Tsutomu ; Murata, Shigeo ; Suhara, Masahiko
|
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| 91.
論文 |
論文
|
Akaza, Tohru
|
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| 92.
論文 |
論文
|
Asai, Masatomo ; Noda, Kunio ; Sado, Akira
|
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| 93.
論文 |
論文
|
Asakura, Koshu
|
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| 94.
論文 |
論文
|
Kawai. Isawo
|
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| 95.
論文 |
論文
|
Senda, Kantaroo
|
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| 96.
論文 |
論文
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手井, 喜久男
|
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| 97.
論文 |
論文
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初島, 住彦
|
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| 98.
論文 |
論文
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Uematsu, Haruo
|
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| 99.
論文 |
論文
|
正宗, 厳敬
|
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| 100.
論文 |
論文
|
Toyokuni, Hideo
|
