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2.
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Hoshikawa, Takaya ; Tanji, Kei ; Matsuo, Jun-ichi ; Ishibashi, Hiroyuki
概要:
Intramolecular [2+2] cycloaddition of γ,δ-unsaturated ketenes derived from hex-5-enoyl chloride derivatives gave bicyclo[2.1.1]hexan-5-ones with complete regioselectivity. © 2012 The Pharmaceutical Society of Japan.
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World Congress of Gastroenterology
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5.
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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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6.
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Nishida, Yuki ; Miyamori, Hisashi ; Thompson, Erik W. ; Takino, Takahisa ; Endo, Yoshio ; Sato, Hiroshi
概要:
金沢大学がん研究所がん病態制御<br />The suggested model for pro-matrix metalloproteinase-2 (proMMP-2) activation by membrane type 1 MMP
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(MT1-MMP) implicates the complex between MT1-MMP and tissue inhibitor of MMP-2 (TIMP-2) as a receptor for proMMP-2. To dissect this model and assess the pathologic significance of MMP-2 activation, an artificial receptor for proMMP-2 was created by replacing the signal sequence of TIMP-2 with cytoplasmic/transmembrane domain of type II transmembrane mosaic serine protease (MSP-T2). Unlike TIMP-2, MSP-T2 served as a receptor for proMMP-2 without inhibiting MT1-MMP, and generated TIMP-2-free active MMP-2 even at a low level of MT1-MMP. Thus, MSP-T2 did not affect direct cleavage of the substrate testican-1 by MT1-MMP, whereas TIMP-2 inhibited it even at the level that stimulates proMMP-2 processing. Expression of MSP-T2 in HT1080 cells enhanced MMP-2 activation by endogenous MT1-MMP and caused intensive hydrolysis of collagen gel. Expression of MSP-T2 in U87 glioma cells, which express a trace level of endogenous MT1-MMP, induced MMP-2 activation and enhanced cell-associated protease activity, activation of extracellular signal-regulated kinase, and metastatic ability into chick embryonic liver and lung. MT1-MMP can exert both maximum MMP-2 activation and direct cleavage of substrates with MSP-T2, which cannot be achieved with TIMP-2. These results suggest that MMP-2 activation by MT1-MMP potentially amplifies protease activity, and combination with direct cleavage of substrate causes effective tissue degradation and enhances tumor invasion and metastasis, which highlights the complex role of TIMP-2. MSP-T2 is a unique tool to analyze physiologic and pathologic roles of MMP-2 and MT1-MMP in comparison with TIMP-2. ©2008 American Association for Cancer Research.全文公開200911
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7.
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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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8.
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Nakamura, Akiko ; Nakajima, Miki ; Higashi, Eriko ; Yamanaka, Hiroyuki ; Yokoi, Tsuyoshi
概要:
医薬保健研究域薬学系<br />OBJECTIVES: Human uridine diphosphate-glucuronosyltransferase 2B7 (UGT2B7) plays important roles in the
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metabolism of some clinical drugs, carcinogens, and steroid hormones. The molecular mechanisms of the inducible expression of UGT2B7 in response to xenobiotics have not been fully clarified. We sought to investigate whether the UGT2B7 is under the control of NF-E2 p45-related factor 2 (Nrf2), a key transcriptional factor regulating the expression of cytoprotective enzymes. METHODS: HepG2, HuH7, HLE, and Caco-2 cells were treated with sulforaphane (SFN), and the UGT2B7 mRNA levels were determined by real-time reverse transcriptase PCR. These cells were genotyped for the UGT2B7*2 (H268Y) allele using the PCR-restriction fragment length polymorphism method. Luciferase analyses and gel shift analyses were performed to identify the responsive regions for Nrf2 signaling. RESULTS: The UGT2B7 mRNA was induced by SFN in HepG2 and HuH7 genotyped as UGT2B7*1/*1, but not in HLE and Caco-2 cells genotyped as UGT2B7*2/*2. In HepG2 cells, the UGT2B7 protein level and morphine glucuronosyltransferase activity were also significantly induced by SFN. The induction was prominently decreased with small interfering RNA for Nrf2. In the 5'-flanking region (-2.5 kb) of the UGT2B7*2 allele, a 324-base pair insertion at -2067 and 12 single nucleotide polymorphisms simultaneously existed. Luciferase analyses and gel shift analyses revealed that an antioxidant responsive element at -1170 was responsible for the transactivation by Nrf2. In addition, a region from -990 to -858 on the UGT2B7*1 allele was also responsible for the transactivation by Nrf2. Abrogation of the Nrf2-dependent transactivation of the UGT2B7*2 allele was owing to the single nucleotide polymorphism -900A>G. CONCLUSION: UGT2B7 is transcriptionally regulated by Nrf2, but the mechanism is hindered by polymorphisms in the promoter region of UGT2B7*2. The allele-specific mechanism may cause variability of the glucuronidation in response to oxidative stress.全文公開200908
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10.
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11.
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12.
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edited with translation and explanatory notes by S.D. Joshi and J.A.F. Roodbergen
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13.
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Yamada, Fumio ; Kawanishi, Atsuko ; Tomita, Akiko ; Somei, Masanori
概要:
1-Hydroxy-2,3-dimethylindole (1) has been prepared for the first time. Under atmospheric oxygen, 1 was converted rapidly into 3-hydroxy-2,3-dimethyl- 3H-indole N-oxide (2). The structure was deduced, based on its products obtained
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by the reaction with Ac2O in pyridine and confirmed by X-ray single crystallographic analysis.
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14.
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Nakano, Takeo ; Soeta, Takahiro ; Endo, Kohei ; Inomata, Katsuhiko ; Ukaji, Yutaka
概要:
The sequential 1,4-elimination reaction of (E)-4-alkoxy-2-butenyl benzoates and [1,2]-Wittig rearrangement gave (2Z,4E)-
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2,4-pentadien-1-ols stereoselectively. Z-Selective formation of intermediary vinyl ethers, whose stereochemistry was well elucidated by the "syn-effect", was achieved by treatment of the 2-butenyl benzoates with KOH in the presence of Pd catalyst. The subsequent [1,2]-Wittg rearrangement by use of n-BuLi proceeded with retention of the stereochemistry of the intermediary vinyl ethers. © 2013 American Chemical Society.
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16.
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17.
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18.
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Murata, Yasue ; Kinoshita, Hideki ; Inomata, Katsuhiko
概要:
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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19.
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Dickens, Brian.
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20.
論文 |
Higuchi, Akihiro ; Erina Oonishi ; Kawakita, Tetsuya ; Tsubota, Kazuo ; 樋口, 明弘
概要:
金沢大学先端科学・社会共創推進機構<br />Purpose: 2-hydroxy estradiol (2-OHE2) is a catechol derivative of 17β -Estradiol (E2) and it is s
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ynthesized from E2 catalyzed by cytochrome P4501A1. Previous studies reported that 2-OHE2 is a physiologic antioxidant in lipoproteins, liver microsomes, and the brain. Catechol derivatives show an anti-inflammatory effect through the inhibition of prostaglandin endoperoxide synthase (PGS) activity. Corneal erosion caused by dry eye is related to an increase in oxidative stress and inflammation in ocular surface cells. We investigated the therapeutic effects of 2-OHE2 on corneal damage caused by dry eye. Methods: Steroidal radical scavenging activity was confirmed through the electron spin resonance (ESR) method. PGS activity was measured using the COX Fluorescent Activity Assay Kit. To evaluate the effect of 2-OHE2 on the treatment for dry eye, 2-OHE2 was applied as an eye drop experiment using dry eye model rats. Results: 2-OHE2 scavenged tyrosyl radical and possibly suppressed oxidative stress in corneal epithelial cells. In addition, 2-OHE2 inhibited PGS activity, and 2-OHE2 is probably a competitive inhibitor of PGS. Corneal PGS activity was upregulated in the dry eye group. Therefore, 2-OHE2 eye drops improved corneal erosion in dry eye model rats. Conclusions: 2-OHE2 is a candidate for the treatment of dry eye through the suppression of inflammation and oxidative stress in the cornea. © 2016 Molecular Vision.
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21.
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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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22.
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Dubuisson, Bernard
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von Gerhard Timpe
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hrsg. von Karl-Heinz Fingerhut, Eduard Haueis und Otfried Hoppe
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27.
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Federation of European Biochemical Societies
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28.
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Nakata, Shunji ; Kato, Takashi ; Ozaki, Shinya ; Kawae, Takeshi ; Morimoto, Akiharu
概要:
Thin film Al2O3/Al-rich Al2O 3/SiO2 structures were fabricated on p-Si substrates. Radio-frequency magnetron co-sputteri
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ng was used to form Al-rich Al 2O3 thin film as the charge-trapping layer of nonvolatile Al2O3 memory. Capacitance-voltage measurements showed a large hysteresis due to charge trapping in the Al-rich Al2O 3 layer. The charge trap density was estimated to be 42.7 × 1018 cm- 3, which is the largest value ever reported for an Al-rich Al2O3 layer; it is six times larger than that of a conventional metal-nitride-oxide-silicon memory. Thermal annealing was found to reduce the leakage current of the Al2O3 blocking layer, thereby providing this structure with better data retention at room temperature than an as-deposited one. In addition, the annealed structure was found to exhibit good data retention even at 100 C. © 2013 Elsevier B.V. All rights reserved.
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29.
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Deutsche Chemische Gesellschaft ; Beilstein, Friedrich Konrad, 1838-1906 ; Richter, Friedrich, 1896-1961
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30.
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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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31.
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Inami, Shinnosuke ; Nishio, Masaki ; Hayashi, Yoshihito ; Isobe, Kiyoshi ; Kameda, Hiroyuki ; Shimoda, Tatsuya
概要:
金沢大学理工研究域物質化学系<br />An all-inorganic complex, [Mn2{(CVO3) 5}2]6- (1), was synthesized, and the structure determination r
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eveals a dinuclear manganese complex coordinated by two cyclic pentavanadate ligands. The cyclic pentavanadate units sandwich the edge-sharing octahedral dimanganese core through, coordination of the oxido group of the pentavanadate. A. dinuclear cobalt complex with, a cyclic decavanadate, [Co 2(OH2)2(VO3)10]6- (2), was also synthesized. The structure analysis reveals a dinuclear cobalt complex with a macrocyclic decavanadate, which is composed of 10 VO4 units joined by the vertex. Sharings. The CoO6 octahedrons are edge-shared, with each cobalt octahedron coordinated to five oxido groups from the decavanadate. The remaining site is occupied by - water. The coordinated water molecules are supported with hydrogen bonds in two directions. Complex 2 in acetonitrile shows no reactivity with dioxygen even at low temperature, and the cyclic voltammogram of 2 shows no redox chemistry in acetonitrile. Complex 2 exhibits chromism by water exposure both, in the solid state and. in acetonitrile. Complex 2 is green-yellow in color, and. the addition of water causes the complex to turn brown. After heating the sample, it returns to its original color in a reversible manner. The EXAFS data in acetonitrile is also reported, and is consistent with the solid-state structure. © Wiley-VCH Verlag GmbH & Co. KGaA.
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32.
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United States. Congress. Senate. Select Committee on Small Business. Subcommittee on Monopoly
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33.
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Sawanomukai, Takashi ; Iwatsubo, Yoshikane ; Naruhashi, Naohiro
概要:
Chromosome counts of 16 species and two varieties of Scutellaria(Lamiaceae)collected from 45 localities in Ja-pan were r
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eported. First counts were the following 11 taxa : S . amabilis(2n=26), S . brachyspica(2n=26), S . in-dica var. parvifolia(2n=26), S . iyoensis(2n=26), S . kiusiana(2n=26), S . laeteviolacea var. laeteviolacea(2n =26), S . laeteviolacea var. maekawae(2n=26), S . muramatsui(2n=26), S . pekinensis var. transitra(2n=28), S . shikokiana(2n=28)and S . tsusimensis(2n=26). New counts were reported in S . dependens(2n=28), S . strigil-losa(2n=30)and S . yezoensis(2n=30). Chromosome counts for S . barbata(2n=26), S . guilielmii(2n=28), S . indica var. indica(2n=26)and S . rubropunctata var. rubropunctata(2n=26)were confirmed.
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34.
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Ikeda, Masazumi ; Ohtani, Shinji ; Okada, Michiyo ; Minakuchi, Emi ; Sato, Tatsunori ; Ishibashi, Hiroyuki
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35.
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Somei, Masanori ; Kodama, Atsushi
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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36.
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Matsuo, Jun-ichi ; Okuno, Ryosuke ; Takeuchi, Kosuke ; Kawano, Mizuki ; Ishibashi, Hiroyuki
概要:
金沢大学医薬保健研究域薬学系<br />Optimized reaction conditions for the preparation of various 2-monosubstituted 3-ethoxycyclobutanone
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s are described. 2-Monoalkyl 3-ethoxycyclobutanones were efficiently prepared by the reaction of the corresponding carboxylic acid chlorides and an excess amount of ethyl vinyl ether in the presence of diisopropylethylamine at 90 °C in a sealed tube. 2-Monoaryl 3-ethoxycyclobutanones were prepared by using 2,6-lutidine as a base in the above-mentioned procedure. © 2010 Published by Elsevier Ltd. All rights reserved.
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37.
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Matsuo, Junichi ; Okuno, Ryosuke ; Takeuchi, Kosuke ; Kawano, Mizuki ; Ishibashi, Hiroyuki
概要:
金沢大学医薬保健研究域薬学系<br />Optimized reaction conditions for the preparation of various 2-monosubstituted 3-ethoxycyclobutanone
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s are described. 2-Monoalkyl 3-ethoxycyclobutanones were efficiently prepared by the reaction of the corresponding carboxylic acid chlorides and an excess amount of ethyl vinyl ether in the presence of diisopropylethylamine at 90 °C in a sealed tube. 2-Monoaryl 3-ethoxycyclobutanones were prepared by using 2,6-lutidine as a base in the above-mentioned procedure. © 2010 Elsevier Ltd. All rights reserved.
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38.
論文 |
Nishida, Y. ; Miyamori, H. ; Thompson, E.W. ; Takino, Takahisa ; Sato, H.
概要:
Division of Molecular Viology and Oncology
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39.
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Алексей Каплер
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40.
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Gustav Ehrismann
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41.
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Tsutiya, Ryokichi
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42.
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Tsutiya, Ryokichi
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43.
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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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44.
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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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45.
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46.
図書 |
herausgegeben von Wolf-Hartmut Friedrich und Walther Killy
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47.
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text, translation and notes by J.A.F. Roodbergen ; edited by S.D. Joshi
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49.
論文 |
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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50.
論文 |
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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