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1.
Seiichi Nishizawa Tomoyuki Kamaishi Tomoyuki Yokobori Ryo Kato Ying-Yu Cui Takeshi Shioya Norio Teramae 《Analytical sciences》2004,20(11):1559-1565
Facilitated SO4(2-) transfers by hydrogen bond-forming ionophores are investigated across the nitrobenzene (NB)-water interface by using polarography with a dropping electrolyte electrode. Bis-thiourea 1, alpha,alpha'-bis(N'-p-nitrophenylthioureylene)-m-xylene, is found to significantly facilitate the transfer of the highly hydrophilic SO4(2-) whereas its counterpart, N-(p-nitrophenyl)-N'-propylthiourea (ionophore 2), cannot. In contrast to the predominant formation of a 1:1 complex with SO4(2-) in the bulk NB phase, the SO4(2-) transfer assisted by 1 is indeed based on the formation of a 1:2 complex between SO4(2-) and ionophore, even under the condition of [SO4(2-)]aq > [1]org. Such an exclusive formation of the 1:2 (SO4(2-) to ionophore) complex at the NB-water interface is not observed with structurally similar bis-thiourea 3, alpha,alpha'-bis(N'-phenylthioureylene)-m-xylene, where p-nitrophenyl moietes of bis-thiourea 1 are simply replaced by phenyl groups. The facilitated transfer of SO4(2-) with bis-thiourea 1 is further compared to that of HPO4(2-) and H2PO4- across the NB-water interface, which was previously shown to be assisted by 1 through the formation of the 1:1 and 2:1 (anion to ionophore) complexes, respectively. On the basis of these examinations, unique binding behaviors of hydrogen bond-forming ionophores at the NB-water interface are discussed, with a view towards development of ionophore-based anion-selective chemical sensors. 相似文献
2.
Haitao Yang Tomoyuki Ogawa Daiji Hasegawa C.N. Chinnasamy Migaku Takahashi 《Journal of magnetism and magnetic materials》2006
Monodisperse bimetallic Pd–Co nanoparticles were prepared via a thermal decomposition of cobalt carbonyl using palladium seeds at the Pd/Co molar ratios 0.5%, 1%, and 5%. The heterogeneously nucleated nanoparticles without any size-selective precipitation are sufficiently uniform to self-assemble into ordered arrays. The as-synthesized nanoparticles are each a single crystal with a complex cubic structure called ε-Co. The presence of Pd seeds seems to improve the stability of Co nanoparticles against oxidation based on the results from time-dependent magnetization measurement. 相似文献
3.
Hidenori Hanaoka Yuka Imamoto Takahiro Hino Tetsuya Kohno Kazunori Yanagi Yoshiaki Oda 《Journal of polymer science. Part A, Polymer chemistry》2007,45(16):3668-3676
Chromium catalysts combined with phosphorous‐bridged bisphenoxy ligands were found to be highly active for ethylene polymerization. The most efficient catalyst precursor among them, generated by combining bis[3‐tert‐butyl‐5‐methyl‐2‐hydroxyphenyl](phenyl)phosphine hydrochloride ( 1a ) and CrCl3(THF)3, was characterized. X‐ray analysis of (3‐tert‐butyl‐5‐methyl‐2‐phenoxy)(3‐tert‐butyl‐5‐methyl‐ 2‐hydroxyphenyl)(phenyl)phosphine bis(tetrahydrofuran)chromium dichloride ( 6 ), obtained by the reaction of 1a and CrCl3(THF)3 in the presence of NaH, revealed a unique structure in which one phenol moiety of the bisphenol did not coordinate to the chromium center. Complex 6 showed higher activities than those observed in the in situ catalyst system. Polyethylene of various molecular weights was obtained with differing activators. The highest activity (113.5 kg mmol (cat)?1 h?1) was observed when TIBA/TB was used as a cocatalyst. A medium molecular weight polymer with narrow molecular weight distribution (Mw = 128,700, Mw/Mn = 1.8) was obtained using a 6 ‐TIBA/B(C6F5)3 system. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3668–3676, 2007 相似文献
4.
The electronic effect on the regioselectivity in the alkynylation of phenyloxiranes was investigated using three kinds of metal acetylides. BF3 mediated lithium acetylide provided either the α- or β-alkynylated products by controlling the effect of the para-substituents of the phenyloxiranes. LiClO4 mediated lithium acetylide and titanium acetylide, on the other hand, afforded predominantly the β- and α-products, respectively. 相似文献
5.
H Fujita Y Sasaki H Kohno Y Ohkubo A Ambo K Suzuki M Hino 《Chemical & pharmaceutical bulletin》1990,38(8):2197-2200
Nine analogs based on a structure of Tyr-D-Arg-Phe-X (X = alkylamides or alkylhydrazide containing electron-withdrawing atoms or groups) were newly synthesized and their biological properties were examined by the opioid receptor binding properties of mu-, delta- and kappa-receptors, guinea-pig ileum (GPI) assay and analgesic activity in the tail pinch test after subcutaneous administration in mice. Analogs with X = NHCF2CF3, Sar-ol, or NH(CH2)2CN showed potent activities in the GPI and analgesic assays and high affinity for mu-receptor. An analog with X = taurinamide was found to possess 4-fold higher mu-receptor selectivity than that of [D-Ala2, MePhe4, Gly-ol5]enkephalin (DAGO). The receptor binding properties of previously reported analogs [Chem. Pharm. Bull., 33, 1528 (1985); ibid., 33, 4865 (1985); ibid., 36, 4834 (1988)] were also examined for overall discussion of the structure-activity relationships of this series of tripeptide amides. 相似文献
6.
The polymerization of isobutyl vinyl ether was studied in a heterogeneous system using iron (II) sulfate calcined in air at various temperatures as a catalyst. The maximum activity was shown by the catalyst calcined at 700°C, which effected the polymerization at room temperature in a few seconds, while the sulfate treated at 750°C was totally inactive. Poly(vinyl ethyl ether) was also obtained by the FeSO4 (700°C) catalyst at room temperature. This catalyst formed the crystalline polymer (melting temperature 135–138°C) when the reaction was performed in toluene as solvent at room temperature. Poisoning experiments with Hammett indicators were carried out with the FeSO4 (700°C) catalyst. The treatment with n-butylamine rendered it inactive in the reaction of isobutyl vinyl ether, while its catalytic activity was little affected by dicinnamalacetone. On the basis of the observed results, the nature of active sites of catalyst is discussed. 相似文献
7.
Shin-ichi Hirano Toshinobu Yogo Wataru Sakamoto Seiji Yamada Tomoyuki Nakamura Tomoe Yamammto Hiroyuki Ukai Kouichi Banno Tomoko Nakafuku Yukari Ando 《Journal of Sol-Gel Science and Technology》2003,26(1-3):35-41
Nano sized crystalline particles/polymer hybrids were synthesized form designed metal-organic precursors. The newly developed method is composed of the synthesis of organic matrix by polymerization and the in situ nucleation and growth of crystalline oxide particles in the organic matrix below 100°C. The design of metal-organic precursor modified with polymerizable ligand and the selection of reaction conditions does influence the size and crystallinity of ceramic particles in organic matrix. The nano-sized magnetic particle/polymer hybrid exhibits the interesting feature of superparamagnetism and quantum size effect. The crystalline particles of BaTiO3/, PbTiO3/, and KNbO3/polymer hybrids behave to be dielectric and show the typical electro-rheological behavior. 相似文献
8.
Tomoyuki Yoshimura 《Tetrahedron letters》2004,45(50):9241-9244
Diastereoselective construction of the 19-epi-C18-C25 segment of (−)-lasonolide A was achieved using a 5-exo-trigonal mode of radical cyclization for the creation of the contiguous quaternary and tertiary stereogenic centers at C22 and C23 as the key reaction step. During the dehydration stage, it was found that an unusual inversion of configuration took place. 相似文献
9.
In a rubidium manganese hexacyanoferrate, RbMn[Fe(CN)(6)], the magnetic susceptibility (chi(M)) decreased at 225 K (=T(1/2)decreasing) and abruptly increased at 300 K (=T(1/2)increasing) in the cooling and warming processes, respectively. X-ray photoelectron spectroscopy and infrared spectroscopy indicated that the high-temperature (HT) and low-temperature (LT) phases were composed of Mn(II)-NC-Fe(III) and Mn(III)-NC-Fe(II), respectively. A structural change from cubic (F43m, a = 10.533 A) to tetragonal (I4m2, a = b = 7.090 A, c = 10.520 A) accompanied the phase transition, and, on the basis of these results, the HT and LT phases were assigned to Mn(II)(t(2g)(3)e(g)(2), (6)A(1g); S = (5)/(2))-NC-Fe(III) (t(2g)(5), (2)T(2g); S = (1)/(2)) and Mn(III)(e(g)(2)b(2g)(1)a(1g)(1), (5)B(1g); S = 2)-NC-Fe(II) (b(2g)(2)e(g)(4), (1)A(1g); S = 0), respectively. This phenomenon is caused by a metal-to-metal charge transfer from Mn(II) to Fe(III) and a Jahn-Teller distortion of the produced Mn(III) ion. The reaction mechanism is discussed, considering the entropy difference between the HT and LT phases. 相似文献
10.
Wright RJ Phillips AD Hino S Power PP 《Journal of the American Chemical Society》2005,127(13):4794-4799
The synthesis and characterization of three new organothallium(I) compounds are reported. Reaction of (Ar'Li)(2) (Ar' = C(6)H(3)-2,6-(C(6)H(3)-2,6-Pr(i)(2))(2)) and Ar"Li (Ar" = C(6)H(3)-2,6-(C(6)H(3)-2,6-Me(2))(2)) with TlCl in Et(2)O afforded (Ar'Tl)(2) (1) and (Ar' 'Tl)(3) (2). The "dithallene" 1 is the heaviest group 13 dimetallene and features a planar, trans-bent structure with Ar'Tl-Tl = 119.74(14) degrees and Tl-Tl = 3.0936(8) A. Compound 2 is the first structurally characterized neutral, three-membered ring species of formula c-(MR)(3) (M = Al-Tl; R = organo group). The Tl(3) ring has Tl-Tl distances in the range ca. 3.21-3.37 A as well as pyramidal Tl geometries. The Tl-Tl bonds in 1 and 2 are outside the range (2.88-2.97 A) of Tl-Tl single bonds in R(2)TlTlR(2) compounds. The weak Tl-Tl bonding in 1 and 2 leads to their dissociation into Ar'Tl and Ar' 'Tl monomers in hexane. The Ar'Tl monomer behaves as a Lewis base and readily forms a 1:1 donor-acceptor complex with B(C(6)F(5))(3) to give Ar'TlB(C(6)F(5))(3), 3. Adduct 3 features an almost linear thallium C(ipso)-Tl-B angle of 174.358(7) degrees and a Tl-B distance of 2.311(2) A, which indicates strong association. Treatment of 1 with a variety of reagents resulted in no reactions. The lower reactivity of 1 is in accord with the reluctance of Tl(I) to undergo oxidation to Tl(III) due to the unreactive character of the 6s(2) electrons. 相似文献