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121.
The formation of a cocrystallized coordination compound, [Pd(3)(D-pen)(3)](2)·[M(en)(3)](ClO(4))(3) (D-H(2)pen = D-penicillamine; M = Co(III) or Rh(III)), from [Pd(3)(D-pen)(3)] and [M(en)(3)](ClO(4))(3) is reported. In this compound, only the Δ-configurational [M(en)(3)](3+) cations were incorporated when its racemic (Δ/Λ) isomer was employed. Besides this enantioselective incorporation of complex cations, this compound was found to show the selective incorporation of ClO(4)(-) as the anion species. 相似文献
122.
Nakamura Y Tanaka S Serizawa R Morohashi N Hattori T 《The Journal of organic chemistry》2011,76(7):2168-2179
Practical methods are described for the preparation of monoamines 4 and 1,3-diamines 5, bearing one or two amino group(s) instead of the hydroxy group(s) at the 28-position or at both the 26- and 28-positions of p-tert-butylcalix[4]arene (1a) and p-tert-butylthiacalix[4]arene (1b), via the Ullmann-type amination or amidation. Thus, the copper-catalyzed or mediated amination of the 1,3-bistriflate ester (2a) of 1a with benzylamine affords either mono(benzylamino) triflate 7a or 1,3-bis(benzylamine) 8 in a high yield, depending on the reaction conditions. On the other hand, the 1,3-bistriflate ester (2b) of 1b resists disubstitution and produces, under stoichiometric conditions, mono(benzylamino) triflate 7b. The disubstitution of 2b is achieved by amidation with tosylamide, giving 1,3-bis(tosylamide) 17b. The hydrogenolysis of the benzylamino moiety of 7a, followed by the hydrolysis of the Tf moiety, affords monoamine 4a, while the hydrogenolysis of 8 affords 1,3-diamine 5a. The amino moiety of 7b can be deprotected under acidic conditions to give, after hydrolysis, monoamine 4b. The hydrolysis of 17b affords 1,3-diamine 5b. The overall yields of compounds 4a, 4b, 5a, and 5b are 72%, 45%, 78%, and 24%, respectively, based on commercially available compounds 1 and are much higher than the ones previously reported in the literature. 相似文献
123.
124.
H Kobayashi H Morita M Yamauchi R Ikeda H Kitagawa Y Kubota K Kato M Takata S Toh S Matsumura 《Journal of the American Chemical Society》2012,134(30):12390-12393
We have synthesized and characterized homogeneous solid-solution alloy nanoparticles of Pd and Rh, which are immiscible with each other in the equilibrium bulk state at around room temperature. The Pd-Rh alloy nanoparticles can absorb hydrogen at ambient pressure and the hydrogen pressure of Pd-Rh alloys for hydrogen storage is dramatically decreased by more than 4 orders of magnitude from the corresponding pressure in the metastable bulk state. The solid-solution state is still maintained in the nanoparticles even after hydrogen absorption/desorption, in contrast to the metastable bulks which are separated into Pd and Rh during the process. 相似文献
125.
Ryuichi Tanaka 《Topology and its Applications》2007,154(15):2849-2855
We describe a finite complex B as I-trivial if there does not exist a Z2-map from Si−1 to S(α) for any vector bundle α over B and any integer i with i>dimα. We prove that the m-fold suspension of projective plane FP2 is I-trivial if and only if m≠0,2,4 for F=C, m≠0,4 for F=H. In the case where F is the Cayley algebra, the m-fold suspension is shown to be I-trivial for every m>0. 相似文献
126.
Tadashi Ikegami Hidefumi Hirai 《Journal of polymer science. Part A, Polymer chemistry》1970,8(2):463-482
Complexes of methyl methacrylate and methacrylonitrile with Lewis acids (SnCl4, AlCl3, and BF3) were copolymerized with styrene at ?75°C under irradiation with a high-pressure mercury lamp in toluene solution. The resulting copolymers consisted of equimolar amount of methyl methacrylate or methacrylonitrile and styrene, regardless of the molar ratio of monomers in the feed. NMR spectroscopy showed the copolymers to have an alternate sequence. The tacticities of the copolymers varied with the complex to have an alternate sequence. The tacticities of the copolymers varied with the complex species: the copolymer from the SnCl4 complex system had a higher cosyndiotactieity, while those from the AlCl3 and the BF3 complex systems showed coisotacticity to predominate over cosyndiotacticity. NMR spectroscopic investigation of the copolymerization system indicated the presence of a charge-transfer complex between the styrene and the methyl methacrylate coordinated to SnCl4. The concentration of the charge-transfer complex was estimated to be about 30% of monomer pairs at ?78°C at a 1:1 molar ratio of feed. The growing end radicals were identified as a methyl methacrylate radical for the AlCl3 complex–styrene system and a styrene radical for the SnCl4 complex–styrene system by the measurement of the ESR spectra of the copolymerization systems under or after irradation with a high-pressure mercury lamp. The tacticity of the resulting polymer appears to be controlled by the structure of the charge transfer complex. In the case of the SnCl4 complex a certain interaction of SnCl4 with the growing end radical seems to be a factor controlling the polymer structure. These copolymerizations can be explained by an alternating charge-transfer complex copolymerization scheme. 相似文献
127.
The effect of the cation concentration, hydrolysis temperature, and composition in the CeO2–ZrO2 system on the direct precipitation of ceria–zirconia solid solutions and the structure of the precipitates from acidic aqueous solutions of (NH4)2Ce(NO3)6 and ZrOCl2 by hydrolysis under hydrothermal conditions were investigated. Nanometer-sized (8–10 nm) ceria–zirconia solid solution particles in a composition range of 0 to 60 mol% ZrO2 were directly precipitated from the solutions with total metal cation concentration less than 0.2 mol/dm3 by simultaneous thermal hydrolysis at 150–240°C. The crystalline phase of the precipitates gradually changed from cubic and/or tetragonal to monoclinic with increasing the cation concentration of the solution from 0.2 to 0.8 mol/dm3 at the starting composition of 50 mol% ZrO2 under hydrolysis condition of 150°C for 48 h, which was attributed to decrease in the supply of hydrolyzed Ce component caused by decrease in the hydrolysis ratio of (NH4)2Ce(NO3)6. Ceria–zirconia solid solutions containing large amount of ZrO2 maintained high specific surface area and small-sized crystallite after heat-treatment at 900–1000°C for 1 h. 相似文献
128.
Tomohiro Yasuda Kenji Miyatake Michiko Hirai Masato Nanasawa Masahiro Watanabe 《Journal of polymer science. Part A, Polymer chemistry》2005,43(19):4439-4445
A series of sulfopropylated and sulfobutylated polyimide copolymers containing fluorenyl groups, SPI‐4, were synthesized to investigate the effect of alkyl side chains on the properties (stability, mechanical strength, water uptake, and proton conductivity) of the polymimide electrolyte membranes. SPI‐4 showed much better hydrolytic stability (in 10% MeOH aq at 100 °C) than the main chain sulfonated polyimide, SPI‐1. Tough, flexible, and ductile membranes were obtained from these copolymers. At high relative humidity all the SPI‐4 membranes showed high mechanical properties (>34 MPa of the maximum stress) and proton conductivity (>0.1 Scm?1). These properties are comparable to or even better than those of the perfluorosulfonic acid ionomer (Nafion 112). The new polyimide ionomers have proved to be a possible candidate as polymer electrolyte membrane for PEFCs and DMFCs. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4439–4445, 2005 相似文献
129.
B 2-groups are special (torsion-free) abelian Butler groups. The interest in this class of groups comes from representation theory. A particular functor, also called Butler functor, connects algebraic properties of the category of free abelian groups with (a few) distinguished subgroups with these Butler groups. This helps to understand Butler groups and caused lots of activities on Butler groups. Butler groups were originally defined for finite rank, however a homological connection discovered by Bican and Salce opened the investigation of Butler groups of infinite rank. Despite the fact that classifications of Butler groups are possible under restriction even for infinite rank (see a forthcoming paper by Files and Göbel [Mathematische Zeitschrift]), general structure theorems are impossible. This is supported by the following very special case of the Main Theorem of this paper, showing that any ring with a free additive group is an endomorphism ring of a Butler group. The result implies the existence of large indecomposable or of large superdecomposable Butler groups as well as the existence of counter-examples for Kaplansky’s test problems. 相似文献
130.