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21.
Yutaka Miura Toshifumi Satoh Atsushi Narumi Osamu Nishizawa Yoshio Okamoto Toyoji Kakuchi 《Journal of polymer science. Part A, Polymer chemistry》2006,44(4):1436-1446
The copper‐mediated atom transfer radical polymerization of methyl methacrylate (MMA) in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) was studied to simultaneously control the molecular weight and tacticity. The polymerization using tris[2‐(dimethylamino)ethyl]amine (Me6TREN) as a ligand was performed even at ?78°C with a number‐average molecular weight (Mn) of 13,400 and a polydispersity (weight‐average molecular weight/number‐average molecular weight) of 1.31, although the measured Mn's were much higher than the theoretical ones. The addition of copper(II) bromide (CuBr2) apparently affected the early stage of the polymerization; that is, the polymerization could proceed in a controlled manner under the condition of [MMA]0/[methyl α‐bromoisobutyrate]0/[CuBr]0/[CuBr2]0/[Me6TREN]0 = 200/1/1/0.2/1.2 at ?20°C with an MMA/HFIP ratio of 1/4 (v/v). For the field desorption mass spectrum of CuIBr/Me6TREN in HFIP, there were [Cu(Me6TREN)Br]+ and [Cu(Me6TREN)OCH(CF3)2]+, indicating that HFIP should coordinate to the CuI/Me6TREN complex. The syndiotacticity of the obtained poly(methyl methacrylate)s increased with the decreasing polymerization temperature; the racemo content was 84% for ?78°C, 77% for ?30°C, 75% for ?20°C, and 63% for 30°C. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1436–1446, 2006 相似文献
22.
Atsushi Kasue 《Potential Analysis》2006,24(2):137-194
We study spectral convergence of compact Riemannian manifolds or more generally certain Dirichlet spaces, obtaining some compactness
results on harmonic functions and harmonic maps.
Mathematics Subject Classifications (2000) 53C21, 58D17, 58J50.
Atsushi Kasue: Partly supported by the Grant-in-Aid for Scientific Research (B) No. 15340053 of the Japan Society for the
Promotion of Science. 相似文献
23.
In this paper, we treat a domain optimization problem in which the boundary-value problem is a Neumann problem. In the case where the domain is in a three-dimensional Euclidean space, the first-order and the second-order necessary conditions which the optimal domain must satisfy are derived under a constraint which is the generalization of the requisite of constant volume.Portions of this paper were presented at the 13th IFIP Conference on System Modelling and Optimization, Tokyo, Japan, 1987. 相似文献
24.
Molecular and electronic structural properties of the hydrogen-bonded complexes of p-quinone dianions (PQ(2)(-)) were investigated by electrochemistry and spectroelectrochemistry of PQ in MeCN combined with ab initio MO calculations. Hydrogen bonding between PQ(2)(-) and MeOH was measured as the continuous positive shift of the apparent second half-wave reduction potentials with increasing concentrations of MeOH. Detailed analyses of the behavior reveal that PQ(2)(-) forms the 1:2 hydrogen-bonded complexes at low concentrations of MeOH and the 1:4 complexes at high concentrations, yielding the formation constants. Temperature dependence of the formation constants allows us to yield the formation energy as 76.6 and 118.9 kJ mol(-)(1) for the 1:2 and 1:4 complex formation of the 1,4-benzoquinone dianion (BQ(2)(-)) with MeOH, respectively. These results show that the pi-dianions involving the quinone carbonyl groups exhibit very strong hydrogen-accepting ability. The longest wavelength band of the spectra of BQ(2)(-) and the chloranil dianion (CL(2)(-)) is assigned to the (1)B(3u) <-- (1)A(g) band mainly contributed from an intramolecular charge-transfer (CT) configuration. Hydrogen bonding allows the band of BQ(2)(-) and CL(2)(-) to be blue-shifted, depending on the strength of the hydrogen bonds. CNDO/S-CI calculations reveal that the blue shift is ascribed to stabilization of the ground state by the hydrogen bonding involving strong n-sigma-type CT interaction. The HF/6-31G(d) calculation results show that the structure of PQ(2)(-) is characterized by a lengthening of the C=O bonds and a benzenoid ring. The geometrical properties of the hydrogen-bonded complexes of PQ(2)(-) are a slight lengthening of the C=O bonds and a short distance of the hydrogen bonds. It is demonstrated that this situation is due to the strong n-sigma CT interaction in the hydrogen bonds. The results suggest that the differing functions and properties of biological quinones are conferred by the n-sigma CT interaction through hydrogen bonding of the dianions with their protein environment. 相似文献
25.
Semidifferential electroanalysis is described for hexacyanoferrate(III), dichromate, copper(II), p-aminophenol, p-benzoquinone, m-dinitrobenzene, guanine, guanosine, adenine, and adenosine at a stationary solid working electrode. Nearly symmetrical, peaked curves are obtained for the electrode processes of all the samples investigated. The predicted dependence of peak height and peak potential on concentration, electrode area, and potential scan rate are confirmed-experimentally for the glassy carbon disk electrode. It is demonstrated that the technique with the solid working electrode provides higher sensitivity and better resolution than ordinary linear sweep voltammetry. The sensitivity is somewhat worse than in differential pulse voltammetry, but the technique has the advantage of Speed. 相似文献
26.
27.
Atsushi Ikeda Tsukasa HatanoToshifumi Konishi Jun-ichi KikuchiSeiji Shinkai 《Tetrahedron》2003,59(19):3537-3540
In a light-to-photocurrent conversion system based on a C60-porphyrin bilayer prepared by electrostatic alternate adsorption, porphyrin units in a porphyrin polymer have been isolated by cyclodextrin utilizing the host-guest interaction. In this system, a high quantum yield was achieved by suppression of self-quenching of porphyrin units. 相似文献
28.
Atsushi Ikeda Masaru Kawaguchi Yoshio Suzuki Tsukasa Hatano Munenori Numata Seiji Shinkai Akio Ohta Makoto Ohta 《Journal of inclusion phenomena and macrocyclic chemistry》2000,38(1-4):163-170
The calixarene-fullerene interaction,which causes only a slight change in the absorptionspectra, has been substantiated by calorimetricmeasurements: the H° values arecomparable with those obtained from the associationconstants estimated by a spectroscopic method. Furthermore, we determined the association constantbetween homooxacalix[3]arene and [60]fullerenederivatives with a porphyrin moiety by fluorescencespectra. 相似文献
29.
Takeshi Ishijima Yoshiki Mizumori Kenji Kikuchi Atsushi Suzuki Takuji Okaya 《Colloid and polymer science》2005,283(7):799-804
Polymerization of vinyl acetate (VAc) in various fatty acids (carbon numbers 4–18) was carried out. Chain transfer constants to the acids were determined to be 20–35×10–4, from which the constant to a methylene group was obtained to be 0.73×10–4. Viscometry in aqueous solution of derived poly (vinyl alcohol) (PVA) showed the usual behavior in terms of Huggins constant obtained by the Schulz–Blaschkes equation for PVAs derived from fatty acid systems lower than hexadecanoic acid. PVA derived from octadecanoic acid system showed abnormality, indicating association of alkyl groups. Contact angles on surfaces of PVAs cast from aqueous solutions were measured. While those of PVA derived from lower acid systems were 62°, those of PVAs derived from higher aids were higher and increased to 92° with increase in carbon number to octadecanoic acid. Alkyl groups in the PVAs were estimated to appear on the surfaces. Surface tension of aqueous solution of the PVA derived from octadecanoic acid showed high surface activity, and depended on pH of the solution, indicating the presence and cleavage of lactone ring at the combined portion between PVA and the acid. 相似文献
30.
Tsuyoshi Miura Satoshi Tsujino Kohtaro Goto Midori Noguchi Manabu Node Nobuyuki Imai 《Tetrahedron》2005,61(27):6518-6526
The use of the bisfluorous chain-type propanoyl (Bfp) group as a fluorous protective group made it possible to rapidly synthesize the Gb2 and Gb3 oligosaccharide derivatives by a simple fluorous-organic extraction purification. Furthermore, the fluorescence-labeled Gb2 and Gb3 oligosaccharides were prepared as a potential Vero Toxins detecting reagent. 相似文献