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31.
Wickramasinghe NP Shaibat M Ishii Y 《Journal of the American Chemical Society》2005,127(16):5796-5797
High-resolution NMR spectroscopy for paramagnetic complexes in solids has been rarely performed because of its limited sensitivity and resolution due to large paramagnetic shifts and associated technical difficulties. The present study demonstrates that magic angle spinning (MAS) at speeds exceeding 20 kHz provides unusually high sensitivity and excellent resolution in 1H solid-state NMR (SSNMR) for paramagnetic systems. Spinning-speed dependence of 1H MAS spectra showed that very fast MAS (VFMAS) at 24-28 kHz enhanced sensitivity by a factor of 12-18, compared with the sensitivity of 1H SSNMR spectra under moderate MAS at 10 kHz, for Cu(dl-alanine)2.H2O and Mn(acac)3, for which the spectral ranges due to 1H paramagnetic shifts reach 200 and 1000 ppm, respectively. It was theoretically and experimentally confirmed that the absolute sensitivity of 1H VFMAS for small paramagnetic complexes such as Cu(dl-alanine)2 can be an order of magnitude higher than that of equimolar diamagnetic ligands because of short 1H T1 ( approximately 1 ms) of the paramagnetic systems and improved sensitivity under VFMAS. On the basis of this demonstrated high sensitivity, 1H SSNMR micro analysis of paramagnetic systems in a nanomole scale is proposed. Applications were performed on two polymorphs of Cu(II)(8-quinolinol)2, which is a suppressor of human cancer cells. It was demonstrated that 1H VFMAS SSNMR spectra accumulated for 20 nmol of the polycrystalline samples in 10 min enabled one to distinguish alpha- and beta-forms of Cu(II)(8-quinolinol)2 on the basis of shift positions and line widths. 相似文献
32.
Hitoshi Kubota Yoshitaka Ogiwara Kei Matsuzaki 《Journal of polymer science. Part A, Polymer chemistry》1974,12(12):2809-2819
The decay behavior of cellulose radicals produced by photo-irradiation at room temperature and the characteristics of photo-irradiated cellulose samples to initiate graft copolymerization of methyl methacrylate (MMA) were investigated. ESR spectra of such untreated, swollen, oximated, and ferric ion-sensitized samples irradiated at room temperature were constructed mainly of a single absorption line with a line width of 20 to 22 gauss and a g value of 2.003, and it is surely conceivable that the radicals showing a singlet spectrum should agree with those of alkoxy end produced at either the C1 or C4 position of the glucose unit by the scission of glucosidic bonds. The decay of radicals was accelerated by contact of various solvents with the samples, the activity decreasing in the order, water ≈ methanol ? acetone > dioxane. On the other hand, the decay of radicals by vinyl monomers became smaller in the order, methacrylic acid > MMA ≈ styrene. Graft copolymerization of MMA by a photo-irradiated sample was effectively initiated with the use of a certain amount of water or methanol, but not with acetone and dioxane. As no initiation can occur with the unirradiated sample, it is concluded that the initiation of graft copolymerization on the photo-irradiated sample is attributable to cellulose radicals showing a singlet spectrum which are formed in photo-irradiation at room temperature. 相似文献
33.
Yuka Wakata Mika Tokumoto Ryo Horiguchi Katsutoshi Ishikawa Yoshitaka Nagahama Toshinobu Tokumoto 《BMC biochemistry》2004,5(1):18
Background
The 26S proteasome is the proteolytic machinery of the ubiquitin-dependent proteolytic system responsible for most of the regulated intracellular protein degradation in eukaryotic cells. Previously, we demonstrated meiotic cell cycle dependent phosphorylation of α4 subunit of the 26S proteasome. In this study, we analyzed the changes in the spotting pattern separated by 2-D gel electrophoresis of α subunits during Xenopus oocyte maturation. 相似文献34.
Yoshitaka Ishimuro Fumiyuki Hamada Akio Nakajima 《Journal of polymer science. Part A, Polymer chemistry》1979,17(6):1811-1819
The scattering function of rods with a constant radius, 8 Å, and a length distribution of the Schulz–Zimm type was calculated on a computer as a model of helical synthetic polypeptide. The influence of length and length distribution on the scattered intensity of small-angle x-ray scattering was clarified. As length grows and length distribution broadens it is difficult to obtain reliable values of molecular weight and radius of gyration from a Zimm plot. The influence of length distribution on the mass per unit length, Mq, and the radius of gyration of the cross section, 〈S〉1/2, from the Guinier plot of the cross-sectional factor decreases as the length increases, and reliable values of Mq and 〈S〉1/2 can be obtained even for rods with wide distribution for rods more than 600 Å long. In particular, it is pointed out that the value of 〈S〉1/2 is little influenced by length and length distribution. 相似文献
35.
Ando K Tsuji E Ando Y Kunitomo J Kobayashi R Yokomizo T Shimizu T Yamashita M Ohta S Nabe T Kohno S Ohishi Y 《Organic & biomolecular chemistry》2005,3(11):2129-2139
Variable benzo[b]furan derivatives having (E)- and (Z)-2-alkylcarbamoyl-1-methylvinyl groups at the 2-, 4- and 5-positions and a carboxylpropoxy or (1-phenyl)ethoxy group at the 7-position were prepared to find novel and selective leukotriene B4(LTB4) receptor antagonists. (E)-2-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (4v) showed selective inhibition to the human BLT2 receptor (hBLT2). On the other hand, (E)-2-acetyl-4-(2-diethylcarbamoyl-1-methylvinyl)-7-(1-phenylethoxy)benzo[b]furan (7v) inhibited both human BLT(1) receptor (hBLT1) and hBLT2. The (E)-2-(2-diethylcarbamoyl-1-methylvinyl) group lay on approximately the same plane as the benzo[b]furan ring, whereas the (E)-4-(2-diethylcarbamoyl-1-methylvinyl) group had the torsion angle (45.7 degree) from the benzo[b]furan ring plane. However, the (Z)-(2-alkylcarbamoyl-1-methylvinyl)benzo[b]furans were inactive. The inhibitory activity depended on the conformation of the 2-diethylcarbamoyl-1-methylvinyl group. 相似文献
36.
Highly dispersed zirconium phosphate was prepared by reacting Cel/ZrO(2) (ZrO(2)=6.7 wt%; 0.56 mmol g(-1) of zirconium atom per gram of the material) with phosphoric acid. High power decoupling magic angle spinning (HPDEC-MAS)(31)P NMR and X-ray photoelectron spectroscopy data indicated that HPO(2-)(4) is the species present on the fiber surface. The X-ray diffraction patterns showed that zirconium hydrogen phosphate particles were amorphous and had an ion-exchange capacity, determined by ammonia gas adsorption, of 0.30 mmol g(-1). The ion-exchange capacities for Li(+), Na(+), and K(+) ions were determined from ion-exchange isotherms at 298 K and showed the following values (in mmol g(-1)): Li(+)=0.01, Na(+)=0.23, and K(+)=0.30. The higher affinity of the surface hydrogen phosphate particles for Na(+) and K(+) is due to its lamelar structure which permits easier diffusion of these two ions whose hydrated radii are smaller than that of Li(+). 相似文献
37.
Yoshitaka Ogiwara Yuji Kimura Zenjiro Osawa Hitoshi Kubota 《Journal of polymer science. Part A, Polymer chemistry》1977,15(7):1667-1675
Effects of ferric chloride (FeCl3) on photodegradation of high-density polyethylene (PE) were investigated by using ESR and infrared spectrometry. In the system with irradiation at light of λ > 220 nm, PE irradiated at 77°K yielded an 8-line spectrum, the intensity of which was markedly weakened by using FeCl3 with the sample, indicating a distinct depression of radical formation. On the other hand, PE with the use of FeCl3 yielded radicals under irradiation only with light of λ > 300 nm, showing a singlet spectrum with a line width of 15 gauss. For photooxidized PE, almost the same effect of FeCl3 was observed. On irradiation at room temperature, PE samples with and without FeCl3 showed a singlet spectrum with line widths of 15 and 25 gauss, respectively. On the other hand, the unsaturated double bond contained in a small amount in PE sample was observed by infrared study to be decreased with photoirradiation; however, the decrease was sharply depressed with the addition of FeCl3 to the sample. The degradation of carbonyl group in a photooxidized sample was markedly affected by photoirradiation, and the decay was obviously reduced for the sample on addition of FeCl3. It is concluded that FeCl3 works upon photodegradation of PE to enhance the Norrish type II reaction and to accelerate the formation of unsaturated double bond in the chain. 相似文献
38.
Oki Michinori Toyofuku Yoshitaka Sakaue Tatsuya Hirose Takanori Asakura Mitsuhiro Morita Nobuhiro Toyota Shinji 《Russian Journal of Organic Chemistry》2003,39(4):542-553
X-ray crystallography of the ap-form of the 1-(9-fluorenyl)-2-(2-methyl-2-oxiranyl)naphthalene has revealed that the carbon atom of the oxirane which is connected to the naphthyl group in this compound is almost planar. The specific structural features of the epoxy ring in this compound are caused by sterical effects and by the presence of a -system in the immediate vicinity of the oxirane ring. Certain differences have been found also in reactivity of rotational isomers of 2-X-substituted 1-[1-(9-fluorenyl)-2-naphthyl]ethyl cations (X = O, S, Se). At X = O arose more deprotonation product from the -position of the oxygen than in reactions of sulfur and selenium-containing analogs. Reactions of epoxides with zinc chloride almost exclusively gave the corresponding aldehydes. 相似文献
39.
40.
Yoshitaka Yoda Yasuhiko Imai Hisao Kobayashi Syunji Goto Kunikazu Takeshita Makoto Seto 《Hyperfine Interactions》2012,206(1-3):83-86
An Upgrade of the nuclear resonant scattering beamline, BL09XU in SPring-8 has been conducted. A liquid nitrogen cooled high-heat load monochromator was installed and a 2nd experimental hutch was constructed. The instruments installed in the hutch allow for a variety of sample conditions. Newly developed high-resolution monochromators with better stability including the back scattering geometry monochromator have opened up the easy access to more isotopes and more precise measurements. 相似文献