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21.
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
22.
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
23.
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
24.
25.
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
26.
Naoya Hosoda Hideaki Kamito Miki Takano Yoshitaka Takebe Yoshitaka Yamaguchi Masatoshi Asami 《Tetrahedron》2013,69(6):1739-1746
Chiral diamines, 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine, were prepared from N-(tert-butoxycarbonyl)pyrrolidine or (S)-proline as a starting material, respectively. These chiral diamines were efficient for the catalytic enantioselective borane reduction of acetophenone. Using (S)-2-(anilinodiphenylmethyl)pyrrolidine, chiral secondary alcohols were obtained from prochiral ketones with good to excellent enantiomeric excesses (up to 98% ee). 相似文献
27.
Dual Catalysis with Copper and Rhenium for Trifluoromethylation of Propargylic Alcohols: Efficient Synthesis of α‐Trifluoromethylated Enones 下载免费PDF全文
Dr. Hiromichi Egami Takafumi Ide Masashi Fujita Toshifumi Tojo Prof.Dr. Yoshitaka Hamashima Prof.Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(38):12061-12065
Trifluoromethylation of propargylic alcohols to provide (Z)‐α‐trifluoromethylated enones and β‐unsubstituted α‐trifluoromethylated enones proceeded with high yield and selectivity in the presence of CuI/Re2O7. The Z isomer was formed under kinetic control, though it is less stable than the E isomer in terms of steric repulsion. 相似文献
28.
Yukiko Yasuoka Yuichiro Izumi Takashi Fukuyama Haruki Omiya Truyen D. Pham Hideki Inoue Tomomi Oshima Taiga Yamazaki Takayuki Uematsu Noritada Kobayashi Yoshitaka Shimada Yasushi Nagaba Tetsuro Yamashita Masashi Mukoyama Yuichi Sato Susan M. Wall Jeff M. Sands Noriko Takahashi Katsumasa Kawahara Hiroshi Nonoguchi 《Molecules (Basel, Switzerland)》2022,27(3)
Anemia is a major complication of chronic renal failure. To treat this anemia, prolylhydroxylase domain enzyme (PHD) inhibitors as well as erythropoiesis-stimulating agents (ESAs) have been used. Although PHD inhibitors rapidly stimulate erythropoietin (Epo) production, the precise sites of Epo production following the administration of these drugs have not been identified. We developed a novel method for the detection of the Epo protein that employs deglycosylation-coupled Western blotting. With protein deglycosylation, tissue Epo contents can be quantified over an extremely wide range. Using this method, we examined the effects of the PHD inhibitor, Roxadustat (ROX), and severe hypoxia on Epo production in various tissues in rats. We observed that ROX increased Epo mRNA expression in both the kidneys and liver. However, Epo protein was detected in the kidneys but not in the liver. Epo protein was also detected in the salivary glands, spleen, epididymis and ovaries. However, both PHD inhibitors (ROX) and severe hypoxia increased the Epo protein abundance only in the kidneys. These data show that, while Epo is produced in many tissues, PHD inhibitors as well as severe hypoxia regulate Epo production only in the kidneys. 相似文献
29.
A systematic perturbation theory is developed for the ESR shift and is applied to the spin-1/2 Heisenberg antiferromagnetic chain with a general anisotropic exchange interaction. Using the Bethe ansatz technique, the resonance shift is obtained exactly for the whole range of temperature and magnetic field in the first order of the anisotropy. The obtained g shift strongly depends on magnetic fields at low temperature, showing a significant deviation from the previous classical result. 相似文献
30.
Yoko Hirohara Yoshitaka OKawa Toshifumi Mihashi Tatsuo Yamaguchi Naoki Nakazawa Yasuko Tsuruga Hiroyuki Aoki Naoyuki Maeda Ichiro Uchida Takashi Fujikado 《Optical Review》2007,14(3):151-158
The purpose of this paper was to investigate the feasibility of a newly developed hyperspectral fundus imaging camera with
a liquid crystal tunable filter. The intensities of different wavelengths of light transmitted through an artery, vein, and
the area surrounding these vessels and reflected out were measured, and the differential spectral absorptions were analyzed.
Measurements were made from 16 normal eyes and from two artificial capillaries. The ratios of absorption (ROA) of arteries
to veins from 500 to 580 nm (range 1) and from 600 to 720 nm (range 2) were calculated. For all eyes, the ROArange1 was larger than ROArange2. The ROA obtained from the artificial capillary filled with blood saturated with oxygen or nitrogen was similar to that of
simulated data of oxy- and deoxyhemoglobin extinction rate. Most ROAs of human eyes were lower than those of the simulated
data and the artificial capillaries. Oxygen saturation analysis by hyperspectral fundus imaging of retinal vessels were qualitatively
in agreement with thein vitro analysis or simulated values. However, further improvements are necessary to evaluate the oxygen saturation quantitatively
in the retinal blood vessels. 相似文献