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21.
The d.c. polarographic current-potential curves of Cd(II)-EDTA complexes were examined in the pH range 0.5–10.0, to elucidate the mechanism of their electrode processes and to determine the relevant electrochemical kinetic parameters. It was shown that the first wave observed below pH 3 at ?0.58 to ?0.65 V vs. SCE is the reversible reduction wave of Cd(II) aquo-ion with kinetically-controlled limiting current, and the second wave observed above pH 1.5 at ?0.75 to ?1.21 V vs. SCE corresponds to the simultaneous irreversible reduction of four complex species, CdH3L+, CdH2L, CdHL? and CdL2?, where CdHpL(p?2)+ and L4? denote the protonated complex species with p protons and the unprotonated EDTA ion, respectively. Analysis of the dependence of limiting current on the hydrogen ion concentration led to the conclusion that the preceding reaction determining the behaviour of limiting current is CdH3L+?Cd2++H3L? with k3d=6.3×102 s?1 and k3f=3.3×106 s?1M?1, where k3d and k3f are the dissociation and formation rate constants, respectively. On the other hand, from analysis of the dependence of half-wave potentials of the second wave on the hydrogen ion concentration, the kinetic parameters of the four complex species were evaluated, and are given in Table 1. Further, it was shown that the cathodic rate constants of these four charge transfer processes at some reference potential together with those of Cd(II)-HEDTA complexes fulfil the linear free energy relationship. 相似文献
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24.
N Shibata T Minouchi Y Hayashi H Shibata T Ono H Shimakawa 《Chemical & pharmaceutical bulletin》1989,37(7):1877-1880
The effects of temperature, hematocrit (Hct), lipid level in plasma and cyclosporin A (CyA) level in whole blood on the concentration of CyA in plasma measured by high-performance liquid chromatography were studied in vitro. With rise in blood storage temperature before cells were removed, the concentration of CyA in plasma was increased in the temperature range between 10 degrees C and 37 degrees C, but was decreased between 4 degrees C and 10 degrees C. With rise in Hct, the concentration of CyA in plasma was decreased, and it was more markedly decreased at the blood storage temperature of 4 degrees C than at 37 degrees C. A lipid supplementation study showed that the concentration of CyA in plasma was increased with rise in plasma triglyceride level and in plasma cholesterol level at the storage temperature of 4 degrees C but not at 37 degrees C. Studies of the effect of CyA concentration in blood on the CyA distribution in blood demonstrated that the cellular/plasma concentration (C/P) ratio at low levels (less than 200 micrograms/ml) of plasma CyA ranged from 4 to 10 and was about 2 times higher than that at higher concentrations at 4 degrees C, but the ratio was relatively constant at 37 degrees C. The saturation capacity of the cellular fraction for CyA showed considerable individual variations, but there was no difference between the capacities at 4 degrees C and 37 degrees C. The separation of plasma after equilibration at 37 degrees C made it possible to avoid the variations in the distribution of CyA in whole blood associated with changes in Hct, lipid level in plasma and CyA level in whole blood, and to obtain a measurement reflecting the physiologically significant concentration of CyA in plasma. 相似文献
25.
M. Takagaki K. Ono S-I. Masunaga Y. Kinashi Y. Sakurai T. Kobayashi S-I. Miyatake N. Hashimoto 《Journal of Radioanalytical and Nuclear Chemistry》2001,247(2):389-392
Quantitative determination of ppb-order 10B was carried out in a small number of cultured tumor cells by particle tracks by the 10B(n,)7Li reactions using solid state nuclear track detector (SSNTD) for boron neutron capture therapy research. The detection limit of 10B concentration in tumor cells is less than 1·10-3 ppm under our experimental conditions which permits the quantitative determination of 10B in a small number of boronated tumor cells (105/ml = ca. 0.1 mg). Boron quantities in tumor cells determined were well compatible with the tumor cell killing effects of boron neutron capture therapy. 相似文献
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Kiyotake Suenaga Tsuyoshi Mutou Takashi Itoh Noboru Takada Masaki Takagi Hideo Kigoshi Kiyoyuki Yamada 《Tetrahedron》2004,60(38):8509-8527
The bioassay-guided fractionation of the cytotoxic constituents of the Japanese sea hare Dollabella auricularia led to the isolation of aurilide (1), a 26-membered cyclodepsipeptide. The gross structure of 1 was established by spectroscopic analysis including 2D NMR techniques. The absolute stereostructure was determined by chiral HPLC analysis of acid hydrolysates of 1 and by the enantioselective synthesis of a degradation product arising from a dihydroxylated fatty acid portion. The enantioselective synthesis of 1 was achieved in 12% overall yield (16 steps) and confirmed the absolute stereostructure of 1. The cytotoxicity of 1 was evaluated using a synthetic sample, which was found to exhibit potent cytotoxicity against HeLa S3 cells with an IC50 of 0.011 μg/mL. Further biological and pharmacological studies of 1 have been carried out by using synthetic 1. 相似文献
28.
Kenji Yokota Hideo Tomioka Teruyuki Ono Fumimasa Kuno 《Journal of polymer science. Part A, Polymer chemistry》1972,10(5):1335-1343
The sensitization effect of tertiary amines on the photopolymerization of methyl methacrylate was studied. N,N-Dimethylbenzylamine, triethylamine, and N,N-dimethylaniline increased the rate of polymerization in this order, but pyridine did not show any effect. A free-radical mechanism was confirmed by the tacticity of polymer, the retarding effect of hydroquinone, and the copolymer composition with styrene. On the basis of the detailed kinetics of the sensitized polymerization and the ultraviolet spectra of the reaction mixtures, a sensitization mechanism is proposed, in which the excited monomer and the amine form a complex and generate an initiating radical. 相似文献
29.
Rikuhei Tanikaga Yoshimasa MatsumotoMaki Sakaguchi Yohei KoyamaKentaro Ono 《Tetrahedron letters》2003,44(35):6781-6783
Lipase-mediated acetylations of trans- and cis-2-substituted cyclohexanols gave the corresponding (1R)-cyclohexyl acetates and (1S)-cyclohexanols in high yields and ee, but c-4-tert-butyl-c-2-ethenyl-r-1-cyclohexanol was unreactive owing to the steric interaction between the axial OH group and the axial H atoms at the 3- and 5-positions. In the cis-isomer the OH group occupies an equatorial position to bind to the lipase, and less bulky axial alkenyl and alkynyl groups might not so much prevent acetylations than an alkyl group. 相似文献
30.
Akiya Karen Noriaki Ikeda Noboru Mataga Fumio Tanaka† 《Photochemistry and photobiology》1983,37(5):495-502
Formation of singlet charge transfer (heteroexcimer) states in the course of the fluorescence quenching of lumiflavin and riboflavin tetrabutyrate by indole and N-methylindole have been directly observed by means of time-resolved absorption spectral measurements using a picosecond laser photolysis method. Similar transient spectra have been observed also in the case of a flavoenzyme, D-amino acid oxidase. 相似文献