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21.
Jun-Ichi Anzai Yoko Sakata Yasuhiro Suzuki Akihiko Ueno Tetsuo Osa 《Journal of polymer science. Part A, Polymer chemistry》1983,21(3):855-864
Crown ether-modified polyethylenimines (PEI-CR) were prepared to elucidate their cation binding efficiency and selectivity by liquid-liquid and solid-liquid extraction methods. With alkali metal cations it was found that polyethylenimines containing benzo-15-crown-5 moieties (Ia and Ib) extracted all cations examined more efficiently than their monomeric analogs, especially in the cases of K+ and Rb+ cations. The solid-liquid extraction revealed clearly that the polymers complexed with K+ and Rb+ cations according to a 1:2 cation-to-crown stoichiometry. The high selectivities of the polymers for K+ and Rb+ were interpreted in terms of the favourable conformation of the polymer chain for the formation of intramolecular 1:2 complexes. On the contrary, these polymers bound alkali earth cations less effectively with low selectivities. 相似文献
22.
DESIGN AND PERFORMANCE OF THE OKAZAKI LARGE SPECTROGRAPH FOR PHOTOBIOLOGICAL RESEARCH 总被引:7,自引:1,他引:7
Masakatsu WatanabeMasaki Furuya†Yasuhiro Miyoshi†Yasunori Inoue†Isao Iwahashi‡Koichi Matsumoto‡ 《Photochemistry and photobiology》1982,36(4):491-498
A computer-operated spectrograph was recently built at Okazaki, Japan. Different specimens can be placed on a horseshoe-shaped focal curve (10 m long) covering a wavelength range of 250 to 1000 nm so they can be irradiated simultaneously. The linear dispersion is about 0.8 nm/cm. The photon fluence rate on the focal curve is 5 x 1015 . photons x cm-2 x s-1 at 300nm and 1 x 1016 photons x cm-2 x s-1 at 600 and at 900 nm. The spectral half width is 5.5 nm or less on the focal curve. The stray light content is about 10-5 of the main peak at the peak wavelength ± 100 nm. Specimens are set in microcomputer-controlled threshold boxes so that wavelengths, photon fluence rates, photon fluences and timing of irradiations are controlled automatically according to a pre-programmed schedule. An optical fiber system is also provided for remote irradiations. 相似文献
23.
Kunihito Miyake Yasuhiro Masaki Ikuya Miyamoto Shozo Yanagida Takeshi Ohno Akio Yoshimura Chyongjin Pac 《Photochemistry and photobiology》1993,58(5):631-636
We have investigated the photosensitized monomerization of the cis,syn -cyclobutane dimer of 1,3-di-methylthymine using riboflavin tetraacetate and a 5-deazaflavin derivative as photosensitizer. Although little monomerization of the dimer is induced by photoexcitation of the flavins in the absence of any additives, the flavins can function as an efficient photosensitizer in the presence of magnesium perchlorate. Mechanistic studies involving spectroscopic, quantum-yield and flash-photolysis measurements demonstrated that the photosensitized monomerization exclusively proceeds through electron transfer from the dimer to the triplet flavins complexed with Mg2+ . The effects of magnesium perchlorate are compared with those on the chloranil-photosensitized monomerization and also with the effects of HClO4 on the flavin-photosensitized reaction. 相似文献
24.
A facile 1,5-migration of a -butyldimethylsilyl group and a new cleavage reaction of -butyldimethylsilyl ether to alcohol in prostaglandin intermediates are described. 相似文献
25.
The bound site of Mo atoms and its local structure in a Mo/HY catalyst have been determined by detailed analysis of extended X-ray absorption fine structure (EXAFS). Molybdenum was introduced in the supercage of HY zeolite by cycles of saturated adsorption of Mo(CO)6 at room temperature and subsequent thermal decomposition at 573 K. Two Mo atoms per supercage were immobilized in each CVD-thermal treatment cycle. The Mo loading increased linearly with the cycles up to three cycles at saturation, where six Mo atoms were supported. Temperature-programmed decomposition of the adsorbed Mo(CO)6 was also characterized by GC, QMS, and FT-IR, respectively. The EXAFS analysis including multiple scattering based on theoretical calculations revealed that Mo bound with two oxygen atoms connects to Al, where one of the two oxygen atoms had been associated with a proton. The bound site is called the S(III)' site. The zeolite framework was significantly distorted by the introduction of low-valent Mo, resulting in isolation of the [MoO2Al] unit from the surrounding zeolite framework due to a quasi-disruption of Si-O bonds adjacent to the unit. In the mild oxidation of the low-valent Mo/HY sample two Mo=O bonds were newly formed and the position of Mo was displaced by 0.06 nm so that the distortion of zeolite framework around the Al atom was relieved. The structures were also supported by DFT calculations. This study is the first example that the position of metal cation in zeolite was determined unambiguously by the EXAFS analysis. 相似文献
26.
Vladislav?Tomi?i?Email author Vjekoslav?Butorac Jadranka?Viher Vladimir?Simeon 《Journal of solution chemistry》2005,34(6):613-616
The effect of temperature on the π∗←π transition band in the UV absorption spectrum of NO3−(aq) centered at ≈200 nm was studied in the temperature range 10–70 ∘C. The observed temperature independence of this band was in contrast to the significant influence of temperature on the nitrate π∗←n transition reported recently by us. However, taking into account the electronic states involved in both the transitions, it was concluded that this finding was in accordance with our previous assumption that interconversion between spectrally distinct (with respect to π∗←n band) nitrate species included the rupture/formation of hydrogen bond(s) in the hydration shell of the nitrate ion. 相似文献
27.
Bertosa B Kojić-Prodić B Wade RC Ramek M Piperaki S Tsantili-Kakoulidou A Tomić S 《Journal of chemical information and computer sciences》2003,43(5):1532-1541
The activity of a biological compound is dependent both on specific binding to a target receptor and its ADME (Absorption, Distribution, Metabolism, Excretion) properties. A challenge to predict biological activity is to consider both contributions simultaneously in deriving quantitative models. We present a novel approach to derive QSAR models combining similarity analysis of molecular interaction fields (MIFs) with prediction of logP and/or logD. This new classification method is applied to a set of about 100 compounds related to the auxin plant hormone. The classification based on similarity of their interaction fields is more successful for the indole than the phenoxy compounds. The classification of the phenoxy compounds is however improved by taking into account the influence of the logP and/or the logD values on biological activity. With the new combined method, the majority (8 out of 10) of the previously misclassified derivatives of phenoxy acetic acid are classified in accord with their bioassays. The recently determined crystal structure of the auxin-binding protein 1 (ABP1) enabled validation of our approach. The results of docking a few auxin related compounds with different biological activity to ABP1 correlate well with the classification based on similarity of MIFs only. Biological activity is, however, better predicted by a combined similarity of MIFs + logP/logD approach. 相似文献
28.
The synthesis and properties of novel anthracene-bridged porphyrin dimers having an oxomolybdenum(V) porphyrin unit, H(2)(DPA)[Mo(V)O(OMe)] (1) and (DPA)[Mo(V)O(OMe)][Zn(II)(MeOH)] (2), and the relevant monomer porphyrin complexes Mo(V)O(MPP)OMe (3) and Zn(II)(MPP) (4) are presented. An oxomolybdenum(V) unit was introduced into one of the two porphyrins in DPA to give 1, which has a free-base porphyrin unit. By introducing a zinc(II) ion to the free-base part, a mixed-metal complex of 2 was prepared and isolated. The structure of 2 was analyzed by X-ray crystallography (2.(7)/(6)CH(2)Cl(2), triclinic, P(-)1 (no. 2), a = 15.2854(12) A, b = 19.9640(15) A, c = 13.6915(12) A, alpha = 90.968(3), beta = 113.108(4), gamma = 96.501(4), Z = 2, R1 = 9.9, wR2 = 19.2). The structure of 2 demonstrated that a methanol is stably coordinated to the Zn(II) ion with the aid of a hydrogen bond to the methoxo ligand on the Mo(V) ion in the binding pocket of DPA. The electrochemical measurements of 2 suggested that the methanol was kept in the pocket of DPA in solution even at the reduced state of the molybdenum ion. 相似文献
29.
Yasuhiro Tachibana Ryusuke Muramoto Hajime Matsumoto Susumu Kuwabata 《Research on Chemical Intermediates》2006,32(5):575-583
We investigated the photoelectrochemical characteristics and photo-stability of Cu2O layered on a copper plate using a hydrophobic ionic liquid. Our findings revealed that Cu2O is stable under white light irradiation, provided water is removed from the electrolyte. Methyl viologen derivative, a well-established
electron acceptor, was introduced to the ionic liquid electrolyte, allowing the photo-induced electron transfer reaction at
the Cu2O/electrolyte interface to be characterized. The methyl viologen derivative exhibited two distinct redox reactions at −0.56
V and −0.98 V vs. Ag/AgCl, clearly indicating that no dimer formation or co-proportionation reaction occurred. The excessive photocurrents
being continuously generated resulted from a viable photo-induced electron transfer reaction from the Cu2O to the acceptor. However, in contrast, the reduction of the Cu2O by water in the aqueous solution causes this electron transfer to be inhibited. We further demonstrate that these findings
are vital to understanding the role of the Cu2O and its photoelectrochemical applications. 相似文献
30.
Ichikawa S Tada M Iwasawa Y Ikariya T 《Chemical communications (Cambridge, England)》2005,(7):924-926
Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed. 相似文献