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161.
Miki T Kori M Tozawa R Nakamura M Sugiyama Y Yukimasa H 《Chemical & pharmaceutical bulletin》2002,50(1):53-58
The (3,5-trans)-7-chloro-5-(2-chlorophenyl)-2-oxo-1,2,3,5-tetrahydro-4,1-benzoxazepine-3-acetic acid derivatives 1 have been previously identified as potent squalene synthase inhibitors. A series of (4,1-benzoxazepin-3-ylidene)acetic acid derivatives were synthesized and evaluated for their inhibition of rat and human squalene synthase, and the (E)-isomers were found to exhibit potent inhibitory activity, with the same potency as 4,1-benzoxazepine-3-acetic acid derivatives. In contrast the (Z)-isomers did not exhibit significant inhibitory activity, and the active conformation of the 4,1-benzoxazepine-3-acetic acid derivatives was deduced from the folded conformation of the (E)-isomers. 相似文献
162.
Hidefumi Hirai Kazuhiko Takeuchi Makoto Komiyama 《Journal of polymer science. Part A, Polymer chemistry》1981,19(10):2581-2594
By the use of various boron compounds methyl methacrylate and styrene were copolymerized under photoirradiations at ?20°C. The alternately regulating activities of the boron compounds in the copolymerizations were in the following order: boron trichloride > ethylboron dichloride > boron trifluoride > diethylboron chloride ? triethylboron (?0). Boron trichloride and ethylboron dichloride exhibited such high regulating activities that their presence in 1 mol% in the charged methyl methacrylate was sufficient to complete equimolar alternating copolymerization. The alternating copolymerization proceeded in the steady state. The copolymerization rates decreased in the following order: boron trichloride ? ethylboron dichloride > diethylboron chloride ? triethylboron (?0). The cotacticities of methyl methacrylate-centered triads in the resulting copolymers were identical to those prepared with boron trichloride, ethylboron dichloride, and diethylboron chloride. The mechanism of the alternating copolymerization is discussed. 相似文献
163.
Shinjiro Okuzawa Hidefumi Hirai Shoji Makishima 《Journal of polymer science. Part A, Polymer chemistry》1969,7(4):1039-1053
Stereoregulation in free-radical polymerization was studied for the polymerization of the 2:1 or 1:1 complex of methyl methacrylate with ZnCl2 or SnCl4. The complexes were polymerized with the use of a free-radical initiator or γ-ray irradiation either in the liquid or solid state at various temperatures ranging from ?196 to 110°C, and the tacticities of the resulting polymers were determined by NMR spectroscopy. The polymers had different and characteristic values of tacticities depending upon the complex species, i.e., the kind of metal chloride and the stoichiometry. The tacticities were found to be independent of the polymerization temperature in both the liquid and solid states, in contrast with the fact that tacticities of the polymer from pure monomer changed markedly with the temperature. A temperature dependence appeared in the polymerization system, which contained more monomer than that corresponding to the 2:1 complex. The effect of the viscosity or the solid phase on the stereoregulation was examined in comparison with the polymerization of a mixture of methyl methacrylate and liquid paraffin. Two possible explanations regarding the stereoregulation mechanism are offered in relation to the structures of the complexes. 相似文献
164.
Tze-Loon Neoh Yasuhiro Noda Hidefumi Yoshii Takeshi Furuta 《Journal of inclusion phenomena and macrocyclic chemistry》2006,56(1-2):117-123
The effect of cyclodextrins (CDs) on water solubility of iodine was investigated. Modified CDs greatly enhanced the solubility of iodine. On the contrary, enhancement by natural CDs was rather moderate whereby the solubility was only doubled at the highest β-CD concentration examined. Desorption experiment of iodine from solution was carried out with addition of various CDs to study the effect of CDs on iodine retention. α-CD was the most efficient in retarding iodine desorption. Later, various concentrations of α-CD were used in the desorption experiment to observe its volatile suppression effect and determine the stability constant of iodine/α-CD complexation. At α-CD concentration of 10.3 mM, no lost of iodine from the solution was detected. A model was developed for desorption of iodine from the solution based on mass transfer theory. The stability constant K given by this model was 3.28×104 M−1 which was in the same order as the value estimated in this study by solubility method and as well those reported by other authors. In release experiments of solid state inclusion complexes, stability of inclusion complex powders decreased in the order of α-CD>β-CD>randomly methylated β-CD (RM-β-CD). 相似文献
165.
Katsuma Hiraki Akihiko Kuroiwa Hidefumi Hirai 《Journal of polymer science. Part A, Polymer chemistry》1971,9(8):2323-2333
Norbornene is polymerized by ruthenium complex–tertiary phosphine catalysts to polymers consisting of trans-and cis-olefinic groups and 1,3-cyclopentylene group. The system derived from dichloro(dodeca-2,6,10-triene-1, 12-diyl)ruthenium-(IV) (1) and triphenylphosphine has a fairly high activity for the polymerization, while I itself has only a very low activity. The system derived from dichlorodi-μ-chlorobis-(2,7-dimethylocta-2,6-diene-1,8-diyl)diruthenium(IV) (II) and more moles of triphenyl-phosphine than four shows almost the same activity as the I-triphenylphosphine system does. However, II and dichloro(2,7-dimethylocta-2,6-diene-1,8-diyl)-(triphenylphosphine)ruthenium(IV) each polymerizes norbornene in a very high yield, in contrast with I. In addition, both dichlorotris(triphenylphosphine)ruthenium(II) and dichlorotetrakis(triphenylphosphine)ruthenium(II) have been found to display a considerably high activity for polymerization of norbornene. On the basis of these facts and the NMR data of the I– and II–triphenylphosphine systems, the mechanism for the polymerization of norbornene has been discussed. 相似文献
166.
Koji Machitani Hidefumi Sakamoto Yoshio Nakahara Keiichi Kimura 《Analytical sciences》2008,24(4):463-469
Tetraazacyclododecane and tetraazacyclotetradecane derivatives bearing a spirobenzopyran and three carboxymethyl moieties, 1 and 2, and a diethylenetriamine derivative bearing a spirobenzopyran and four carboxymethyl moieties 3 were synthesized. The isomerization behaviors based on the spirobenzopyran moiety of these ligands were studied by UV-visible spectrophotometry in aqueous solutions containing various metal ions at neutral pH. These ligands formed stable 1:1 complexes with lanthanide ions, while the spirobenzopyran moiety was isomerized to its corresponding merocyanine form even under dark conditions. In aqueous solutions containing a lanthanide ion, the absorption spectra of 1 or 2 showed remarkable blue shifts, while absorbances at the maximum absorption wavelengths in the visible region were enhanced; such changes are attributable to the isomerization to the merocyanine form of the spirobenzopyran moiety. These results suggest that the phenolate anion of the merocyanine moiety interacts very strongly with a lanthanide ion bound by the complexing moiety because of the high charge density of lanthanide ions. In contrast, the absorbance of merocyanine form was decreased by the complexation of the macrocyclic ligand with transition metal ions, such as Cu2+ and Zn2+. This result indicates that macrocyclic ligands, 1 and 2, formed complexes with transition metal ions only by the aminocarboxylate moieties, and the phenolate ion of merocyanine moiety was not able to participate in the complexation. This conclusion was also demonstrated by density functional theory calculations. 相似文献
167.
168.
Yoshihiro Mohri Taiji Yamada Keiji Morimura Tsunashi Kamo Hidefumi Makabe 《Tetrahedron letters》2007,48(33):5891-5894
Stereoselective synthesis of catechin and epicatechin dimers under intermolecular condensation is achieved by an equimolar amount of coupling catalyzed by Yb(OTf)3. The coupled products were successfully converted to procyanidin B1, B2, B3, and B4. 相似文献
169.
Junko Usukura Miyabi Hiyama Maki Kurata Yuji Hazama Xing-Ping Qiu Francoise M. Winnik Hidefumi Akiyama Nobuaki Koga 《Photochemistry and photobiology》2020,96(4):805-814
The equilibrium structures and optical properties of the photolabile caged luciferin, (7-diethylaminocoumarin-4-yl)methyl caged D-luciferin (DEACM-caged D-luciferin), in aqueous solution were investigated via quantum chemical calculations. The probable conformers of DEACM-caged D-luciferin were determined by potential energy curve scans and structural optimizations. We identified 40 possible conformers of DEACM-caged D-luciferin in water by comparing the Gibbs free energy of the optimized structures. Despite the difference in their structures, the conformers were similar in terms of assignments, oscillator strengths and energies of the three low-lying excited states. From the concentrations of the conformers and their oscillator strengths, we obtained a theoretical UV/Vis spectrum of DEACM-caged D-luciferin that has two main bands of shape nearly identical to the experimental UV/Vis spectrum. The absorption bands with maxima ~ 384 and 339 nm were attributed to the electronic excitations of the caged group and the luciferin moiety, respectively, by analysis of the theoretical UV/Vis spectrum. Furthermore, the analysis showed that DEACM-caged D-luciferin is excited in the caged group only by light of wavelength ranging within 400–430 nm, which is in the long-wavelength tail of the 384 nm band. This should be tested to lower damage upon photocleavage. 相似文献
170.
Kota Sato Hidefumi Hirai 《Journal of polymer science. Part A, Polymer chemistry》1991,29(10):1507-1514
The stereo and the electronic structures of methyl methacrylate and the binary molecular complex composed of methyl methacrylate and boron trichloride are determined by quantum chemical calculations based on ab initio molecular orbital methods with the STO-3G basis set. The Stable structures of methyl methacrylate in the free state are a transoid from and a cisoid form. The transoid form is slightly (0.5 kcal/mol) more stable than the cisoid form. The total energy change accompanying binary molecular complex formation is calculated to be ?43 kcal/mol. The most stable structure of the binary molecular complex composed of methyl methacrylate and boron trichloride is a twisted form in which the dihedral angle between the vinyl group and the ester group is 19.7°. A large amount of electron transfer from methyl methacrylate to boron trichloride is calculated to occur on binary molecular complex formation. Mulliken's population analysis shows the electron transfer to be the origin of the twist of the binary molecular complex. The energy level of the lowest unoccupied molecular orbital is substantially lowered by the coordination of boron trichloride. 相似文献