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281.
Zhao M Bai L Toki A Hasegawa R Sakai J Hasegawa T Ogura H Kataoka T Bai Y Ando M Hirose K Ando M 《Chemical & pharmaceutical bulletin》2011,59(3):371-377
A new cardenolide diglycoside (1) was isolated from Nerium oleander together with ten known cardenolide diglycosides 2-11. The structure of compound 1 was established on the basis of their spectroscopic data. The in vitro anti-inflammatory activity of compounds 1-11 was examined on the basis of inhibitory activity against the induction of the intercellular adhesion molecule-1 (ICAM-1). Compounds 2-5 were active at an IC(50) value of less than 0.8 μM. The cytotoxicity of compounds 1-11 was evaluated against three human cell lines normal human fibroblast cells (WI-38), malignant tumor cells induced from WI-38 (VA-13), and human liver tumor cells (HepG2). Compound 3 was active toward VA-13 cells, and compounds 2-5 were active toward HepG2 cells at IC(50) values of less than 1.3 μM. The multidrug resistance (MDR)-reversal activity of compounds 1-11 was evaluated on the basis of the amount of calcein in MDR human ovarian cancer 2780AD cells in the presence of each compound. Compounds 1 and 8 showed moderate effects on calcein accumulation. 相似文献
282.
Upon reaction of the 3',4'-unsaturated adenosine derivative 2 with N-iodosuccinimide (NIS) and thiophenol, an unexpected electrophilic hydrophenylsulfanylation proceeded to provide 4'-phenylsulfanylcordycepin 7 in 79% yield with the ratio 7a/7b = 6.6/1. A study of the reaction mechanism revealed that hydrogen iodide (HI) generated from NIS and PhSH acted as an active species. On the basis of a deuterium experiment using PhSD, initial protonation occurred at the β face of the double bond to furnish the β-π complex III, which underwent anti addition of PhSH as a major pathway. Nucleophilic substitution of N(6)-pivaloylated 9 with various alcohols in the presence of N-bromosuccinimide (NBS) gave the respective 4'-α-alkoxycordycepins 15a-21a as the major stereoisomers. Use of DAST in place of an alcohol gave the 4'-α-fluoro analogue 23a stereoselectively. Radical-mediated carbon-carbon bond construction was also applicable to 7, giving 4'-α-allylcordycepin (24a) and 4'-α-cyanoethylcordycepin (25) derivatives. 相似文献
283.
Prof. Dr. Kenshu Fujiwara Yuki Suzuki Nao Koseki Yu‐ichi Aki Yuta Kikuchi Shun‐ichi Murata Fuyuki Yamamoto Mariko Kawamura Prof. Dr. Toshio Norikura Prof. Dr. Hajime Matsue Prof. Dr. Akio Murai Prof. Dr. Ryo Katoono Prof. Dr. Hidetoshi Kawai Prof. Dr. Takanori Suzuki 《Angewandte Chemie (International ed. in English)》2014,53(3):780-784
Pectenotoxin‐2 (PTX2) is a shellfish toxin and has a non‐anomeric spiroacetal, which is not stabilized by an anomeric effect. The selective construction of the non‐anomeric spiroacetal has been a major problem in the synthesis of PTX2. Described herein is the stereoselective total synthesis of PTX2 via the isomerization of anomeric spiroacetal pectenotoxin‐2b (PTX2b). The synthesis of PTX2b was achieved by a simple process including sulfone‐mediated assembly of spirocyclic and bicyclic acetals and subsequent macrocyclization by ring‐closing olefin metathesis. Finally, the selective construction of PTX2 was accomplished by the early termination of a dynamic transition process to equilibrium in the acid‐catalyzed isomerization of anomeric PTX2b. [6,6]‐Spiroacetal pectenotoxin‐2c (PTX2c) was also synthesized from PTX2b. The cytotoxicity assay of the synthetic compounds against HepG2 and Caco2 cancer cells showed a potency of the order: PTX2?PTX2b>PTX2c. 相似文献
284.
Two types of naphthalene trimers linked by 1,3,4-oxadiazole spacers were synthesized and investigated for their physical and electronic properties. 2,6- and 2,7-isomers on central naphthalene moieties were obtained in the forms of pale yellow solids and colorless crystals, respectively. The melting point of the 2,6-isomer was higher than that of the 2,7-isomer. An X-ray crystallographic analysis revealed a π-stacked column with a short intermolecular distance in the crystals of the 2,6-isomer. The absorption maximum of the 2,6-isomer was red-shifted as compared to that of the 2,7-isomer, indicating a π-conjugation between di-2-naphthyloxadiazole moieties in the 2,6-isomer. The quantum yields of the 2,6- and 2,7-isomers were measured to be 0.97 and 0.74, relative to that of 2,5-di-2-naphthyl-1,3,4-oxadiazole (0.85). Molecular orbital (MO) calculations demonstrated that the 2,6-isomer had a higher electron affinity than the 2,7-isomer. Thus, the crosslinking of building blocks is important for the design of functional materials. 相似文献
285.
Sato Y Hayashi H Okazaki M Aso M Karasawa S Ueki S Suemune H Koga N 《Magnetic resonance in chemistry : MRC》2008,46(11):1055-1058
5-Uridine derivative carrying a TEMPO radical (UST) was prepared and its single strand (ssUST) and a double strand (dsUST) with its complementary strand were obtained. Similarly, single strands carrying two and five radicals (ssUST2 and ssUST5, respectively) and the corresponding double strands (dsUST2 and dsUST5) were prepared. Their electron paramagnetic resonance (EPR) spectra showed typical anisotropic broadening in the high field line. The rotational correlation times, tau(R), estimated by analyzing the EPR spectra are 1.1 x 10(-10), 5.9 x 10(-10), and 14 x 10(-10) s for UST, ssUSTm, and dsUSTm, respectively. The water-proton relaxivities, r(1) and r(2), at 25 MHz, 0.59 T, and 25 degrees C, also increased in the same order and the r(1) values were 0.26, 0.41, and 0.56 mM(-1) s(-1) for UST, ssUSTm, and dsUSTm, respectively. The r(1) values of 1.00 and 2.06 mM(-1) s(-1) for dsUST2 and dsUST5, respectively, were obtained. 相似文献
286.
Naokatsu Yamamoto Kouichi Akahane Naoki Ohtani 《Physica E: Low-dimensional Systems and Nanostructures》2004,21(2-4):322
We discuss a technique that allows us to grow high-density GaSb and InGaSb quantum dots (QDs) on (0 0 1)-oriented GaAs substrates. We study the use of Si atom irradiation on the substrate surface as an anti-surfactant before the QDs fabrication. It is clear that the densities of GaSb and InGaSb QDs are drastically enhanced with the Si atom irradiation. Photoluminescence intensities from these QDs are also increased with the Si atom irradiation. These results indicate that the Si atom irradiation technique is useful to improve the properties of the Sb-based QDs. 相似文献
287.
Shin-ichiro Gozu Kouichi Akahane Naokatsu Yamamoto Akio Ueta Naoki Ohtani 《Physica E: Low-dimensional Systems and Nanostructures》2006,32(1-2):230
InGaAs/AlAsSb systems lattice matched to InP have two distinguishable features: a high conduction band offset and type-II band configuration. Although, the former results in a large intersubband transition (ISBT) at conduction band, the latter makes it difficult to use the effective interband transition (IBT). To overcome this latter problem, the effect of the Sb was investigated because Sb would act as a band modulator from type-II to type-I. In0.57Ga0.43As1-xSbx/AlAs0.48Sb0.52 single quantum well (SQW) samples with various Sb compositions x, were grown on GaAs substrates via AlAs0.48Sb0.52 buffer layer. Their photoluminescence (PL) properties were examined to identify their band configurations. When the excitation laser power was increased, the PL property of In0.57Ga0.43As SQW sample, showed a larger blue shift than that of ones. This indicates that the band configuration modulates from type-II to type-I when the antimonide composition is larger than 0.13. These findings indicate that new functional devices can be fabricated using a combination of IBT and ISBT. 相似文献
288.
Onuki Y Morishita M Chiba Y Tokiwa S Takayama K 《Chemical & pharmaceutical bulletin》2006,54(1):68-71
We investigated the effect of fatty acids such as stearic acid (SA, 18:0), oleic acid (OA, 18:1), eicosapentaenoic acid (EPA, 20:5), and docosahexaenoic acid (DHA, 22:6) on a dipalmitoylphosphatidylcholine (DPPC) bilayer by determining the phase transition temperature, fluorescence anisotropy of 1,6-diphenyl-1,3,5-hexatriene (DPH), and detergent insolubility. Treatment with unsaturated fatty acid broadened and shifted the phase transitions of the DPPC bilayer to a lower temperature. The phase transition temperature and the value of fluorescence anisotropy of DPH at 37 degrees C decreased progressively with increasing treatment amounts of unsaturated fatty acid. A large amount of the DPPC bilayer treated with unsaturated fatty acid was dissolved in Triton X-100, obtaining a low level of detergent insolubility. These modifications of the bilayer physical properties were most pronounced with DHA and EPA treatment. These data show that unsaturated fatty acids, particularly DHA and EPA, induce a marked change in the lipid bilayer structure. The composition of fatty acids in the DPPC bilayer was similar after treatment with various unsaturated fatty acids, suggesting that the different actions of unsaturated fatty acids are attributed to change in the molecular structure (e.g., kinked conformation by double bonds). We further explored the change in physical properties induced by fatty acids dispersed in a water-in-oil-in-water multiple emulsion and found that unsaturated fatty acids acted efficiently on the DPPC bilayer, even when incorporated in emulsion form. 相似文献