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排序方式: 共有326条查询结果,搜索用时 15 毫秒
1.
Kento Nishikibe Keisuke Nishikawa Momochika Kumagai Matsumi Doe Yoshiki Morimoto 《化学:亚洲杂志》2022,17(1):e202101137
There are marine cytotoxic bromotriterpenoids, named the thyrsiferol family that are structurally characterized by some tetrahydropyran (THP) and tetrahydrofuran (THF) rings. The thyrsiferol family belongs to natural products that are often difficult to determine their stereostructures even by the current, highly advanced spectroscopic methods, especially in acyclic systems including stereogenic tetrasubstituted carbon centers. In such cases, it is effective to predict and synthesize the possible stereostructures. Herein, to elucidate ambiguous stereostructures and unassigned absolute configurations of aplysiol B, laurenmariannol, and saiyacenol A, members of the thyrsiferol family, we carried out their asymmetric chemical syntheses featuring 6-exo and 5-exo oxacyclizations of epoxy alcohol precursors and 6-endo bromoetherification of a bishomoallylic alcohol. In this paper, we report total assignments of their stereostructures through their asymmetric chemical syntheses and also their preliminary cytotoxic activities against some tumor cells. These results could not have been achieved without depending on asymmetric total synthesis. 相似文献
2.
A flow-injection system for the determination of 3-hydroxybutyrate in serum is described. 3-Hydroxybutyrate dehydrogenase is immobilized on poly(vinyl alcohol) beads and incorporated in a flow-injection system. 1-Methoxy-5-methylphenazinium methylsulphate reacts with enzymatically generated NADH to give H2O2, which is detected chemiluminometrically with the reaction of luminol and hexacynoferrate(III). Serum is diluted and filtered through an ultrafiltration membrane. The system responds linearly to injected samples (80 μl) in the concentration range 0.5–300 μM; the detection limit is 0.1 μM. The within-day relative standard deviation (n = 90) for 58 μM 3-hydroxybutyrate in serum is 0.8%. The maximum throughout is 20 samples per hour. The immobilized enzyme is stable for at least 1 month. 相似文献
3.
K. M. A. Salam Hidekazu Konishi Masahiro Mizuno Hisashi Fukuda Shigeru Nomura 《Applied Surface Science》2002,190(1-4):88-95
Polycrystalline (1−x)Ta2O5−xTiO2 thin films were formed on Si by metalorganic decomposition (MOD) and annealed at various temperatures. As-deposited films were in the amorphous state and were completely transformed to crystalline after annealing above 600 °C. During crystallization, a thin interfacial SiO2 layer was formed at the (1−x)Ta2O5−xTiO2/Si interface. Thin films with 0.92Ta2O5–0.08TiO2 composition exhibited superior insulating properties. The measured dielectric constant and dissipation factor at 1 MHz were 9 and 0.015, respectively, for films annealed at 900 °C. The interface trap density was 2.5×1011 cm−2 eV−1, and flatband voltage was −0.38 V. A charge storage density of 22.8 fC/μm2 was obtained at an applied electric field of 3 MV/cm. The leakage current density was lower than 4×10−9 A/cm2 up to an applied electric field of 6 MV/cm. 相似文献
4.
[reaction: see text] A newly developed strategy for construction of eight-membered carbocycles via [6 + 2] annulation that involves the combination of beta-alkenoyl acylsilanes and a vinyllithium derivative is described. A unique feature of this annulative approach is that it enables in one operation and a stereoselective manner construction of eight-membered ring systems containing useful functionalities for further synthetic elaboration from readily available six- and two-carbon components. 相似文献
5.
Akiko Sekihara Hidekazu Honma Tadahiro Fukuju Kiminori Maeda Hisao Murai 《Research on Chemical Intermediates》1998,24(8):859-877
Photooxidation (charge transfer) reactions of carbazole derivatives by maleic anhydride (MA) in alcoholic media are studied
by a time-resolved cw-ESR (TRESR) and Fourier transform ESR (FTESR) techniques. The CIDEP spectra observed in the systems
(methyl-, ethyl-, and phenyl-substituted carbazoles with MA) remarkably depend on the MA concentration. Under the high concentration
conditions, an emissive TM (triplet mechanism) polarization with a slight A/E (absorption/emission) pattern of the RPM (radical
pair mechanism) is observed. In the low concentration of MA, a TM-like absorptive polarization is superimposed on the A/E
pattern of the RPM. Since this reaction takes place exclusively through the triplet state, this spectral phase reveals that
the singlet state of the radical-ion pair (RIP) has an energy higher than that of the triplet state, in other words, the sign
of the apparent exchange interaction of the present RIP systems is positive. The total absorptive polarization observed in
the low concentration of MA is tentatively explained by the polarization transfer from the excited triplet state of carbazoles
in thermal equilibrium. 相似文献
6.
Nakao Y Imanaka H Sahoo AK Yada A Hiyama T 《Journal of the American Chemical Society》2005,127(19):6952-6953
Alkenyl- and aryl[2-(hydroxymethyl)phenyl]dimethylsilanes, highly stable tetraorganosilicon reagents, are found to react with aryl and alkenyl iodides in the presence of a palladium catalyst and K2CO3 as a base, significantly milder conditions compared with those ever reported for the silicon-based cross-coupling reactions. The reaction tolerates a wide range of functional groups, including silyl protectors, and allows a gram-scale synthesis to recover and reuse the silicon residue. 相似文献
7.
Yoshiaki Hidaka Hiromitsu Masaoka Hidekazu Oshita Takuji Nakamura Koji Tanaka Hiroyuki Kawano 《国际化学动力学杂志》1992,24(10):871-885
The thermal decomposition of vinylacetylene (C4H4) was studied behind reflected shock waves using both a single-pulse method (reaction time between 0.8 and 3.3 ms) and a time-resolved UV-absorption method (230 nm). The studies were done over the temperature range of 1170–1690 K at the total pressure range of 1.3–2.3 atm. The mechanism was used to interpret both the early and late stages of vinylacetylene decomposition at the high temperatures. It was confirmed that C4H4 dissociation proceeded through the following three channels. The rate constant expression of reaction (1) was determined as k1 = 6.3 × 1013 exp(?87.1 kcal/RT) s?1. The rate constants of the succeeding reactions (chain reaction, C4H4 + H → i-C4H3 + H2 and C4H4 + H → C2H2 + C2H3 and decomposition reactions of free radicals, i-C4H3 + M → C4H2 + H + M) were confirmed or estimated. © John Wiley & Sons, Inc. 相似文献
8.
Koichiro Nakanishi Susumu Okazaki Kenji Ikari Hidekazu Touhara 《Chemical physics letters》1981,84(3):428-432
Monte Carlo calculations have been carried out for pure water and an infinitely dilute aqueous solution of methanol at 298.15 K at ordinary density by the Metropolis method in NTV ensemble. The hydration structure around methanol revealed by a graphic display technique indicates a structure-forming effect near the hydrophobic group. 相似文献
9.
Tanaka H Yamada T Sugiyama S Shiratori H Hino R 《Journal of colloid and interface science》2005,286(2):812-815
Using a hydroxyl group appended free base porphyrin derivative (HP), porphyrin-introduced silica gels were synthesized by a sol-gel process. The HP content in the materials linearly increased with increasing the HP concentration. Meanwhile, free base tetraphenylporphyrin (TPP) with no hydroxyl groups were almost not incorporated into the silica gels. These facts suggested that the interaction between hydroxyl groups of the HP molecules and silica network is considerably strong. The UV-vis characters of HP-introduced materials were almost the same as pure HP molecules. The Beer's plot indicated that the HP molecules in the materials are dispersed. 相似文献
10.
[reaction: see text] A concise and stereoselective synthesis of the chiral building block, dioxanylpiperidene 4 as a precursor for deoxyazasugars, starting from the Garner aldehyde 5 using catalytic ring-closing metathesis (RCM) for the construction of the piperidine ring is described. The asymmetric synthesis of 1-deoxygalactonojirimycin and its congeners 1-3 was carried out via the use of 4 in a highly stereocontrolled mode. 相似文献