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81.
Atsunori Morigaki Kazuki Tsukade Satoru Arimitsu Tsutomu Konno Toshio Kubota 《Tetrahedron》2013,69(5):1521-1525
The reaction of β-fluoroalkylated α,β-unsaturated ketones with various enamines gave 4-fluoroalkylated 3,4-dihydro-2H-pyrans as a major product in good yields by a one-pot operation, and these products display the high diastereoselection just after single recrystallization. This unexpected result is rationalized by the unique reactivity of β-fluoroalkylated α,β-unsaturated ketones. As the synthetic application, 4-trifluoromethyl tetrahydropyran was synthesized in moderate isolated yield with high diastereoselectivity. 相似文献
82.
Yutaka Kubota Yuri Kaneda Kazuhiro Haraguchi Mirei Mizuno Hiroshi Abe Satoshi Shuto Takayuki Hamasaki Masanori Baba Hiromichi Tanaka 《Tetrahedron》2013
The key glycosyl donor for the target molecule 12 was prepared by two-step sequences; (1) acetalization of tert-butyldimethylsilyloxyacetaldehyde with 3-bromopropanediol, (2) DBN-initiated β-elimination of the resulting 2-(tert-butyldimethylsilyloxy)methyl-4-bromomethyl-1,3-dioxolane 11. Electrophilic glycosidation between 12 and silylated pyrimidine nucleobase proceeded efficiently to provide a mixture of β- and α-anomers of the respective glycosides 14 and 15. Tin radical-mediated reduction of the bromomethyl functional group of 14 and 15 gave protected 4′-C-methyl-dioxorane uracil- 16 and thymine nucleoside 17. The respective cytosine nucleoside 18 was synthesized from 16. De-silylation of 4′-methyl-1′,3′-dioxolane pyrimidine nucleosides 16–18 gave the target molecules. Evaluation of the anti-HIV-1 activity of the β- and α-anomers of the novel 4′-C-methyl-1′,3′-dioxolane nucleosides 22β,α–24β,α revealed that none of the nucleoside derivatives possess anti-viral activity against HIV-1 and show cytotoxicity against MT-4 cells at 100 μM. 相似文献
83.
The local molecular orientation in the electroclinic effect of the chiral smectic A phase in a surface-stabilised cell has been determined using a time-resolved synchrotron X-ray microbeam diffraction technique. Space- and time-resolved X-ray wide-angle halo scattering under an electric field reveals the static and dynamic intralayer molecular orientation. The molecular orientation varies spatially in accordance with the stripe texture and is dependent on the applied voltage. It has been found that the deviation of the molecular orientation from the rubbing direction depends strongly on the sample history. The relation between the apparent molecular orientation and the layer structure is discussed. 相似文献
84.
A novel oligonucleotide delivery system that is based on oligonucleotide–nanoparticle conjugates has been described. Installed oligonucleotides were modified with the carbohydrate at the 3′ terminus, accordingly, constructed nanoparticles display clustered carbohydrates on their outer layer for the targeted delivery of oligonucleotides. The method for the construction of ligand-functionalized nanoparticle was simple and reproducible. The stability of the nanoparticles displaying clustered carbohydrates greatly increased in serum compared to nanoparticles without carbohydrates. In order to investigate the targetability of oligonucleotide–nanoparticle conjugates into primary hepatic parenchymal cells, freshly isolated rat hepatocytes were incubated with nanoparticles and the amount of internalized gold nanoparticles was evaluated by an inductively coupled plasma mass spectroscopy analysis. Nanoparticles displaying clustered carbohydrates internalized more efficiently than nanoparticles without carbohydrate modifications. In particular, the cellular uptakes of oligonucleotide-conjugated gold nanoparticle increased 1.7 ~2.0-fold by galactose modification. Competition assay revealed that clustered galactose enhanced the internalization of the nanoparticle into primary hepatic parenchymal cells by a receptor-mediated process. Figure
A novel oligonucleotide delivery system that is based on oligonucleotide-nanoparticle conjugates has been described. Constructed nanoparticles display clustered carbohydrates on their outer layer. The stability of the nanoparticles displaying clustered carbohydrates increased in serum, and clustered galactose enhanced the internalization of the nanoparticle to hepatic parenchymal cells by a receptor-mediated process 相似文献
85.
Dr. Emi Uchida Dr. Kouji Sakaki Dr. Yumiko Nakamura Dr. Reiko Azumi Dr. Yuki Hirai Dr. Haruhisa Akiyama Dr. Masaru Yoshida Dr. Yasuo Norikane 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(51):17391-17397
Photoinduced phase transitions caused by photochromic reactions bring about a change in the state of matter at constant temperature. Herein, we report the photoinduced phase transitions of crystals of a photoresponsive macrocyclic compound bearing two azobenzene groups ( 1 ) at room temperature on irradiation with UV (365 nm) and visible (436 nm) light. The trans/trans isomer undergoes photoinduced phase transitions (crystal–isotropic phase–crystal) on UV light irradiation. The photochemically generated crystal exhibited reversible phase transitions between the crystal and the mesophase on UV and visible light irradiation. The molecular order of the randomly oriented crystals could be increased by irradiating with linearly polarized visible light, and the value of the order parameter was determined to be ?0.84. Heating enhances the thermal cis‐to‐trans isomerization and subsequent cooling returned crystals of the trans/trans isomer. 相似文献
86.
Yoshihiro Kon Toshiyuki Yokoi Masato Yoshioka Shinji Tanaka Yumiko Uesaka Takehisa Mochizuki Kazuhiko Sato Takashi Tatsumi 《Tetrahedron》2014
Selective oxidation of sulfides to sulfoxides and sulfones with hydrogen peroxide under organic solvent-free conditions was demonstrated by the MWW-type titanosilicate zeolite catalyst. Sulfides were oxidized smoothly to give sulfoxides with good selectivities at ambient temperature using 1.0–1.2 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst. Especially, the Ti-MWW with an interlayer-expanded structure (Ti-IEZ-MWW) catalyst showed high activity with good chemoselectivity for the oxidation of various sulfides. The catalyst is recyclable for at least five cycles, and the only byproduct is water. Sulfides were directly oxidized to give sulfones in high yields by 2.5 equiv of hydrogen peroxide with the MWW-type titanosilicate zeolite catalyst under organic solvent-free conditions. 相似文献
87.
Tomohiro Sakata Shingo Ogawa Keiko Inoue Yumiko Shimizu Yusaku Tanahashi 《Surface and interface analysis : SIA》2022,54(6):661-666
To systematically evaluate the quality of SiNx films in multi-stacked structures, we investigated the effects of post-deposition annealing (PDA) on the film properties of SiNx within the SiO2/SiNx/SiO2/Si stacked structure by performing X-ray photoelectron spectroscopy (XPS), X-ray reflectivity (XRR), Fourier transform infrared (FT-IR) spectroscopy, and scanning transmission electron microscope–electron energy loss spectroscopy (STEM-EELS) analyses. The XPS results showed that PDA induces the oxidation of the SiNx layer. In particular, new finding is that Si-rich SiNx in the SiNx layer is preferentially oxidized by PDA even in multi-stacked structure. The XRR results showed that the SiNx layer becomes thinner, whereas the interface layer between the SiNx layer and Si becomes thicker. It is concluded by STEM-EELS and XPS that this interface layer is SiON layer. The density of N–H and Si–H bonding within the stacked structure strongly depends on the PDA temperature. Our study helps elucidate the properties of SiNx films in stacked structures from various perspectives. 相似文献
88.
Keiichi Hirano Yoshiki Yamashita Yumiko Takahashi Hiroshi Sugiyama 《Journal of synchrotron radiation》2015,22(4):956-960
A novel X‐ray Bragg optics is proposed for variable‐magnification of an X‐ray beam. This X‐ray Bragg optics is composed of two magnifiers in a crossed arrangement, and the magnification factor, M, is controlled through the azimuth angle of each magnifier. The basic properties of the X‐ray optics such as the magnification factor, image transformation matrix and intrinsic acceptance angle are described based on the dynamical theory of X‐ray diffraction. The feasibility of the variable‐magnification X‐ray Bragg optics was verified at the vertical‐wiggler beamline BL‐14B of the Photon Factory. For X‐ray Bragg magnifiers, Si(220) crystals with an asymmetric angle of 14° were used. The magnification factor was calculated to be tunable between 0.1 and 10.0 at a wavelength of 0.112 nm. At various magnification factors (M≥ 1.0), X‐ray images of a nylon mesh were observed with an air‐cooled X‐ray CCD camera. Image deformation caused by the optics could be corrected by using a 2 × 2 transformation matrix and bilinear interpolation method. Not only absorption‐contrast but also edge‐contrast due to Fresnel diffraction was observed in the magnified images. 相似文献
89.
Bobo Dang Dr. Tomoya Kubota Prof. Dr. Ana M. Correa Prof. Dr. Francisco Bezanilla Prof. Dr. Stephen B. H. Kent 《Angewandte Chemie (International ed. in English)》2014,53(34):8970-8974
Ts1 toxin is a protein found in the venom of the Brazilian scorpion Tityus serrulatus. Ts1 binds to the domain II voltage sensor in the voltage‐gated sodium channel Nav and modifies its voltage dependence. In the work reported here, we established an efficient total chemical synthesis of the Ts1 protein using modern chemical ligation methods and demonstrated that it was fully active in modifying the voltage dependence of the rat skeletal muscle voltage‐gated sodium channel rNav1.4 expressed in oocytes. Total synthesis combined with click chemistry was used to label the Ts1 protein molecule with the fluorescent dyes Alexa‐Fluor 488 and Bodipy. Dye‐labeled Ts1 proteins retained their optical properties and bound to and modified the voltage dependence of the sodium channel Nav. Because of the highly specific binding of Ts1 toxin to Nav, successful chemical synthesis and labeling of Ts1 toxin provides an important tool for biophysical studies, histochemical studies, and opto‐pharmacological studies of the Nav protein. 相似文献
90.