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341.
Zhaoma Shu Iku Tanaka Azumi Ota Daichi Fushihara Naoko Abe Saki Kawaguchi Kosuke Nakamoto Fumiaki Tomoike Seiichi Tada Yoshihiro Ito Yasuaki Kimura Hiroshi Abe 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(20):6683-6687
Development of intracellular delivery methods for antisense DNA and siRNA is important. Previously reported methods using liposomes or receptor‐ligands take several hours or more to deliver oligonucleotides to the cytoplasm due to their retention in endosomes. Oligonucleotides modified with low molecular weight disulfide units at a terminus reach the cytoplasm 10 minutes after administration to cultured cells. This rapid cytoplasmic internalization of disulfide‐modified oligonucleotides suggests the existence of an uptake pathway other than endocytosis. Mechanistic analysis revealed that the modified oligonucleotides are efficiently internalized into the cytoplasm through disulfide exchange reactions with the thiol groups on the cellular surface. This approach solves several critical problems with the currently available methods for enhancing cellular uptake of oligonucleotides and may be an effective approach in the medicinal application of antisense DNA and siRNA. 相似文献
342.
Koji Kimura Koichi Hayashi Lada V. Yashina Naohisa Happo Takumi Nishioka Yuta Yamamoto Yoshihiro Ebisu Toru Ozaki Shinya Hosokawa Tomohiro Matsushita Hiroo Tajiri 《Surface and interface analysis : SIA》2019,51(1):51-55
We performed X-ray fluorescence holography measurements on an In-doped Bi2Se3 topological insulator and obtained an in-plane atomic image in the vicinity of In. We found that atomic images at the positions of the first nearest neighbors (NNs) are very weak whereas those at the positions of the second and the third NNs are relatively strong. On the basis of the fact that In is half of the atomic number of Bi, we attributed the origin of this feature to the clustering of the In atoms in the Bi plane. We calculated the intensity of the atomic images and confirmed that the formation of In cluster results in a decrease by 30% in the first NN atomic image intensity. However, the decrease in the magnitude is not enough to explain the experimental results, suggesting another contribution such as the lattice distortions. The effect of the lattice distortion on the atomic image intensity is discussed on the basis of the simulation including the positional fluctuation of In atoms. 相似文献
343.
A novel thermosetting imide compound having a respective phenylethynyl carbonyl group at both terminal ends was newly synthesized from an acid anhydride having a phenylethynyl carbonyl group and various diamine compounds. The thermosetting behavior of the obtained novel thermosetting imide compound having phenylethynyl carbonyl groups was analyzed through differential scanning calorimetry measurements and infrared spectroscopic analysis. As a result, it became clear that a curing reaction of phenylethynyl carbonyl groups proceeds at approximately 200°C and that the curing reaction thereof proceeds at a temperature that is lower by 150°C or more compared with that of phenylethynyl groups. Examination of the polymerization reaction of the imide compounds having phenylethynyl carbonyl groups using model compounds revealed that a reaction that imparted an alkene C=C and polycyclic aromatic structure progressed. Moreover, a network polymer obtained from a thermosetting imide compound having respective phenylethynyl carbonyl groups at both terminal ends exhibited extremely superior heat resistance and thermal decomposition resistance. These superior thermal properties are thought to be due to the strong molecular interaction (molecular packing) that results from the polycyclic aromatic structures and alkenes produced through polymerization of the phenylethynyl carbonyl groups and to the suppression of the movement of the molecular chains. 相似文献
344.
Hitoshi Abe Yasuhiro Niwa Yasuo Takeichi Masao Kimura 《Chemical record (New York, N.Y.)》2019,19(7):1457-1461
X‐ray absorption fine structure (XAFS) spectroscopy is one of the most widely used methods at synchrotron radiation facilities. XAFS gives us information on chemical states and local structures. Fundamentally, XAFS is bulk sensitive, not surface sensitive. If a surface sensitive XAFS method was available, surface chemical reactions can be observed under realistic conditions. Here, we report the development and present status of a type of surface sensitive x‐ray spectroscopy, which is named total reflection x‐ray spectroscopy, TREXS. 相似文献
345.
Masao Kimura Yasuo Takeichi Toshiki Watanabe Yasuhiro Niwa Ken'ichi Kimijima 《Chemical record (New York, N.Y.)》2019,19(7):1462-1468
Macroscopic properties of carbon fiber‐reinforced plastic (CFRP) and environmental barrier coating (EBC), widely used for airplanes, can be deteriorated by local cracks or degradation (“trigger sites”). We have tried to find these trigger sites using x‐ray microscopy (XM), which can provide the 2D or 3D images of the chemical states and microstructures. Crack initiation in CFRP was observed in a non‐destructive manner in multi‐scales (nm‐mm). 3D chemical‐state mapping of Yb in EBC was achieved with high resolution (<50 nm). In addition to XM, in‐situ observations at high temperatures were conducted for obtaining complementary information. X‐ray absorption spectroscopy (XAS) and x‐ray diffraction (XRD) analysis were performed simultaneously up to 1773 K. Dynamic XAS with short time‐resolution (<10 ns) was conducted to investigate changes in the local structure of metal. These approaches can help us identify degradation trigger sites in the materials. 相似文献
346.
Im HJ Ito T Kim HD Kimura S Lee KE Hong JB Kwon YS Yasui A Yamagami H 《Physical review letters》2008,100(17):176402
Ce 4d-4f resonant angle-resolved photoemission spectroscopy was carried out to study the electronic structure of strongly correlated Ce 4f electrons in a quasi-two-dimensional nonmagnetic heavy-fermion system CeCoGe1.2Si0.8. For the first time, dispersive coherent peaks of an f state crossing the Fermi level, the so-called Kondo resonance, are directly observed together with the hybridized conduction band. Moreover, the experimental band dispersion is quantitatively in good agreement with a simple hybridization-band picture based on the periodic Anderson model. The obtained physical quantities, i.e., coherent temperature, Kondo temperature, and mass enhancement, are comparable to the results of thermodynamic measurements. These results manifest an itinerant nature of Ce 4f electrons in heavy-fermion systems and clarify their microscopic hybridization mechanism. 相似文献
347.
Kimihiro Kimura Hiroyuki Iwashita Shinichiro Asayama Masahiro Sugimoto Gumpei Kikuchi Hideo Ogawa 《International Journal of Infrared and Millimeter Waves》2008,29(8):713-723
We have developed a 150 GHz band corrugated feed horn. These corrugated feed horns have been established by a new machining
method, which involves digging corrugations through a metal material. We were able to realize E plane and H plane symmetry,
low side lobe level, and low cross-polarization level. Measured co-polarization beam patterns above − 35 dB were consistent
with the simulated patterns within a designed frequency range. The peak levels of cross-polarization beam patterns were less
than − 30 dB. And, the performances were uniform in several horns. In the present paper, we describe the corrugated horn produced
by this methods. 相似文献
348.
Takeshi Kimura Shinya Ito Takashi Sasaki Satoshi Ogawa Ryu Sato Yasushi Kawai 《Heteroatom Chemistry》2008,19(4):394-401
4,9‐Diethyl[1,4]dihydrodithiino[5,6‐f]benzotrithiole (DTBT) gave a radical cation, DTBT(•+), and a dication, DTBT(2+), on treatment with a single‐electron oxidizing reagent. Both compounds showed an ESR signal, whereas the dication, generated by this procedure, was silent for 1H NMR. Hydrolysis of DTBT(2+) gave DTBT 1‐oxide (DTBT 1‐O) and 2‐oxide (DTBT 2‐O) together with DTBT and a mixture of several dioxides. A singlet‐state dication, DTBT(2+)‐S, which was generated upon treatment of DTBT 5‐oxide (DTBT 5‐O) with concentrated D2SO4, was detected by 1H and 13C NMR. After 20 h, the NMR signals disappeared while the solution was active for ESR. The results suggest that (i) a species generated from DTBT by oxidation with the single‐electron oxidizing reagent is a triplet‐state dication, DTBT(2+)‐T, and (ii) DTBT(2+)‐S, initially generated, gradually isomerizes to DTBT(2+)‐T in the solution, and DTBT(2+)‐T forms a partial spin pair. © 2008 Wiley Periodicals, Inc. Heteroatom Chem 19:394–401, 2008; Published online in Wiley InterScience ( www.interscience.wiley.com ). DOI 10.1002/hc.20445 相似文献
349.
350.
Masanari Kimura 《Tetrahedron letters》2018,59(14):1295-1300
β-Keto carboxylic acids are key intermediates in organic syntheses, used for the development of fine chemicals, natural products, and various biologically relevant molecules. Their utilities stem from the structural features and facile bond formations, e.g., asymmetric reduction of carbonyl groups for the synthesis of β-hydroxy carboxylic acids and conjugated addition reactions through decarboxylative enolate nucleophiles, which utilize the amphiphilic reactivity of β-keto carboxylic acids. Despite their versatility and utilities, development of efficient and straightforward synthetic methods for β-keto carboxylic acids has not attracted considerable attention owing to their instability. As efficient synthetic strategies for β-keto carboxylic acids and their derivatives, reactions of α-diazoesters, acylation of malonate anions, cross-coupling reactions, and CO2 insertion reactions are summarized in this review. 相似文献