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Genki Namba Yuki Mimura Prof. Yoshitane Imai Dr. Ryo Inoue Prof. Yasuhiro Morisaki 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(65):14871-14877
Optically active X-shaped molecules based on the planar chiral [2.2]paracyclophane building block were prepared, in which di(methoxy)terphenyl units were stacked on the central benzene rings. At 25 °C, anisolyl rings freely rotate in solution, while in the crystal form, they are fixed by intramolecular CH–π interactions, thereby leading to the expression of the axial chirality, i.e., propeller chirality was exhibited by the planar chiral [2.2]paracyclophane moiety. The X-shaped molecule exhibited good circularly polarized luminescence (CPL) profiles with moderate ΦPL and a large glum value in the order of 10−3 at 25 °C, in solution. In contrast, at −120 °C, dual CPL emission with opposite signs was observed. According to the theoretical studies, the rotary motion of the anisolyl units is suppressed in the excited states, and so emission from two isomers could be observed. These results demonstrate that the axial chirality was controlled by the planar chirality, leading ultimately to propeller chirality. 相似文献
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Method development for the determination of 24S‐hydroxycholesterol in human plasma without derivatization by high‐performance liquid chromatography with tandem mass spectrometry in atmospheric pressure chemical ionization mode 下载免费PDF全文
Hiroshi Sugimoto Masaaki Kakehi Yoshinori Satomi Hidenori Kamiguchi Fumihiro Jinno 《Journal of separation science》2015,38(20):3516-3524
We developed a highly sensitive and specific high‐performance liquid chromatography with tandem mass spectrometry method with an atmospheric pressure chemical ionization interface to determine 24S‐hydroxycholesterol, a major metabolite of cholesterol formed by cytochrome P450 family 46A1, in human plasma without any derivatization step. Phosphate buffered saline including 1% Tween 80 was used as the surrogate matrix for preparation of calibration curves and quality control samples. The saponification process to convert esterified 24S‐hydroxycholesterol to free sterols was optimized, followed by liquid–liquid extraction using hexane. Chromatographic separation of 24S‐hydroxycholesterol from other isobaric endogenous oxysterols was successfully achieved with gradient mobile phase comprised of 0.1% propionic acid and acetonitrile using L‐column2 ODS (2 μm, 2.1 mm id × 150 mm). This assay was capable of determining 24S‐hydroxycholesterol in human plasma (200 μL) ranging from 1 to 100 ng/mL with acceptable intra‐ and inter‐day precision and accuracy. The potential risk of in vitro formation of 24S‐hydroxycholesterol by oxidation from endogenous cholesterol in human plasma was found to be negligible. The stability of 24S‐hydroxycholesterol in relevant solvents and human plasma was confirmed. This method was successfully applied to quantify the plasma concentrations of 24S‐hydroxycholesterol in male and female volunteers. 相似文献
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Hidenori Hasimoto 《Fluid Dynamics Research》1988,3(1-4):1-12
Several aspects of vortex motion are considered, with a special stress on the present status of idealization, such as point vortices or vortex filament. As an introduction, elements of vortices induced by the transient flow past an obstacle are considered and their role and development are stated.
Following this introduction, a general survey of the issues in this symposium is made sketchily. As an example, the motion of point vortices in the presence of an external flow or a boundary is discussed on the basis of the Hamiltonian formalism. The cases of linear flow and semicircular boundary are taken as examples of regular and chaotic motions. Secular behaviour of a pair of vortices in the flow is remarked. 相似文献
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Hidenori Okamura Antony Crisp Sarah Hübner Sidney Becker Petra Rov Thomas Carell 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(51):18864-18869
The RNA world hypothesis assumes that life on Earth began with nucleotides that formed information‐carrying RNA oligomers able to self‐replicate. Prebiotic reactions leading to the contemporary nucleosides are now known, but their execution often requires specific starting materials and lengthy reaction sequences. It was therefore proposed that the RNA world was likely proceeded by a proto‐RNA world constructed from molecules that were likely present on the early Earth in greater abundance. Herein, we show that the prebiotic starting molecules bis‐urea (biuret) and tris‐urea (triuret) are able to directly react with ribose. The urea‐ribosides are remarkably stable because they are held together by a network of intramolecular, bifurcated hydrogen bonds. This even allowed the synthesis of phosphoramidite building blocks and incorporation of the units into RNA. Investigations of the nucleotides’ base‐pairing potential showed that triuret:G RNA base pairs closely resemble U:G wobble base pairs. Based on the probable abundance of urea on the early Earth, we postulate that urea‐containing RNA bases are good candidates for a proto‐RNA world. 相似文献
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Hidenori Kinoshita Kazuki Yaguchi Takayuki Tohjima Katsukiyo Miura 《Tetrahedron letters》2017,58(16):1607-1610
The diisobutylaluminum hydride (DIBAL-H)-promoted benzocyclization, recently developed by this group, was adopted for the synthesis of a natural product containing a 9,10-dihydrophenanthrene skeleton to demonstrate its synthetic utility. One of the extracts from the roots of Salvia hydrangea DC. ex Bentham (Lamiaceae), a 20-norabietane derivative, was selected as the target molecule. The key step forming the 9,10-dihydrophenanthrene skeleton was achieved by the DIBAL-H-promoted cyclization of a silylated 1,3-dien-5-yne easily accessible from a substituted α-tetralone. 相似文献
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Mohammad Salim Hidenori UbukataTakao Kimura Michinori Karikomi 《Tetrahedron letters》2011,52(49):6591-6593
The reaction of helical quinone with alcohols in the presence of Brønsted acid such as para-toluenesulfonic acid (pTSA) or HCl proceeded smoothly to produce the corresponding alkoxy substituted oxa[9]helicenes in good yields. 相似文献