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133.
Dr. Chaolu Eerdun Thi Hien Thuy Nguyen Takuya Okayama Satoshi Hisanaga Prof. Dr. Jun-ichiro Setsune 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(22):5777-5786
The hexapyrrole-α,ω-dicarbaldehydes 1 a and 1 b were metallated with CuII, NiII, and PdII to give bimetallic complexes where a pair of 3 N+O four-coordinate metal planes are helically distorted and the central 2,2′-bipyrrole subunit adopts a cis or trans conformation. X-ray crystallographic analysis of the bisCu complex revealed a closed form with a cis-2,2′-bipyrrole subunit and an open form with a trans-2,2′-bipyrrole subunit. The bisPd complexes took a closed form both in the solid state and in solution. They are regarded as single helicates of two turns and the energy barrier for the interchange between an M helix and a P helix was remarkably influenced by the bulky 3,3′-substituent of the central 2,2′-bipyrrole subunit. Although the bisNi complexes adopt a closed form in the solid state, they exist as a homohelical open C2-symmetric form or a heterohelical open Ci-symmetric form in solution. A theoretical study suggested that the closed form of 1 a Pd was stabilized by the Pd–Pd interaction. Compound 1 a Pd was reversibly oxidized by one electron at 0.14 V versus ferrocene/ferrocenium (Fc/Fc+) and this oxidized species showed Vis/NIR absorption bands at λ=767 and 1408 nm. 相似文献
134.
Dr. Yusaku Nomura Dr. Frédéric Thuaud Dr. Daisuke Sekine Prof. Dr. Akihiro Ito Satoko Maeda Dr. Hiroyuki Koshino Dr. Daisuke Hashizume Dr. Atsuya Muranaka Dr. Thomas Cruchter Prof. Dr. Masanobu Uchiyama Prof. Dr. Satoshi Ichikawa Prof. Dr. Akira Matsuda Prof. Dr. Minoru Yoshida Prof. Dr. Go Hirai Prof. Dr. Mikiko Sodeoka 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(35):8387-8392
A synthetic methodology to access all possible stereoisomers of spectomycin A1 (SMA1) and A2 (SMA2) has been established through late-stage diversification. The key reaction for the construction of all four diastereomers is an intramolecular cyclization based on the umpolung of π-allyl palladium species with bis(pinacolato)diborane (B2(pin)2). Silyl group assisted direct benzylic oxidation of each isomer enabled construction of the fragile β-hydroxytetralone skeleton to provide the SMAs. The relative and absolute stereochemistry of SMA2 was also determined, and the absolute stereochemistry of SMA1 was extrapolated based on the optical rotation of SMA2. The axial chirality of SMAs is discussed based on circular dichroism spectra and DFT calculations, and it is concluded that the M isomer is predominant in solution. Biochemical assessment of all isomers in vitro revealed that the C9 hydroxyl group and dimeric structure were both important for protein SUMOylation-inhibitory activity. 相似文献
135.
To prepare cross‐linked silicone (silicone rubber) particles in an aqueous medium, we investigated two synthesis methods involving a miniemulsion system. The first method was based on cationic ring‐opening polymerization of cyclic siloxane, which is a common synthetic route for linear silicone oil and uses octamethylcyclotetrasiloxane (D4) as the monomer and dimeric D4 (bis‐D4) as the cross‐linker. Although this method produces silicone particles, the particles do not remain in the particulate state after drying because of low cross‐linking density. The polymerization mechanism of this method was also investigated, which proceeds under the ring‐opening reaction of D4 in monomer droplets and upon polycondensation of hydrolyzed D4, which occurs in the water phase (ie, outside the monomer droplets). This mechanism implied that introducing the cross‐linking structure into particles is difficult because of the low solubility of bis‐D4 in water. To overcome these difficulties, we demonstrated a second method of preparing silicone particles based on the thiol‐Michael addition reaction between thiol‐terminated silicone oil and triacrylate in miniemulsion systems. Transmission electron microscopy images indicated that the silicone particles obtained in the particulate state upon drying and the aggregates of these particles showed elasticity. 相似文献
136.
Katsuya Hyodo Yoshinori Arisaka Satoshi Yamaguchi Tetsuya Yoda Nobuhiko Yui 《Macromolecular bioscience》2019,19(4)
Modulation of material properties and growth factor application are critical in constructing suitable cell culture environments to induce desired cellular functions. Sulfonated polyrotaxane (PRX) surfaces with immobilized vascular endothelial growth factors (VEGFs) are prepared to improve network formation in vascular endothelial cells. Sulfonated PRXs, whereby sulfonated α‐cyclodextrins (α‐CDs) are threaded onto a linear poly(ethylene glycol) chain capped with bulky groups at both terminals, are coated onto surfaces. The molecular mobility of sulfonated PRX surfaces is modulated by tuning the number of threading α‐CDs. VEGF is immobilized onto surfaces with varying mobility. Low mobility and VEGF‐immobilization reinforce cell proliferation, yes‐associated protein activity, and rhoA, pdgf, ang‐1, and pecam‐1 gene expression. Highly mobile surfaces and soluble VEGF weakly affect these cell responses. Network formation is strongly stimulated in vascular endothelial cells only on low‐mobility VEGF‐immobilized surfaces, suggesting that molecular mobility and VEGF immobilization synergistically control cell function. 相似文献
137.
Dr. Yohei Hattori Tatsuya Maejima Yumi Sawae Jun-ichiro Kitai Prof. Masakazu Morimoto Dr. Ryojun Toyoda Prof. Hiroshi Nishihara Prof. Satoshi Yokojima Dr. Shinichiro Nakamura Prof. Kingo Uchida 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(50):11441-11450
The cyclization reaction of diarylethenes having an azulene ring occurs only via higher excited states. Novel diarylethenes having an azulene ring with a strong donor or acceptor were synthesized and examined in these reactions. A derivative having an electron-donating 1,3-benzodithiol-2-ylidenemethyl group at the 1-position of the azulene ring showed photochromism, whereas neither a derivative having a π-conjugated electron-donating group at the 3-position of the azulene ring nor derivatives having a π-conjugated electron-withdrawing group at the 1- or 3-position of the azulene ring showed any photochromism. The photoreactivities of these compounds were explained by calculating forces and bond orders on the excited states using density functional theory (DFT) and time-dependent (TD)-DFT. 相似文献
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139.
Dr. Yui Sasaki Satoshi Ito Zhoujie Zhang Xiaojun Lyu Dr. Shin-ya Takizawa Dr. Riku Kubota Prof. Dr. Tsuyoshi Minami 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(69):16236-16240
An artificial tongue that detects astringent components for a comprehensive evaluation of taste has not been established to date. Herein, we first propose fluorescent polythiophene (PT) derivatives ( S1 – S3 ) modified with 3-pyridinium boronic acid as supramolecular chemosensors for wine components including astringent procyanidin C1. After numerous attempts for the synthetic conditions, more than 95 mol % of the PT unit was modified with the pyridinium boronic acid moiety. To evaluate the PT derivatives as chemosensors of the artificial tongue, qualitative and quantitative analyses were performed with four types of wine components (i.e., sweet, sour, bitter, and astringent tastes) in combination with pattern recognition models. Notably, procyanidin C1 in the actual wine sample was successfully detected in a quantitative manner. In other words, we have established an authentic artificial tongue using PT based supramolecular chemosensors. 相似文献
140.
Satoshi Goshima Masayuki Kanematsu Hiroshi Kondo Yusuke Tsuge Haruo Watanabe Yoshimune Shiratori Minoru Onozuka Noriyuki Moriyama 《Magnetic resonance imaging》2009,27(9):1230-1235
The purpose of this study was to compare observer interpreted steady-state coherent coronal images and gadolinium-enhanced axial images in terms of the detection and grading of esophageal varices. Magnetic resonance imaging (MRI) and gastrointestinal endoscopy were performed within 2 weeks in 90 patients with chronic liver damage, including 55 with untreated esophageal varices, for periodic screening purposes. Two blinded readers retrospectively reviewed T1- and T2-weighted images with gadolinium-enhanced (gadolinium image set) and steady-state coherent (coherent image set) images. Sensitivity for the detection of esophageal varices was higher (P<.001) in the gadolinium image set (76%) than in the coherent image set (35%); on the other hand, specificity was higher (P<.001) in the coherent image set (91%) than in the gadolinium image set (66%). Furthermore, area under the ROC curve was higher for the gadolinium image set (Az=0.823) than the coherent image set (Az=0.761) (P=.48). Moderate and weak positive correlations with endoscopic grades were found for the gadolinium image (r=0.48, P<.01) and coherent image sets (r=0.34, P=.018). The addition of steady-state coherent imaging to the current routine liver imaging protocol did not improve the detection or grading of esophageal varices, whereas gadolinium-enhanced imaging was found to be potentially valuable. Nevertheless, endoscopy was confirmed to be mandatory in patients with esophageal varices suspected by MRI of the liver. 相似文献