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41.
Mechanistic Investigation of Catalyst‐Transfer Suzuki–Miyaura Condensation Polymerization of Thiophene–Pyridine Biaryl Monomers with the Aid of Model Reactions
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Yu Tokita Masaru Katoh Dr. Yoshihiro Ohta Prof. Tsutomu Yokozawa 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(48):17436-17444
We have investigated the requirements for efficient Pd‐catalyzed Suzuki–Miyaura catalyst‐transfer condensation polymerization (Pd‐CTCP) reactions of 2‐alkoxypropyl‐6‐(5‐bromothiophen‐2‐yl)‐3‐(4,4,5,5‐tetramethyl‐1,3,2‐dioxaborolan‐2‐yl)pyridine ( 12 ) as a donor–acceptor (D –A) biaryl monomer. As model reactions, we first carried out the Suzuki–Miyaura coupling reaction of X–Py–Th–X′ (Th=thiophene, Py=pyridine, X, X′=Br or I) 1 with phenylboronic acid ester 2 by using tBu3PPd0 as the catalyst. Monosubstitution with a phenyl group at Th‐I mainly took place in the reaction of Br–Py–Th–I ( 1 b ) with 2 , whereas disubstitution selectively occurred in the reaction of I–Py–Th–Br ( 1 c ) with 2 , indicating that the Pd catalyst is intramolecularly transferred from acceptor Py to donor Th. Therefore, we synthesized monomer 12 by introduction of a boronate moiety and bromine into Py and Th, respectively. However, examination of the relationship between monomer conversion and the Mn of the obtained polymer, as well as the matrix‐assisted laser desorption ionization time‐of‐flight (MALDI‐TOF) mass spectra, indicated that Suzuki–Miyaura coupling polymerization of 12 with (o‐tolyl)tBu3PPdBr initiator 13 proceeded in a step‐growth polymerization manner through intermolecular transfer of the Pd catalyst. To understand the discrepancy between the model reactions and polymerization reaction, Suzuki–Miyaura coupling reactions of 1 c with thiopheneboronic acid ester instead of 2 were carried out. This resulted in a decrease of the disubstitution product. Therefore, step‐growth polymerization appears to be due to intermolecular transfer of the Pd catalyst from Th after reductive elimination of the Th‐Pd‐Py complex formed by transmetalation of polymer Th–Br with (Pin)B–Py–Th–Br monomer 12 (Pin=pinacol). Catalysts with similar stabilization energies of metal–arene η2‐coordination for D and A monomers may be needed for CTCP reactions of biaryl D–A monomers. 相似文献
42.
Plasma-enhanced MOCVD in which metal-organic compounds are sublimated directly into the growth chamber is studied for the first time as a new low-temperature process for growing superconducting YBa2Cu3O--x thin films. Y(THD)3, Ba(THD)2, Cu(THD)2 and oxygen are used as metal sources and oxydizing agent. Emission spectroscopy reveals that activated metal-organic compounds and activated oxygen species are present during film growth. Superconducting YBa2Cu3O7-x films whose zero-resistivity temperature are 50 K and 82 K are grown at 550°C and 600°C. 相似文献
43.
We developed a CZE method for simultaneous determination of pyridine-triphenylborane (PTPB) anti-fouling agent and its degradation products such as diphenylborinic acid (DPB), phenylboronic acid (MPB), and phenol in artificial seawater (ASW) with no extraction procedure. The ASW samples, in which 20 % (v/v) acetonitrile was added, were injected directly into the capillary using vacuum injection. As the background electrolyte, 60 mM sodium tetraborate adjusted to pH 9.8 was used. The LODs (S/N = 3) for PTPB, DPB, MPB, and phenol were, respectively, 55, 78, 126, and 30 μg L?1. The RSDs (n = 4) for analytes listed above were in the respective ranges of 2.7–5.7, 0.68–6.1, and 0.69–1.1 % for the peak area, peak height, and migration time. Simple degradation experiments were conducted to verify the usefulness of the proposed method. The PTPB samples dissolved in ASW were put in the open air, and rooms with and without light. The sample solutions were analyzed over time. We inferred that PTPB in ASW was more degraded by photolysis than by hydrolysis. The proposed CZE method has been demonstrated as a useful tool to elucidate the PTPB degradation process and its degradation products in ASW. 相似文献
44.
Dr. Yoji Horii Dr. Keiichi Katoh Dr. Kunihisa Sugimoto Dr. Ryo Nakanishi Dr. Brian K. Breedlove Prof. Dr. Masahiro Yamashita 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(12):3098-3104
In the research field of single-molecule magnets (SMMs), lanthanoid–lanthanoid interactions, so-called f–f interactions, are known to affect the SMM properties, although their magnitudes are small. In this article, an SMM with very weak f–f interactions is reported, and the effects of the interactions on the SMM properties are discussed. X-ray structural analysis of the DyIII-CdII-phthalocyaninato sextuple-decker complex (Dy2Cd3) reveals that the intramolecular Dy−Dy length in Dy2Cd3 is more than 13 Å, which is longer than the intermolecular Dy−Dy length. Even though the two DyIII ions are far apart, intermolecular ferromagnetic dipole–dipole interactions are observed in Dy2Cd3. From detailed analysis of ac magnetic susceptibilities, quantum tunneling of the magnetization (QTM) in Dy2Cd3 is partially suppressed owing to the existence of very weak Dy−Dy interactions. Our results show that even very weak Dy−Dy interactions act as a dipolar bias, suppressing QTM. 相似文献
45.
Shinpei Kado Yuuhei Takeshima Yoshio Nakahara Keiichi Kimura 《Journal of inclusion phenomena and macrocyclic chemistry》2012,72(1-2):227-232
It is well-known that cholesteric liquid crystals have an optical property, selective reflection, due to changes in the pitch of their helical structure. This unique property of cholesteric liquid crystals can be used to attain a visual sensing system showing color changes as the detection signal. In this paper, we report a visual sensing membrane comprising cholesteric liquid crystals, in which a 15-crown-5 derivative was incorporated as ion recognizing sites, for K+ in aqueous solution. The resulting CLC membrane showed a shift of the reflection peak sensitive to K+ in water. We have also designed polymer-dispersed liquid crystal membranes that showed ion-selective reflection peak shifts with improved response time. 相似文献
46.
Jun Kawahara Peter Andersson Ersman David Nilsson Kazuya Katoh Yasukazu Nakata Mats Sandberg Marie Nilsson Göran Gustafsson Magnus Berggren 《Journal of Polymer Science.Polymer Physics》2013,51(4):265-271
A flexible electrochromic active matrix addressed display, including 8 × 8 pixels, is demonstrated by using solution processing based on standard printing and coating manufacturing techniques. Each organic electrochromic display (OECD) pixel and its corresponding organic electrochemical transistor (OECT) are located on different sides of the flexible PET substrate. Electronic vias generated through the plastic substrate connects each OECD pixel with one addressing OECT. When comparing this display with actively addressed OECDs with all its components located on the same side, the present approach based on this electronic via substrate provides an enhanced pixel resolution and a relatively more simplified manufacturing process. © 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012 相似文献
47.
48.
Kisuke Tabata Naoya Jinno Keiichi Noda Masahiko Hashimoto Kazuhiko Tsukagoshi 《Chromatographia》2012,75(7-8):423-428
Tube radical distribution chromatography (TRDC) uses an untreated open tubular capillary tube and a ternary mixture of solvents (water and hydrophilic/hydrophobic organic solvents) as a carrier solution. A model analyte mixture comprising 1-naphthol, 1-naphthoic acid, 1-naphthalenesulfonic acid, 2,6-naphthalenedisulfonic acid, and 1,3,6-naphthalenetrisulfonic acid was examined by the TRDC and capillary zone electrophoresis (CZE) systems that comprised mainly a capillary tube and a detector. In the TRDC system the elution order of analytes could be changed by altering the component ratios of the solvents, whereas in the CZE system the elution order was changed by altering the electroosmotic flow direction. The experimental data obtained provide clues about the features and utility of TRDC as a new separation method. 相似文献
49.
Makoto Tsuruya Yoshimi Niwano Keisuke Nakamura Taro Kanno Takuji Nakashima Hiroshi Egusa Keiichi Sasaki 《Applied biochemistry and biotechnology》2014,174(6):2223-2235
Under the hypothesis that photo-irradiated proanthocyanidin could accelerate wound healing through reactive oxygen species (ROS) formation, we examined the effect of proanthocyanidin on 3T3-L1 mouse fibroblasts with or without photo-irradiation. As a result, irrespective of presence or absence of photo-irradiation, only 1 min exposure of the cells to proanthocyanidin resulted in accelerated proliferation of the cells in a concentration-dependent manner. Similarly to proanthocyanidin, 1 min pretreatment with catechin, caffeic acid, and chlorogenic acid accelerated the proliferative response, but gallic acid, epicatechin gallate, epigallocatechin, and epigallocatechin gallate failed. If incorporated active ingredient such as proanthocyanidin for such a short time as 1 min accelerates the proliferation response, a bioassay was conducted by utilizing antioxidant potential of proanthocyanidin. That is, intracellular oxidation of 2′,7′-dichlorodihydrofluorescin induced by H2O2 was significantly inhibited when the cells were pretreated with proanthocyanidin for 1 min, suggesting that incorporated proanthocyanidin into the cells exerted antioxidant effect. This was also supported by a liquid chromatography/mass spectrometry analysis in which incorporation of proanthocyanidin components such as catechin monomers and dimers into the cells within 1 min was confirmed. These results suggest that active polyphenolic compounds such as proanthocyanidin, catechin, caffeic acid, and chlorogenic acid incorporated into the cells in such a short time as 1 min could accelerate the proliferative response of the cells. 相似文献
50.