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151.
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Hideyuki Higashimura Kiyoshi Fujisawa Shuhei Namekawa Masaaki Kubota Akinobu Shiga Yoshihiko Moro‐Oka Hiroshi Uyama Shiro Kobayashi 《Journal of polymer science. Part A, Polymer chemistry》2000,38(Z1):4792-4804
Various effects on the coupling selectivity of the oxidative polymerization of 4‐phenoxyphenol catalyzed by (1,4,7‐triisopropyl‐1,4,7‐triazacyclononane)copper(II) halogeno complex [Cu(tacn)X2] are described. With respect to the amount of the catalyst and the nature of the halide ion (X) of Cu(tacn)X2, the coupling selectivity hardly changed. The Cu(tacn) catalyst possessed a turnover number greater than 1860. As the temperature of the reaction and the polarity of the reaction solvent were elevated, the C O coupling at the o‐position increased, but the C C coupling was not involved. For the polymerization in toluene at 80 °C, poly(1,4‐phenylene oxide), obtained as a methanol‐insoluble part, showed the highest number‐average molecular weight of 4000 with a melting point (Tm) of 195 °C. Only a slight change in the coupling selectivity was observed in the presence or absence of hindered amines as the base. Surprisingly, however, the C O selectivity decreased from 100 to 24% with less hindered amines, indicating that the selectivity drastically changed from a preference for C O coupling to a preference for C C coupling. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 4792–4804, 2000 相似文献
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155.
Keiji Konno Mitsuru Ueda Paul Youngman John W. Fitch Patrick E. Cassidy 《Journal of polymer science. Part A, Polymer chemistry》1997,35(11):2267-2272
Poly(arylene ether)s ( 3 ), ( 4 ) containing pendant benzoyl groups as precursors for novel polyxanthenes ( 7 ), ( 8 ) were prepared by nucleophilic substitution reaction of 2,5-difluoro-4-benzoylbenzophenone ( 1 ) or 2,5-difluoro-4-(4-dodecylbenzoyl)-4′-dodecylbenzophenone ( 2 ) with hydroquinone derivatives in the presence of potassium carbonate in N,N-dimethylacetamide. The polycondensation proceeded smoothly at 165°C and produced poly(arylene ether)s with inherent viscosities up to 0.80 dL/g. The novel polyxanthenes were synthesized via the reduction of poly(arylene ether)s followed by the Friedel-Crafts cyclization of diol polymers. The structure of the polyxanthenes was characterized by 1H-NMR and IR spectroscopies. Polyxanthene 8 was quite soluble in chloroform and THF. The 10% weight loss temperature of polyxanthene 7 was 510°C in nitrogen and it was 90°C higher than the corresponding poly(arylene ether) 3 . © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 2267–2272, 1997 相似文献
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157.
Makito Miyake Masazumi Ishii Kiyotaka Kawashima Tetsuro Kodama Kokichi Sugano Kiyohide Fujimoto Yoshihiko Hirao 《Photochemistry and photobiology》2009,85(4):1020-1027
Photodynamic therapy mediated by 5-aminolevulinic acid (ALA-PDT) has been developed as a therapeutic modality for refractory superficial bladder cancers. Here, in experiments using urothelial cancer cell lines, we investigated the effects of siRNA modulating heme-synthetic and degradation pathways for ALA-PDT. Targeted knockdown of ferrochelatase (FECH) suppressed heme synthesis and significantly increased intracellular protoporphyrin IX (PpIX) accumulation, leading to enhanced phototoxicity in four of five cell lines. Heme oxygenase-1 (HO-1) is recognized as important for cytoprotection against oxidative stress such as PDT. Targeted knockdown of HO-1 leads to decreased intracellular PpIX accumulation, resulting in a failure to enhance ALA-PDT effect in four cell lines. Knockdown of HO-1 caused marked growth inhibition in UM-UC-2 overexpressing HO-1, whereas no inhibitory effect was observed in UM-UC-3 lacking HO-1 expression. Moreover, HO-1 protein levels and (GT) n repeat polymorphism of the HO-1 gene promoter region were examined with the implication that the constitutive expressions of HO-1 protein were associated with a shorter (GT) n repeat. Our results suggested that (1) FECH siRNA improved the phototoxicity of ALA-PDT, (2) overexpression of HO-1 was associated with shorter (GT) n repeat of the promoter region, and (3) siRNA-mediated knockdown of HO-1 could suppress the growth of bladder cancer cells overexpressing HO-1. 相似文献
158.
Nakata Y Honda Y Ninomiya S Seki T Aoki T Matsuo J 《Journal of mass spectrometry : JMS》2009,44(1):128-136
The importance of imaging mass spectrometry (MS) for visualizing the spatial distribution of molecular species in biological tissues and cells is growing. We have developed a new system for imaging MS using MeV ion beams, termed MeV-secondary ion mass spectrometry (MeV-SIMS) here, and demonstrated more than 1000-fold increase in molecular ion yield from a peptide sample (1154 Da), compared to keV ion irradiation. This significant enhancement of the molecular ion yield is attributed to electronic excitation induced in the near-surface region by the impact of high energy ions. In addition, the secondary ion efficiency for biologically important compounds (>1 kDa) increased to more than 10(10) cm(-2), demonstrating that the current technique could, in principle, achieve micrometer lateral resolution. In addition to MeV-SIMS, peptide compounds were also analyzed with cluster-SIMS and the results indicated that in the former method the molecular ion yields increased substantially compared to the latter. To assess the capability of MeV-SIMS to acquire heavy-ion images, we have prepared a micropatterned peptide surface and successfully obtained mass spectrometric imaging of the deprotonated peptides (m/z 1153) without any matrix enhancement. The results obtained in this study indicate that the MeV-SIMS technique can be a powerful tool for high-resolution imaging in the mass range from 100 to over 1000 Da. 相似文献
159.
Yoshihiko Katayama Dr. Ondrej Burkacky Dr. Martin Meyer Dr. Christoph Bräuchle Prof. Enrico Gratton Prof. Don C. Lamb Prof. 《Chemphyschem》2009,10(14):2458-2464
We developed a new method for real‐time, three‐dimensional tracking of fluorescent particles. The instrument is based on a laser‐scanning confocal microscope where the focus of the laser beam is scanned or orbited around the particle. Two confocal pinholes are used to simultaneously monitor regions immediately above and below the particle and a feedback loop is used to keep the orbit centered on the particle. For moderate count rates, this system can track particles with 15 nm spatial resolution in the lateral dimensions and 50 nm in the axial dimension at a temporal resolution of 32 ms. To investigate the interaction of the tracked particles with cellular components, we have combined our orbital tracking microscope with a dual‐color, wide‐field setup. Dual‐color fluorescence wide‐field images are recorded simultaneously in the same image plane as the particle being tracked. The functionality of the system was demonstrated by tracking fluorescent‐labeled artificial viruses in tubulin‐eGFP expressing HUH7 cells. The resulting trajectories can be used to investigate the microtubule network with super resolution. 相似文献
160.
Yoshihiko Nishimori Katsuhiko Kanaizuka Dr. Tomochika Kurita Toshiaki Nagatsu Yu Segawa Fumiyuki Toshimitsu Satoshi Muratsugu Dr. Mitsuya Utsuno Dr. Shoko Kume Dr. Masaki Murata Dr. Hiroshi Nishihara Prof. 《化学:亚洲杂志》2009,4(8):1361-1367
Electronic conductivity of molecular wires is a critical fundamental issue in molecular electronics. π‐Conjugated redox molecular wires with the superior long‐range electron‐transport ability could be constructed on a gold surface through the stepwise ligand–metal coordination method. The βd value, indicating the degree of decrease in the electron‐transfer rate constant with distance along the molecular wire between the electrode and the redox active species at the terminal of the wire, were 0.008–0.07 Å?1 and 0.002–0.004 Å?1 for molecular wires of bis(terpyridine)iron and bis(terpyridine)cobalt complex oligomers, respectively. The influences on βd by the chemical structure of molecular wires and the terminal redox units, temperature, electric field, and electrolyte concentration were clarified. The results indicate that facile sequential electron hopping between neighboring metal–complex units within the wire is responsible for the high electron‐transport ability. 相似文献