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71.
Formation of One‐Dimensional Helical Columns and Excimerlike Excited States by Racemic Quinoxaline‐Fused [7]Carbohelicenes in the Crystal
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Dr. Hayato Sakai Sho Shinto Prof. Yasuyuki Araki Prof. Takehiko Wada Prof. Tomo Sakanoue Prof. Taishi Takenobu Prof. Taku Hasobe 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(32):10099-10109
A series of quinoxaline‐fused [7]carbohelicenes (HeQu derivatives) was designed and synthesized to evaluate their structural and photophysical properties in the crystal state. The quinoxaline units were expected to enhance the light‐emitting properties and to control the packing structures in the crystal. The electrochemical and spectroscopic properties and excited‐state dynamics of these compounds were investigated in detail. The first oxidation potentials of HeQu derivatives are approximately the same as that of unsubstituted reference [7]carbohelicene (Heli), whereas their first reduction potentials are shifted to the positive by about 0.7 V. The steady‐state absorption, fluorescence, and circular dichroism spectra also became redshifted compared to those of Heli. The molecular orbitals and energy levels of the HOMO and LUMO states, calculated by DFT methods, support these trends. Moreover, the absolute fluorescence quantum yields of HeQu derivatives are about four times larger than that of Heli. The structural properties of the aggregated states were analyzed by single‐crystal analysis. Introduction of appropriate substituents (i.e., 4‐methoxyphenyl) in the HeQu unit enabled the construction of one‐dimensional helical columns of racemic HeQu derivatives in the crystal state. Helix formation is based on intracolumn π‐stacking between two neighboring [7]carbohelicenes and intercolumn CH ??? N interaction between a nitrogen atom of a quinoxaline unit and a hydrogen atom of a helicene unit. The time‐resolved fluorescence spectra of single crystals clearly showed an excimerlike delocalized excited state owing to the short distance between neighboring [7]carbohelicene units. 相似文献
72.
In order to improve the performance and durability of polymer electrolyte fuel cells (PEFCs), various improvements in the microstructures of cathode catalyst layers (CLs) were initiated in the early 1990s. More recent advances in CL materials are highlighted, including carbon supports for improved accessibility of Pt nanoparticles (NPs), adsorption of ionomer on the Pt surface, high-oxygen-permeability ionomers, corrosion resistance of mesoporous and microporous carbons, and conductive ceramic supports with a fused-aggregate network structure. These approaches are summarized as stepwise improvements. The influences of the support structure on the distribution of Pt NPs and ionomer are reviewed, as well as their effects on performance and durability. These approaches for carbon supports are extended to conductive ceramic supports and the unique advantages are discussed. 相似文献
73.
Raku Watanabe Dr. Nobuki Kato Kengo Hayashi Sho Tozawa Dr. Yusuke Ogura Prof. Shigefumi Kuwahara Prof. Minoru Ueda 《ChemistryOpen》2020,9(10):1008-1017
An efficient and stereoselective syntheses of all the possible stereoisomers of coronafacic acid (CFA) has been developed. The stereochemistries of C3a and C7a were controlled in a diastereoselective Diels-Alder type cycloaddition using a chiral auxiliary. CFA and 6-epi-CFA were synthesized by hydrogenation of a common intermediate. During the synthesis of 6-epi-CFA, we established that its cis-fused configuration is important for the introduction of C4-C5 double bond by dehydration. This report is the first practical synthesis of both 6-epi-CFA, and its enantiomer. 相似文献
74.
Yu Hoshino Shohei Taniguchi Hinata Takimoto Sotaro Akashi Sho Katakami Yusuke Yonamine Yoshiko Miura 《Angewandte Chemie (International ed. in English)》2020,59(2):679-683
Abiotic ligands that bind to specific biomolecules have attracted attention as substitutes for biomolecular ligands, such as antibodies and aptamers. Radical polymerization enables the production of robust polymeric ligands from inexpensive functional monomers. However, little has been reported about the production of monodispersed polymeric ligands. Herein, we present homogeneous ligands prepared via radical polymerization that recognize epitope sequences on a target peptide and neutralize the toxicity of the peptide. Taking advantage of controlled radical polymerization and separation, a library of multifunctional oligomers with discrete numbers of functional groups was prepared. Affinity screening revealed that the sequence specificity of the oligomer ligands strongly depended on the number of functional groups. The process reported here will become a general step for the development of abiotic ligands that recognize specific peptide sequences. 相似文献
75.
Dr. Masahiro Ikeshita Sho Furukawa Takahiro Ishikawa Kana Matsudaira Prof.Dr. Yoshitane Imai Prof.Dr. Takashi Tsuno 《ChemistryOpen》2022,11(4)
The Front Cover shows the comparison of circularly polarized luminescence (CPL) properties of square planar platinum(II) complexes with different coordination geometries. Computational studies have revealed that the distortion of the coordination geometry is key to enhancement of the chiroptical responses of these compounds. More information can be found in the Research Article by Masahiro Ikeshita et al. 相似文献
76.
Yuzuru Uchida Katsumi Onoue Nobuaki Tada Fumio Nagao Hideaki Kozawa Shigeru Oae 《Heteroatom Chemistry》1990,1(4):295-306
Phosphine oxides bearing two or three 2-pyridyl groups react with organometallic reagents affording 2,2′-bipyridyl, 2-substituted pyridines and pyridine in good yields. Phosphonium salts and phosphine oxides, bearing at least two 2-pyridyl or substituted 2-pyridyl groups also give the corresponding 2,2′-bipyridyls and pyridines upon treatment with acid or neutral solvents such as water and alcohols in substantial yields. The 2,2′-bipyridyls are considered to be formed by ligand coupling within the pentacoordinated phosphorus intermediate formed incipiently during the reaction. 相似文献
77.
M. H. Wang Y. Sawada K. Saito S. Horie T. Uchida M. Ohtsuka S. Seki S. Kobayashi T. Arii A. Kishi T. Takahashi Y. Nishimoto T. Wakimoto K. Monzen I. Kashima T. Nishikiori L. X. Sun R. Ozao 《Journal of Thermal Analysis and Calorimetry》2007,89(2):363-366
The thermal change of the tris(8-hydroxyquinolinato)aluminum (Alq3) is currently investigated by XRD-DSC and TG. The phase transition of Alq3 from α-phase to γ-phase takes place at 643–669 K. A very sharp peak with the peak temperature at approx. 709 K is ascribed
to the melting of the Alq3. The decomposition of the Alq3 was observed accompanied with the melting and evaporation at >703K. The effect of the atmospheres on the mass loss procedure
was studied by TG. It was found that thermal process of Alq3 was strongly influenced by the partial pressure of water vapor in the atmosphere instead of oxygen. 相似文献
78.
Susumu Tajima Yukiyoshi Nagai Osamu Sekiguchi Masao Fujishige Nozomu Uchida 《Journal of the American Society for Mass Spectrometry》1995,6(3):202-206
The spontaneous unimolecular dissociation reaction of methyl lactate (1) ionized by electron impact was investigated by a combination of mass-analyzed ion kinetic energy spectrometry and deuterium labeling. The metastable ions 1+· decompose in a variety of ways: four fragment peaks are observed at m/z 89, 76, 61, and 45, which correspond to the losses of ?H3, CO, CH3?O, and ?OOCH3, respectively. Double hydrogen atom transfer occurs in the third reaction. The source-generated m/z 61 ions decompose into oxygen-protonated methanols at m/z 33 ([CH3OH 2 + ]) by the loss of CO with double hydrogen atom migration. Both hydroxyl and methyne hydrogen atoms in 1 +· are present in the resultant protonated methanols. 相似文献
79.
80.
Krishnamohan T. Krivokapic Z. Uchida K. Nishi Y. Saraswat K.C. 《Electron Devices, IEEE Transactions on》2006,53(5):990-999
For the first time, the tradeoffs between higher mobility (smaller bandgap) channel and lower band-to-band tunneling (BTBT) leakage have been investigated. In particular, through detailed experiments and simulations, the transport and leakage in ultrathin (UT) strained germanium (Ge) MOSFETs on bulk and silicon-on-insulator (SOI) have been examined. In the case of strained Ge MOSFETs on bulk Si, the resulting optimal structure obtained was a UT low-defect 2-nm fully strained Ge epi channel on relaxed Si, with a 4-nm Si cap layer. The fabricated device shows very high mobility enhancements >3.5/spl times/ over bulk Si devices, 2/spl times/ mobility enhancement and >10/spl times/ BTBT reduction over 4-nm strained Ge, and surface channel 50% strained SiGe devices. Strained SiGe MOSFETs having UT (T/sub Ge/<3 nm) very high Ge fraction (/spl sim/ 80%) channel and Si cap (T/sub Si cap/<3 nm) have also been successfully fabricated on thin relaxed SOI substrates (T/sub SOI/=9 nm). The tradeoffs in obtaining a high-mobility (smaller bandgap) channel with low tunneling leakage on UT-SOI have been investigated in detail. The fabricated device shows very high mobility enhancements of >4/spl times/ over bulk Si devices, >2.5/spl times/ over strained silicon directly on insulator (SSDOI; strained to 20% relaxed SiGe) devices, and >1.5/spl times/ over 60% strained SiGe (on relaxed bulk Si) devices. 相似文献