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61.
Daisuke Sawai Mika Miyamoto Tetsuo Kanamoto Masayoshi Ito 《Journal of Polymer Science.Polymer Physics》2000,38(19):2571-2579
No systematic study has been reported on the lamellar thickening in atactic poly(acrylonitrile) (PAN) upon annealing because PAN, in the form of solution‐cast films or their drawn products, generally shows no small‐angle X‐ray scattering (SAXS) maximum corresponding to the lamellar thickness. In this work, PAN crystals were precipitated during the thermal polymerization of acrylonitrile in solution. The nascent PAN film, obtained by the filtration of the crystal suspension, exhibited a clear SAXS maximum revealing the lamellar structure. The lamellar thickening upon annealing of the nascent PAN films was studied in the temperature range 100–180 °C, where the degradation was minimal, as confirmed by the absence of an IR absorption band at 1605 cm−1 ascribed to the cyclized nitrile groups. Above 190 °C, the degradation of the samples was significant, and the SAXS became too broad to determine the scattering maximum. The long period was significantly affected by the annealing time (ta) and the temperature (Ta). Depending on ta, three stages were observed for the lamellar thickening behavior. The lamellar thickness stayed constant in stage I (ta = 0.5–3 min, depending on Ta), rapidly increased in stage II (ta = 0.5–8 min), and stayed at a constant value characteristic for each Ta at yet longer ta's in stage III. The lamellar thickness characteristic for Ta increased rapidly with increasing Ta at 165 °C (or higher), which was 152 °C lower than the estimated melting temperature of PAN (Tm = 317 °C). A possible mechanism for such lamellar thickening in PAN far below the Tm is discussed on the basis of the enhanced chain mobility in the crystalline phase above the crystal/crystal reversible transition at 165–170 °C detected by differential scanning calorimetry and wide‐angle X‐ray diffraction. The structural changes associated with annealing are also discussed. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 2571–2579, 2000 相似文献
62.
Yu Suzuki Takanori Higashi Takahiro Yamamoto Hideyasu Okamura Takehiro K. Sato Tetsuo Asakura 《Molecules (Basel, Switzerland)》2022,27(2)
Spider dragline silk is a biopolymer with excellent mechanical properties. The development of recombinant spider silk protein (RSP)-based materials with these properties is desirable. Formic acid (FA) is a spinning solvent for regenerated Bombyx mori silk fiber with excellent mechanical properties. To use FA as a spinning solvent for RSP with the sequence of major ampullate spider silk protein from Araneus diadematus, we determined the conformation of RSP in FA using solution NMR to determine the role of FA as a spinning solvent. We assigned 1H, 13C, and 15N chemical shifts to 32-residue repetitive sequences, including polyAla and Gly-rich regions of RSP. Chemical shift evaluation revealed that RSP is in mainly random coil conformation with partially type II β-turn structure in the Gly-Pro-Gly-X motifs of the Gly-rich region in FA, which was confirmed by the 15N NOE data. In addition, formylation at the Ser OH groups occurred in FA. Furthermore, we evaluated the conformation of the as-cast film of RSP dissolved in FA using solid-state NMR and found that β-sheet structure was predominantly formed. 相似文献
63.
A delayed coincidence method, time-interval analysis (TIA), has been applied to successive – decay events on the millisecond time-scale. Such decay events are part of the 220Rn216Po (T1/2 145 ms) (Th-series) and 219Rn215Po (T1/2 1.78 ms) (Ac-series). By using TIA in addition to measurement of 226Ra (U-series) from -spectrometry by liquid scintillation counting (LSC), two natural decay series could be identified and separated. The TIA detection efficiency was improved by using the pulse-shape discrimination technique (PSD) to reject -pulses, by solvent extraction of Ra combined with simple chemical separation, and by purging the scintillation solution with dry N2 gas. The U- and Th-series together with the Ac-series were determined, respectively, from alpha spectra and TIA carried out immediately after Ra-extraction. Using the 221Fr217At (T1/2 32.3 ms) decay process as a tracer, overall yields were estimated from application of TIA to the 225Ra (Np-decay series) at the time of maximum growth. The present method has proven useful for simultaneous determination of three radioactive decay series in environmental samples. 相似文献
64.
Inside Cover: Spontaneous Formation of Microgroove Arrays on the Surface of p‐Type Porous Silicon Induced by a Turing Instability in Electrochemical Dissolution (ChemPhysChem 8/2015) 下载免费PDF全文
65.
Kaoru Iwai Fukuo Takemura Masaoki Furue Shun-Ichi Nozakura 《Journal of polymer science. Part A, Polymer chemistry》1985,23(1):27-36
The emission properties of 1-(4-dimethylaminophenyl)-3-(9-phenanthryl)propane, Ph(CH2)3 DMA, and 1,3-di-(9-phenanthyrl)propane, Ph(CH2)3Ph, were studied in comparison with those of poly(9-vinylphenanthrene-co-p-N,N-dimethylaminostyrene). Ph(CH2)3DMA showed an intense intramolecular exciplex fluorescence in dioxane. Ph(CH2)3Ph did not exhibit a clear intramolecular excimer fluorescence. The quenching of the intramolecular exciplex by several electron acceptors was studied. As a result moderate electron acceptors, such as cyanobenzene, methyl benzoate, and acrylonitrile, selectively quenched the intramolecular exciplex, and in the case of cyanobenzene the subsequent formation of another fluorescent exciplex was observed. The results were discussed in terms of the reduction potentials of electron accepting quenchers. 相似文献
66.
Homogeneous palladium catalyst suppressing Pd black formation in air oxidation of alcohols 总被引:1,自引:0,他引:1
Iwasawa T Tokunaga M Obora Y Tsuji Y 《Journal of the American Chemical Society》2004,126(21):6554-6555
In homogeneous catalyst systems, there is the persistent problem that metal aggregation and precipitation cause catalyst decomposition and considerable loss of catalytic activity. Pd black formation is a typical example. Pd catalysts are known to easily aggregate and form Pd black, although they realize a wide variety of useful reactions in organic synthesis. In order to overcome this intrinsic problem of homogeneous Pd catalysis, we explored a new class of Pd catalyst by adopting aerobic oxidation of alcohols as a probe reaction. Herein we report a new catalyst system that suppresses the Pd black formation even under air and with a high substrate to catalyst molar ratio (S/C: more than 1000) in oxidation of alcohols. The novel pyridine derivatives having a 2,3,4,5-tetraphenylphenyl substituent and its higher dendritic unit at the 3-position of the pyridine ring were found to be excellent ligands with Pd(OAc)2 in the palladium-catalyzed air (balloon) oxidation of alcohols in toluene at 80 degrees C. Comparison with structurally related pyridine ligands revealed that introduction of the 2,3,4,5-tetraphenylphenyl substituent at the 3-position of pyridine ring effectively suppresses the Pd black formation, maintaining the catalytic activity for a long time to give aldehydes or ketones as products in high yields. 相似文献
67.
A direct benzylic oxidation of alkylarenes via C-H bond abstraction was developed using alkali metal bromides and oxidants under mild conditions. This reaction proceeded with excellent selectivity by thermal oxidation or photooxidation to provide a broad range of carbonyl compounds containing electron-deficient aryl carbonyl compounds in high yields. 相似文献
68.
Nishikimi A Uruno T Duan X Cao Q Okamura Y Saitoh T Saito N Sakaoka S Du Y Suenaga A Kukimoto-Niino M Miyano K Gotoh K Okabe T Sanematsu F Tanaka Y Sumimoto H Honma T Yokoyama S Nagano T Kohda D Kanai M Fukui Y 《Chemistry & biology》2012,19(4):488-497
Highlights? CPYPP binds to DOCK2 DHR-2 domain and inhibits its catalytic activity ? CPYPP inhibits DOCK2-mediated Rac activation in cells ? The structural features of CPYPP required for its inhibitory effect were revealed ? CPYPP inhibits lymphocyte migration and activation in vitro and in vivo 相似文献
69.
Ogihara H Okagaki J Saji T 《Langmuir : the ACS journal of surfaces and colloids》2011,27(15):9069-9072
Superhydrophobic coatings were prepared by spraying a pigment nanoparticle suspension. By changing the type of pigment nanoparticles, the colors of the coating could be controlled. The particle size of the pigments, which determines the surface structure of the coatings, played an important role in exhibiting superhydrophobicity. The spray-coating process is applicable to a variety of materials (e.g., copper, glass, paper, coiled wire, and tied thread), and the superhydrophobicity was repairable. 相似文献
70.
Hiroaki Aizawa Ken Hatano Hitoshi Saeki Nobuaki Honsho Tetsuo Koyama Koji Matsuoka Daiyo Terunuma 《Tetrahedron letters》2010,51(12):1545-6442
A new compound having a 2,3,4,5-tetraphenylsilole derivative on the center silicon of Dumbbell(1)6Gb3; Silole-Dumbbell(1)6Gb3 (1) was previously reported. It was found that 1 exhibited strongly increased fluorescence both in water and in a 96% acetone/water mixed solvent. The physical behavior of 1 in water and in the 96% acetone/water mixed solvent was investigated, and analyses including fluorescence quantum yields, dynamic-light-scattering (DLS), atomic-force-microscopy (AFM), and fluorescence microscopy were carried out. It was clarified that 1 dynamically formed different types of aggregates in water and in higher acetone concentrations to yield high aggregation-induced emission (AIE) effects due to the formation of micelle-like particles in water and inversion-type micelles in the acetone/water mixed solvent, respectively. 相似文献