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581.
Naokazu Yoshikawa Shinichi Yamabe Nobuko Kanehisa Tsuyoshi Inoue Hiroshi Takashima Keiichi Tsukahara 《Journal of Physical Organic Chemistry》2010,23(5):431-439
A series of new metal‐free blue emission compounds, i.e., diprotonated terpyH2ClPF6 ( 1 ), tterpyH2ClPF6 ( 2 ), ClterpyH2ClPF6 ( 3 ), and BterpyH2(PF6)2 ( 4 ), were prepared and characterized by electrospray ionization mass spectrometry, UV–vis spectroscopy, and cyclic voltammetry (CV). Abbreviations used are terpy = 2,2′:6′,2″‐terpyridine, tterpy = 4′‐(4‐tolyl)‐2,2′:6′,2″‐terpyridine, Clterpy = 4′‐chloro‐2,2′:6′,2″‐terpyridine, and Bterpy = 4,4′,4″‐tert‐butyl‐2,2′:6′,2″‐terpyridine. The X‐ray crystal structures of the three new compounds 1, 2, and 4 were determined. Both protonated pyridine rings of the terpyridine derivatives are hydrogen bonded intermolecularly to the adjacent Cl? ion in compounds 1 , 2, and 3 . The π–π* absorption bands in the UV region for 1, 2, 3, and 4 in acetonitrile were red‐shifted relative to those of the corresponding neutral compounds. All the compounds exhibited stronger emissions (around 400 nm) than their neutral counterparts. All the CVs for the diprotonated species, terpyH, tterpyH, ClterpyH, and BterpyH, showed the first reduction waves around ?0.6 V, which were more positive than those of the neutral ones. Density functional theory was applied to interpret the remarkable differences in the interaction of the Cl? ion. The attachment of two protons to the two terminal Bterpy nitrogens in 4 elicits remarkable characteristics. Both positive charges on the nitrogens are delocalized over the conjugated pyridine systems and the tertiary carbonium ions are stabilized to lead to stronger emission (Φ = 0.35) than the corresponding neutral Bterpy (Φ = 0.045). CCDC 732045–732047 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
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583.
Kazuhiko Okitsu Yasuhiro Hayakawa Tomuo Yamaguchi Masashi Kumagawa Akira Hirata Syogo Fujiwara Yasunori Okano Nobuyuki Imaishi Shinichi Yoda Toshihiko Oida 《Crystal Research and Technology》1996,31(8):969-978
A mixing experiment of multicomponents melts was performed using a uniform temperature furnace in the Second International Microgravity Laboratories (IML-2) mission. Growth morphologies and Ga concentration profiles were analyzed for the samples with the compositional ratio of 0.5 In–0.5 Ga–1.0 Sb grown under microgravity and on earth. The sample with free surface grown under microgravity was nearly spherical in shape, except some parts with projections. Ga was dispersed homogeneously in the bulk because the mixing was enhanced by Marangoni convection due to the concentration gradient. On the other hand, the sample grown on earth was a double cylindrical shape with different diameters, and Ga concentration decreased from top to bottom, showing clearly the effect of gravity. Many needle crystals were formed in both space and earth samples due to rapid cooling. The average size of the needle crystals grown in space was larger than that of the earth sample. 相似文献
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Tetsu Mitsumata Masashi Yuge Shinichi Morino Kenji Iwakura Kiyohito Koyama 《Macromolecular rapid communications》2002,23(17):1045-1048
The storage moduli, shear moduli and surface morphologies of poly(vinyl alcohol) (PVA) and alumina hybrid hydrogels were investigated. The storage moduli of hybrid hydrogels with higher alumina contents were found to be 1.5 times higher than those of PVA gels. This increase in modulus might be attributed to the cohesion of alumina to the PVA network.
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Kazunari Akiyoshi Masaharu Kohara Kensuke Ito Shinichi Kitamura Junzo Sunamoto 《Macromolecular rapid communications》1999,20(3):112-115
Amphiphilic A‐B block copolymers, ω‐methoxypoly(ethylene oxide)‐amylose copolymers (MPEO‐amylose), were synthesized by an enzymatic reaction using potato phosphorylase from an MPEO (Mw = 5.0×103)‐maltopentaosylamine derivative as a primer and α‐D ‐glucose‐1‐phosphate as a substrate. MPEO‐amyloses with various molecular weights of amylose (DP = 26, 36, 73 and 112) were obtained. None of the MPEO‐amyloses (5 mg/ml) precipitate in water containing 10 vol.‐% DMSO even after 24 h. The MPEO‐amyloses effectively form complexes with iodine in water. 相似文献
590.
An enantiopure 1,2-diamine having two phenolic hydroxy groups was synthesized, and attached to chloromethylated poly(styrene) through a benzyl ether linkage. The polymer-supported Ru precatalysts were prepared from the polymeric chiral 1,2-diamine and RuCl2/BINAP complex. In the presence of t-BuOK the polymeric catalyst system worked well in asymmetric hydrogenation of aromatic ketones in a mixed solvent of 2-propanol and DMF. The insoluble polymeric catalyst was readily separated from the reaction mixture and reused at least several times without loss of the catalytic activity. 相似文献