Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 84 , Issue 3
Showing 1-16 articles out of 16 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2009
  • Hidetoshi Oikawa
    2011 Volume 84 Issue 3 Pages 233-250
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 26, 2011
    JOURNALS FREE ACCESS
    Organic nanocrystals (NCs) are in the mesoscopic phase between a single molecule and the corresponding bulk crystals, and are expected to exhibit peculiar optical properties, depending on crystal size and shape. In the present Award Accounts, recent progress on hybridized organic NCs and ordered array structure of encapsulated organic NCs will be introduced in detail for optically functional materials toward next-generation organic device application. Hybrid material (or hybridization) is an important area in current material science. Our attention is now focused on core–shell type hybridized organic NCs, which seem to be the best suited nanostructure for providing novel optoelectronic properties and photonic function induced by core–shell interface interaction. On the other hand, it may be necessary to arrange and integrate organic NCs, including hybridized materials, on a substrate so as to receive and transmit input and output signals by electronically and/or optically accessing organic devices. Hence, encapsulations of organic NCs, patterned substrates, and tapered cell method have been employed suitably to fabricate and control ordered array structure of organic NCs on a substrate. Finally, the future scope in the relevant fields of optoelectronics and photonics will be discussed in brief.
    Recent progress on hybridized organic nanocrystals and on ordered array structure of encapsulated organic nanocrystals on a patterned substrate will be introduced in detail for optically functional materials toward next-generation organic device application in optoelectronics and photonics. Fullsize Image
BCSJ Award Article
  • Yohei Kashiwame, Megumi Watanabe, Kenjirou Araki, Shigeki Kuwata, Taka ...
    2011 Volume 84 Issue 3 Pages 251-258
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 11, 2011
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    A reaction of [{Cp*Ru(μ3-Cl)}4] (Cp*: η5-C5(CH3)5) with 5-phenyl-3-(2-pyridyl)-1H-pyrazole (PhpypzH) afforded a chelating pyrazole complex [Cp*RuCl(PhpypzH)] (2) bearing an NH proton at the β-position to the metal. Treatment of 2 with an equimolar amount of silver nitrite followed by anion exchange with KOTf (OTf: OSO2CF3) gave the pyrazolato–nitrosyl complex [Cp*Ru(NO)(Phpypz)](OTf) (3) through a proton shift from the pyrazole ligand to the nitrite ion. In contrast, simple ligand exchange took place in the reaction of silver nitrite and [Cp*RuCl(bipy)] (bipy: 2,2′-bipyridine) without the protic chelate ligand to give the nitro complex [Cp*Ru(NO2N)(bipy)] (4). Protonation of 4 with triflic acid led to the formation of the nitrosyl complex [Cp*Ru(NO)(bipy)](OTf)2 (5). The pyrazolato complex 3 was also obtained by the reaction of [Cp*Ru(NO)Cl2] with PhpypzH and KOTf in water. Reversible protonation of 3 resulted in the formation of the dicationic pyrazole complex [Cp*Ru(NO)(PhpypzH)](OTf)2 (6). The detailed structures of 24 and 6 have been determined by X-ray crystallography.
    Novel N–N chelating protic pyrazole complexes of ruthenium bearing a Brønsted acidic β-NH group have been synthesized. Their detailed structures and proton-transfer reactions have been described. Fullsize Image
 
  • Shoichi Katsuta, Hajime Nomura, Takuya Egashira, Takahiro Imoto, Yoshi ...
    2011 Volume 84 Issue 3 Pages 259-265
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 26, 2011
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    A series of macrocyclic trinuclear complexes of (η6-alkylbenzene)ruthenium(II) bridged by 2,3-pyridinediolato ligands were synthesized and their liquid–liquid extraction properties for Li+ and Na+ were investigated at 25 °C. The alkylbenzenes used were p-cymene, 1,2,3-trimethylbenzene, 1,3,5-trimethylbenzene, 1,3,5-triethylbenzene, 1,2,4,5-tetramethylbenzene, and hexamethylbenzene. Most of the trinuclear complexes were stable for 48 h or more in a dichloromethane–water system. The extraction constants (Kex = [ML+A]o/([M+][A][L]o); M+: alkali metal ion, L: trinuclear complex, A: counter anion (picrate), and o: organic phase (dichloromethane)) were determined from analysis of the extraction equilibria. Each trinuclear complex exhibited a larger Kex value for Li+ than for Na+; particularly large separation factor, SF = Kex(Li+)/Kex(Na+), was observed for the complexes of Ru(1,3,5-trimethylbenzene) (SF = 1.7 × 103) and Ru(1,2,4,5-tetramethylbenzene) (SF = 1.6 × 103). The extraction separation of Li+ from seawater could be achieved by using the trinuclear complex of Ru(1,3,5-trimethylbenzene) with the aid of washing the organic phase with water to remove co-extracted Na+.
  • Take-aki Koizumi, Rieko Kuwahara, Isao Yamaguchi, Takakazu Yamamoto
    2011 Volume 84 Issue 3 Pages 266-268
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 11, 2011
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    Inclusion compounds of Br–Th–Py–Br and (RO)2B–Th–Py–Br ((OR)2: –OCH2C(CH3)2CH2O–) with γ-cyclodextrin (CD), denoted by Br–ThPy–Br–CD and (RO)2B–ThPy–Br–CD, respectively, were prepared. Ni(0)-promoted dehalogenative coupling of Br–ThPy–Br–CD gave an oligomeric inclusion product, Oligo(ThPy–CD). Oligo(ThPy–CD) was soluble in organic solvents, and 1H- and CP/MAS 13C{1H} NMR spectra as well as the powder XRD pattern of Oligo(ThPy–CD) supported the CD-encapsulated structure.
  • Tsuyoshi Gushiken, Seiji Ujiie, Takashi Ubukata, Yasushi Yokoyama
    2011 Volume 84 Issue 3 Pages 269-282
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 19, 2011
    JOURNALS OPEN ACCESS
    Eleven novel thermotropic rod-shaped liquid crystals composed of alkoxyphenyl (methoxy to decyloxy) or hexanoyloxyphenyl groups on both ends of the diamantane core have been synthesized and their liquid crystalline properties investigated. All of them behaved as liquid crystals at considerably high temperatures. When the alkoxy side chains are propyloxy or shorter, the clearing points are over 300 °C. The clearing point of a liquid crystalline compound with two hexanoyloxy groups also exceeds 300 °C. When the alkoxy groups on both ends of the molecule are octyloxy or longer, they showed only smectic phases as the mesophase. When they are shorter than octyloxy, the compounds showed nematic phases just below their clearing points. A nematic phase was also observed for the hexanoyloxy compound as well as the smectic A and B phases. However, as the bent-shaped adamantane-derived hexyloxyphenyl molecule did not show any liquid crystalline properties, the linear structures of the diamantane-derived molecules were crucial in generating liquid crystalline phases.
  • Satoshi Nakata, Ayaka Ikeguchi, Takaya Shiota, Ryouhei Komori, Noriyuk ...
    2011 Volume 84 Issue 3 Pages 283-289
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 19, 2011
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    The interactions between sex hormones (estradiol and testosterone) and a 1,2-di-O-myristoyl-sn-glycero-3-phosphocholine (DMPC) molecular layer were investigated by observing the liposome and the surface area (A) vs. surface pressure (π) of the DMPC monolayer at an air–water interface. The shape and size of the liposome changed with the addition of estradiol and testosterone. The π–A isotherm, the time variation of the surface pressure, and the microscopic observation of monolayer were examined to clarify the different effects of the steroid hormones. These experimental results are discussed in relation to the formation of a rigid membrane due to hydrogen bonding between estradiol and DMPC.
  • Sanyo Hamai
    2011 Volume 84 Issue 3 Pages 290-297
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: March 04, 2011
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    In aqueous solution, γ-CD forms a 1:1 inclusion complex with phenanthrene analogs (phenanthrene (Phen), phenanthridine (Phent), and benzo[c]cinnoline (Bcc)). The equilibrium constants, K1, for the formation of the 1:1 inclusion complex for the phenanthrene analogs have been evaluated from the fluorescence intensity change. The K1 values for the phenanthrene analogs are in the range from 100 to 150 mol−1 dm3. The 1:1 inclusion complexes further associate with an alkyltrimethylammonium cation (alkyl sulfate or alkanesulfonate) to form a 1:1:1 γ-CD–phenanthrene analog–alkyltrimethylammonium cation (alkyl sulfate or alkanesulfonate) inclusion complex. The equilibrium constants, K2, for the formation of the 1:1:1 inclusion complex have been evaluated from a simulation for the fluorescence intensity change. The K2 value for the same alkyltrimethylammonium cation is decreased on going from Phen to Bcc. The K2 value of the phenanthrene analog is increased with the alkyl chain length of the alkyltrimethylammonium cation (alkyl sulfate or alkanesulfonate). In the case of Phen, the K2 value for an alkyltrimethylammonium cation is less than that for alkyl sulfate or alkanesulfonate having the same alkyl group as the alkyltrimethylammonium cation.
  • Yuki Naito, Yutaka Yoshikawa, Hiroyuki Yasui
    2011 Volume 84 Issue 3 Pages 298-305
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 26, 2011
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    Zinc complexes exhibit high insulin-like and antidiabetic activities in animals with type 2 diabetes mellitus (DM). However, molecular mechanisms underlying these activities have not yet been determined. In this study, we investigated activation of the insulin signaling pathway by Zn in 3T3-L1 adipocytes using di(hinokitiolato)zinc complex (hinokitiol: 2-hydroxy-4-isopropylcyclohepta-2,4,6-trienone, [Zn(hnk)2]), which exhibits antidiabetic effect in animals with type 2 DM. Our results show that [Zn(hnk)2] strongly induced Akt/protein kinase B (Akt/PKB) phosphorylation, and optimal phosphorylation was achieved at a concentration of 50 µM. The [Zn(hnk)2]-induced Akt/PKB phosphorylation was almost completely inhibited by wortmannin, whereas [Zn(hnk)2]-induced phosphorylation of glycogen synthase kinase-3β (GSK3β) was partially inhibited by wortmannin. Further, we examined cellular Zn uptake by [Zn(hnk)2] stimulation and evaluated cellular glucose uptake at the same time point. The intracellular Zn concentration incubated with [Zn(hnk)2] was approximately 4.7-fold higher than that in the control cells. Moreover, the glucose uptake of [Zn(hnk)2]-treated adipocytes was 3.7-fold higher than that of the control adipocytes. These results suggest that [Zn(hnk)2] was able to translocate glucose transporter 4 (GLUT4) protein to the plasma membrane. Thus, we propose that [Zn(hnk)2] produces the antidiabetic effect by inducing insulin signaling pathways and glucose uptake.
  • Hiroaki Hagiwara, Koshiro Nishi, Naohide Matsumoto, Yukinari Sunatsuki ...
    2011 Volume 84 Issue 3 Pages 306-311
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 26, 2011
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    A low-spin FeIII complex, [FeIII(H2L5-Me)(HL5-Me)](ClO4)2·EtOH, was prepared by the reaction of FeII(ClO4)2·6H2O and H2L5-Me in ethanol with 1:2 molar ratio and in air, where H2L5-Me: N-[(5-methylimidazol-4-yl)methylidene]histamine. Each complex molecule of [Fe(H2L5-Me)(HL5-Me)]2+ has both fully protonated ligand and mono-deprotonated ligand and acts as a chiral self-complementary building block to produce the homochiral imidazole–imidazolate-bridged zigzag-chain structure. The X-ray analysis confirmed that the adjacent chains with the same chirality are stacked in a crystal lattice to give a chiral crystal (conglomerate). Low-spin FeIII was revealed by the magnetic susceptibility and Mössbauer measurements.
  • Kotaro Dai, Kuniharu Nomoto, Shinji Ueno, Kazuaki Tomono, Kazuo Miyamu ...
    2011 Volume 84 Issue 3 Pages 312-319
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: March 04, 2011
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    A series of [Ni(dmit)2] (dmit: 1,3-dithiole-2-thione-4,5-dithiolato) salts of alkyltrimethylammonium (Cn: n represents the alkyl chain length; n = 3 and 5–18) have been prepared and analyzed by X-ray structural analysis. All complex salts have been found to be composed of alternate sheets of [Ni(dmit)2] anions and sheets of cations with a pronounced interdigitation of the alkyl chains. However, molecular arrangement differed between (C3)[Ni(dmit)2] and other (Cn)[Ni(dmit)2] (n = 5–18). Adjacent cations were aligned along the long axis of [Ni(dmit)2] anion in C3 complex salt, while in others (C5C18 complex salts), they were aligned toward the short axis. Such a difference in arrangement arose from correlativity between the lengths of the long axis of cation and anion, namely CLCA. Furthermore, relative orientation between the alkyl chain of cation and [Ni(dmit)2] anion differed between the odd- and even-numbered cations for C10C18. Whereas the plane of alkyl chain for odd-numbered cation was normal to the plane of [Ni(dmit)2] anion, that of even-numbered cation was parallel. It was also found that C12 analog behaved like odd-numbered cations. However, in C12 salt, the end methyl group of the dodecyl group adopted unusual end-gauche conformation.
  • Aliasghar Jarrahpour, Abdolhamid Fadavi, Maaroof Zarei
    2011 Volume 84 Issue 3 Pages 320-327
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 26, 2011
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    Trimellitic anhydride was attached to Merrifield resin and a ketene was generated from polymer-bound phthaloylglycine. Then this polymer reacted with imines in the presence of Vilsmeier reagent and triethylamine to afford the solid-phase-tethered β-lactam products. Selective cleavage of supported β-lactams by trifluoroacetic acid and methylhydrazine gave 4-carboxyphthalimido- and 3-amino-β-lactams, respectively. The trans-stereochemistry was found in all products.
  • Kentaro Okuma, Akiko Nojima, Yuki Nakamura, Nahoko Matsunaga, Noriyosh ...
    2011 Volume 84 Issue 3 Pages 328-332
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 26, 2011
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    The reaction of DMF with o-trimethylsilylphenyl triflate in the presence of CsF afforded dimethyldiphenylammonium triflate, xanthene, and xanthone in 62%, 16%, and 24% yields, respectively. On the other hand, the reaction of dimethylthioformamide with triflate and CsF resulted in diphenyl sulfide, xanthene, and xanthone in 62%, 10%, and 12% yields, respectively. The reaction of acetylimidazole with benzyne gave 9-N,N-diphenylaminoanthracene in 85% yield.
  • Masahiro Tojo, Shinsuke Fukuoka, Hiroshi Tsukube
    2011 Volume 84 Issue 3 Pages 333-340
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: March 04, 2011
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    The chemical reactivity and reaction mechanism of fluorobenzene synthesis via dehydrofluoro–dehydrogenation of 1,1-difluorocyclohexane was investigated. 1,1-Difluorocyclohexane reacted with molecular oxygen to give fluorobenzene in good yields in the presence of both Pd and metal fluoride catalysts. The reaction proceeded with dehydrofluorination of 1,1-difluorocyclohexane to yield 1-fluorocyclohexene as the sole intermediate species, followed by oxidative dehydrogenation. The present system offers a selective synthesis of fluorobenzene.
  • Haibo Wang, Linlin Jing, Zhuo Xiang, Peng Liu, Xiaoli Sun, Ru Jiang
    2011 Volume 84 Issue 3 Pages 341-343
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: February 11, 2011
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    Four novel nitroxides were synthesized, and the fluorescence tuning of these molecules with the action of different chemical inputs was investigated; the results suggested that these nitroxides could serve as a redox fluorescence switch.
  • Natsumi Kamiya, Fumiaki Tsunomori, Hiroyuki Kagi, Kenji Notsu
    2011 Volume 84 Issue 3 Pages 344-348
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: March 04, 2011
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    This study reports the first application of dynamic light scattering to observations of crystal growth of calcium carbonate from a supersaturated solution. Crystal size distributions around the critical nucleus radius (≈2 nm at Ω = 18) were measured in La-free and 5 µM La-doped conditions. In the former, the intensity of scattered light increased smoothly and particle size increased with time. In the case of La-doped condition, the total scattering volume of particles was smaller, and grew very slowly compared with the La-free condition. These results show that the inhibiting effect of La3+ on calcium carbonate occurred from the initial stage of crystal growth.
  • Samaresh Ghosh, Mridula Acharyya, Rajkumar Manna, Chandan K. Dey
    2011 Volume 84 Issue 3 Pages 349-351
    Published: March 15, 2011
    Released: March 15, 2011
    [Advance publication] Released: March 04, 2011
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    Synthesis of novolac resin based novel network polymer 1 based on the reaction between novolac epoxy resin and ethylenediamine has been achieved for the first time and its sorption characteristics toward methyl orange as azo dye source have been investigated.
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