Updated on 2022/07/08

写真a

 
TAJIMA Tomoyuki
 
Organization
Faculty of Environmental and Life Science Lecturer
Position
Lecturer
External link

Degree

  • 博士(理学) ( 京都大学 )

Research Interests

  • Photoinduced Electron Transfer

  • 有機無機ナノハイブリッド

  • ホウ素クラスター

  • 近赤外光

  • photocatalyst

  • overall water splitting

  • ホウ素中性子捕捉療法剤

  • 自己組織化

  • Hydrogen evolution

  • Carbon nanotubes

  • Main group element

  • Dendrimer

  • Fullerene

  • 典型元素化学

  • 有機構造化学

  • デンドリマー

  • フラーレン

Research Areas

  • Nanotechnology/Materials / Functional solid state chemistry

  • Nanotechnology/Materials / Nanometer-scale chemistry

  • Nanotechnology/Materials / Nanostructural physics

  • Nanotechnology/Materials / Energy chemistry

  • Nanotechnology/Materials / Organic functional materials

  • Nanotechnology/Materials / Nanobioscience

  • Nanotechnology/Materials / Polymer chemistry

  • Life Science / Bioorganic chemistry

  • Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

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Research History

  • Okayama University   Graduate School of Environmental and Life Science   Lecturer

    2021.4

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  • Okayama University   The Graduate School of Environmental and Life Science

    2012.4 - 2021.3

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  • 岡山大学 大学院環境学研究科 講師

    2009.4 - 2012.3

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  • - Senior Assistant Professor,Graduate School of Environmental and life Science,Okayama University

    2009

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  • Kyoto University   Pionnering Research Unit for Next Generation

    2008.4 - 2009.3

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  • Research Associate

    2008 - 2009

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  • Nagoya University   Research Center for Materials Science

    2007.8 - 2008.3

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  • Researcher

    2007 - 2008

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  • Saitama University   Graduate School of Science and Engineering

    2006.4 - 2007.7

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  • Saitama University   Faculty of Science

    2006.1 - 2006.3

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  • 京都大学化学研究所 日本学術振興会特別研究員

    2005.4 - 2005.12

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  • Postdoctoral Fellowships of Japan Society for the Promotion of Science

    2005

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  • Kyoto University   Graduate School of Science

    2004.4 - 2005.3

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  • Postdoctoral Fellowships of Japan Society for the Promotion of Science

    2004 - 2005

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Professional Memberships

 

Papers

  • Dye-sensitized H-2 evolution from water facilitated by photoinduced electron transfer between molecules on the inside and the outside of a carbon nanotube

    Tomoyuki Tajima, Masahiro Yamagami, Ryohei Sagawa, Hideaki Miyake, Yutaka Takaguchi

    JOURNAL OF APPLIED PHYSICS   129 ( 1 )   2021.1

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER INST PHYSICS  

    Dye-encapsulated single-walled carbon nanotubes (dye@SWCNTs) were physically modified to fabricate a water-dispersible dye@SWCNT/dendrimer hybrid. A photocatalytic H-2 evolution reaction that uses this dye@SWCNT hybrid as a particulate photocatalyst was conducted in the presence of an electron-relay molecule [methyl viologen (MV2+)], a co-catalyst [PVP-Pt; poly(vinylpyrrolidone)], and a sacrificial donor [1-benzyl-1,4-dihydronicotinamide]. Photoinduced electron transfer occurs between the encapsulated dye molecule inside the SWCNT and the MV2+ ion outside the SWCNT. This is followed by the relay of the electron to the co-catalyst, which reduces H+ to generate H-2. The external quantum yield of the H-2 evolution reached a maximum of 8.5% under irradiation with light at 510nm. Notably, the photoinduced electron transfer between the molecules on the inside and the outside of the SWCNT proceeded smoothly despite the possibility of energy migration from the encapsulated dye to the SWCNT or the possibility of charge recombination.

    DOI: 10.1063/5.0026896

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  • Photoinduced Electron Transfer in a MoS2/Anthracene Mixed-Dimensional Heterojunction in Aqueous Media

    Tomoyuki Tajima, Shogo Okabe, Yutaka Takaguchi

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   93 ( 6 )   745 - 750   2020.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

    Mixed-dimensional (0D/2D) van der Waals heterojunctions were constructed by physical adsorption of anthracene (Anth) onto few-layer MoS2 nanosheets. The physical modification of few-layer MoS2 nanosheets using anthryl dendron 1, i.e., a poly(amidoamine) dendrimer having an anthracene core, via a simple yet efficient exfoliation approach afforded MoS2/1 hybrids, which are stable for at least one month. The emission quenching typical for anthracene is also observed in the MoS2/anthracene mixed-dimensional heterojunctions. Transient absorption measurements on MoS2/1 hybrids proved that photoinduced electron transfer occurs at the MoS2/anthracene interface. The lifetime of the singlet excited state (tau(S1)((1)Anth*)) for MoS2/1 was evaluated to be 4.1 ns, which is shorter than that of anthryl dendron 1 (13 ns). Interestingly, a remarkably long lifetime was observed for the anthracene cation radical (6.1 mu s). Relatively long lifetimes of charge-separate states of MoS2/1 hybrids would be beneficial design features for efficient photovoltaics, photocatalysts, and related optoelectronic applications.

    DOI: 10.1246/bcsj.20200026

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  • Molecular design of benzothiadiazole-based dyes for working with carbon nanotube photocatalysts Reviewed

    Takaguchi Yutaka, Miyake Hideaki, Izawa Takumi, Miyamoto Daiki, Sagawa Ryohei, Tajima Tomoyuki

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS   194 ( 7 )   707 - 711   2019.7

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:TAYLOR & FRANCIS LTD  

    A donor-acceptor-donor (D-A-D) dye consisting of ferrocene units (donors) and a benzothiadiazole unit (acceptor) was synthesized to use the photosensitizer for hydrogen evolution reaction (HER) from water within semiconducting single-walled carbon nanotube (s-SWCNT). The dye was easily encapsulated into s-SWCNT by a solution method to form dye-encapsulated s-SWCNTs (dye@SWCNTs). Subsequently, physical modification of dye@SWCNTs by a fullerodendron gave dye@SWCNT/fullerodendron nanohybrids having dye/s-SWCNT/C-60 coaxial heterojunction. Interestingly, dye@SWCNT/fullerodendron nanohybrids act as the photosensitizer for HER in the presence of sacrificial donor, electron relay, and co-catalyst due to the mobile carrier generation upon photoexcitation of the dye molecules.

    DOI: 10.1080/10426507.2019.1603716

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  • Disproportionation-induced solid-state fluorescence in 6,13-dihydropentacenes Reviewed

    Tajima Tomoyuki, Sanda Rai, Nishihara Katsuya, Shirai Hitoshi, Okuda Yasuhiro, Orita Akihiro, Takaguchi Yutaka

    RSC ADVANCES   9 ( 30 )   17035 - 17039   2019.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    The thermally and photolytically induced disproportionation of 6,13-dihydropentacene derivatives into tetrahydropentacenes and pentacenes results in unique solid-state fluorescence. The fluorescence thereby depends on the molecular structure and the molecular arrangement in the solid state.

    DOI: 10.1039/c9ra03297e

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  • Carbon-nanotube-based Photocatalysts for Water Splitting in Cooperation with BiVO4 and [Co(bpy)(3)](3+/2+) Reviewed

    Izawa Takumi, Kalousek Vit, Miyamoto Daiki, Murakami Noritake, Miyake Hideaki, Tajima Tomoyuki, Kurashige Wataru, Negishi Yuichi, Ikeue Keita, Ohkubo Takahiro, Takaguchi Yutaka

    CHEMISTRY LETTERS   48 ( 5 )   410 - 413   2019.5

  • Physical modification of carbon nanotubes with a dendrimer bearing terminal mercaptoundecahydrododecaborates (Na2B12H11S) Reviewed

    Masahiro Yamagami, Tomoyuki Tajima, Kango Ishimoto, Hideaki Miyake, Hiroyuki Michiue, Yutaka Takaguchi

    HETEROATOM CHEMISTRY   29 ( 5-6 )   2018.12

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-HINDAWI  

    The thiol-substituted B-12-cluster mercaptoundecahydro-closo-dodecaborate Na-2[B12H11SH] (BSH) was successfully attached to a poly(amido)amine (PAMAM) dendrimer, which contains a bis(decyloxy)decane core. The physical modification of single-walled carbon nanotubes (SWCNTs) with dendrimer(SB12)(4) afforded a SWCNT/dendrimer(SB12)(4) nanohybrid that exhibited NIR-I-to-NIR-II fluorescence. Herein, we describe a promising strategy for in vivo imaging of boron clusters that may be widely applicable to boron neutron capture therapy.

    DOI: 10.1002/hc.21467

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  • A facile synthesis of a SnO2/Graphene oxide nano-nano composite and its photoreactivity Reviewed

    Tomoyuki Tajima, Haruko Goto, Masayasu Nishi, Takahiro Ohkubo, Yuta Nishina, Hideaki Miyake, Yutaka Takaguchi

    Materials Chemistry and Physics   212   149 - 154   2018.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Elsevier Ltd  

    A novel SnO2/graphene oxide (GO) nano-nano composite was prepared by a facile sol–gel process. X-Ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy, and nitrogen adsorption–desorption isotherms measurements confirmed the formation of a SnO2/GO nano-nano composite. The photoreaction of this SnO2/GO nano-nano composite was studied via the photodegradation of rhodamine B (RhB). Interestingly, the degradation mode of RhB in oxygen-saturated solution is photocatalytic reaction, but the degradation mode in argon-saturated solution is not photocatalytic reaction.

    DOI: 10.1016/j.matchemphys.2018.03.046

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  • Apatite coating on dendrimer-modified buckypaper and the formation of nanoapatite on MWCNTs Reviewed

    Tomoyuki Tajima, Tomoaki Tanaka, Hideaki Miyake, Ill Yong Kim, Chikara Ohtsuki, Yutaka Takaguchi

    Polymer Journal   50 ( 9 )   1 - 7   2018.5

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Nature Publishing Group  

    Multi-walled carbon nanotube (MWCNT)/dendrimer sheet scaffolds, i.e., dendrimers attached to the surface of MWCNT buckypaper, were fabricated, and a hydroxyapatite (HAp) coating prepared on dendrimer-modified buckypaper using an alternate soaking process (ASP) is described. The amount of the HAp that is retained on the surface of the MWCNT/dendrimer sheet scaffolds depends on the modification method
    i.e., surface modification performed after the formation of the buckypaper is much more effective in producing MWCNT/HAp hybrid materials than surface modification prior to the formation of the buckypaper. Moreover, biomimetic crystallization of calcium phosphate on buckypaper in simulated body fluid (SBF) was carried out. TEM analysis of the resulting MWCNT/dendrimer sheet scaffolds revealed that the MWCNT backbone was covered with scaly crystals.

    DOI: 10.1038/s41428-018-0056-4

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  • Enhanced Photosensitized Hydrogen Production by Encapsulation of Ferrocenyl Dyes into Single-Walled Carbon Nanotubes Reviewed

    Noritake Murakami, Hideaki Miyake, Tomoyuki Tajima, Kakeru Nishikawa, Ryutaro Hirayama, Yutaka Takaguchi

    Journal of the American Chemical Society   140 ( 11 )   3821 - 3824   2018.3

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society  

    Dye-encapsulated single-walled carbon nanotubes (SWCNTs) were employed for the construction of a coaxial three-component dye/SWCNT/C60 heterojunction. Despite the larger diameter (∼1.4 nm) of the SWCNTs relative to that set by Flavel's rule (0.95 nm), the photoinduced electron transfer from dye-encapsulated SWCNTs to C60 proceeded smoothly, resulting in the photosensitized evolution of H2 from H2O using a ferrocenyl-based photosensitizer, which was confirmed by the action spectra.

    DOI: 10.1021/jacs.7b12845

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  • Photo-induced H2 evolution from water: Via the dissociation of excitons in water-dispersible single-walled carbon nanotube sensitizers Reviewed

    Kango Ishimoto, Tomoyuki Tajima, Hideaki Miyake, Masahiro Yamagami, Wataru Kurashige, Yuichi Negishi, Yutaka Takaguchi

    Chemical Communications   54 ( 4 )   393 - 396   2018

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry  

    To observe a clear-cut example of the formation of mobile carriers from excitons on semiconducting single-walled carbon nanotubes (s-SWCNTs) surrounded by a medium with a high dielectric constant, water-dispersible s-SWCNT nanocomposites were fabricated by physical modifications using poly(amidoamine) dendrimers that contain an aliphatic core. The evolution of H2 from water using these s-SWCNT/dendrimer nanocomposites as photosensitizers under irradiation with visible light demonstrated a photo-induced electron transfer from the s-SWCNTs to the co-catalysts.

    DOI: 10.1039/c7cc07194a

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  • Synthesis and Properties of (Terthiophene)(4)-Poly(amidoamine)-C-60 Pentad Reviewed

    Tomoyuki Tajima, Takuya Nishihama, Shogo Miyake, Nobuhiro Takahashi, Yutaka Takaguchi

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   88 ( 5 )   736 - 745   2015.5

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

    (Terthiophene)(4)-poly(amidoamine)-C-60 pentad 8a and (terthiophene)(2)-poly(amidoamine)-C-60 triad 8b have been synthesized with the aim of developing novel precursors for photoinduced polymerization. The electrochemical oxidation of pentad 8a by repetitive cyclic voltammogram scans gave a polymeric 8a film on a FTO electrode, which showed electrochemical activity and photoelectric response. When a monomer film of 8 on FTO was irradiated with visible light, the photoinduced polymerization of the terthiophene moiety was observed. The photoanodic features of an electropolymerized film of 8a on a FTO (poly-8a(electro)/FTO) and 8a/FTO were investigated regarding photocurrent response to light irradiation. The photocurrent of a photopolymerized 8a film on a FTO (poly-8a(photo)/FTO) electrode formed by photoreaction of 8a/FTO, is approximately 6 times greater than that of the 8a/FTO electrode.

    DOI: 10.1246/bcsj.20140283

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  • Synthesis and structures of monomeric group 14 triols and their reactivity Reviewed

    Lucian-Cristian Pop, Nobuaki Kurokawa, Hiroaki Ebata, Katsuya Tomizawa, Tomoyuki Tajima, Masatoshi Ikeda, Michikazu Yoshioka, Monique Biesemans, Rudolph Willem, Mao Minoura, Masaichi Saito

    CANADIAN JOURNAL OF CHEMISTRY   92 ( 6 )   542 - 548   2014.6

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:CANADIAN SCIENCE PUBLISHING, NRC RESEARCH PRESS  

    The first stable stannanetriol and germanetriol bearing sterically congested aryl groups were synthesized by hydrolysis of the corresponding trichloro-stannane and -germane. The stannanetriol is monomeric in solution as well as in the crystalline state, as evidenced by X-ray diffraction analysis and CP-MAS NMR spectroscopy. The stannanetriol reacted with silicone grease to afford a cagelike compound having three Sn-O-Si-O-Sn linkages in the molecule. All the group 14 triols can be converted to the corresponding trihalo compounds in good yields.

    DOI: 10.1139/cjc-2013-0496

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  • A Convenient Route to Synthetic Analogues of the Oxidized Form of High-Potential Iron-Sulfur Proteins Reviewed

    Kazuki Tanifuji, Norihiro Yamada, Tomoyuki Tajima, Takahiro Sasamori, Norihiro Tokitoh, Tsukasa Matsuo, Kohei Tamao, Yasuhiro Ohki, Kazuyuki Tatsumi

    INORGANIC CHEMISTRY   53 ( 8 )   4000 - 4009   2014.4

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:AMER CHEMICAL SOC  

    An amide-bound [Fe4S4](3+). cluster, [Fe4S4{N-(SiMe3)(2)}(4)](-) (1), was found to serve as a convenient precursor for synthetic analogues of the oxidized form of high-potential iron sulfur proteins. Treatment of 1 with 4 equiv of bulky thiols led to replacement of the amide ligands with thiolates, giving rise to a series of [Fe4S4(SR)(4)](-) clusters (R = Dmp (2a), Tbt (2b), Eind (2c), Dxp (2d), Dpp (2e); Dmp = 2,6-di(mesityl)phenyl, Tbt = 2,4,6-tris[bis(trimethylsily)methyl]phenyl, Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl, Dxp = 2,6-di(m-xylyl)phenyl, Dpp = 2,6-diphenylphenyl). These clusters were characterized by the mass spectrum, the EPR spectrum, and X-ray crystallography. The redox potentials of the [Fe4S4](3+/2+) couple, -0.82 V (2a), -0.86 V (2b), -0.84 V (2c), -0.74 V (2d), and -0.63 V (2e) vs Ag/Ag+ in THF, are significantly more negative than that of [Fe4S4(SPh)(4)](-/2-) (-0.21 V).

    DOI: 10.1021/ic402890k

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  • Spectroscopic Characterization of Nanohybrids Consisting of Single-walled Carbon Nanotubes and Fullerodendron Reviewed

    Hironori Suzuki, Yoko Iizumi, Masayoshi Tange, Soon-Kil Joung, Akihiro Furube, Takaaki Wada, Tomoyuki Tajima, Yutaka Takaguchi, Toshiya Okazaki

    FULLERENES NANOTUBES AND CARBON NANOSTRUCTURES   22 ( 1-3 )   75 - 87   2014.1

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:TAYLOR & FRANCIS INC  

    Hydrogen gas, which can be used in fuel cells to generate electricity, is considered the ultimate clean energy source. Recently, it was reported that a photo-induced electron transfer system consisting of single-walled carbon nanotubes (SWCNTs) and fullerodendrons shows photo-catalytic activity with a very high quantum yield for splitting water under visible light irradiation. However, the mechanism of high efficiency hydrogen generation is not yet clearly understood. We report here the spectroscopic characterizations of the SWCNT-fullerodendron composites. The results indicate two important fundamental properties of the composite system. First, fullerodendrons preferentially interact with the semiconducting SWCNTs instead of with their metallic counterparts. Second, the photo-induced electron transfer process from the C-60 moiety of fullerodendrons to SWCNTs occurs more efficiently with an increasing tube diameter.

    DOI: 10.1080/1536383X.2013.794340

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  • Preparation and Optical and Electrochemical Properties of Phthalocyanines with the Ttf Unit Reviewed

    Takeshi Kimura, Nobuhiro Takahashi, Tomoyuki Tajima, Yutaka Takaguchi

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS   188 ( 4 )   408 - 412   2013.4

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:TAYLOR & FRANCIS LTD  

    Tetrathiafluvalene (TTF)-annulated symmetrical and unsymmetrical phthalocyanines (4), (5), and (6) were prepared from 3,6-dioctylphthalonitrile (1) with a TTF unit, 4,5-dioctyloxyphthalonitrile (2), and 3,6-dioctyloxyphthalonitrile (3). Tetra-TTF-annulated phthalocyanine (4) and iodine produced an electron transfer complex which showed a radical cationic character.

    DOI: 10.1080/10426507.2012.729115

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  • Template-free fabrication of a cylindrical macropore array in SnO2 Reviewed

    Yushi Ozawa, Tomoyuki Tajima, Masayasu Nishi, Takahiro Ohkubo, Yutaka Takaguchi

    RSC ADVANCES   3 ( 45 )   22949 - 22952   2013

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    A simple sol-gel condensation of tin(IV) tert-butoxide led to the formation of meso/macroporous membranes. SEM observation clearly shows the cylindrical macropore array, of which mean pore diameter is controllable between 200 and 800 nm. The existence of slit-shaped mesopores (12 nm) was confirmed by a N-2 adsorption-desorption experiment.

    DOI: 10.1039/c3ra43642j

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  • Photosensitized hydrogen evolution from water using single-walled carbon nanotube/fullerodendron/Pt(II) coaxial nanohybrids Reviewed

    Yukari Sasada, Tomoyuki Tajima, Takaaki Wada, Tetsuya Uchida, Masayasu Nishi, Takahiro Ohkubo, Yutaka Takaguchi

    NEW JOURNAL OF CHEMISTRY   37 ( 12 )   4214 - 4219   2013

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    Direct incorporation of a Pt(II) complex into the shell of SWCNT/fullerodendron coaxial nanohybrids produces a new coaxial nanowire, SWCNT/fullerodendron/Pt(II), that shows efficient photocatalytic activity for hydrogen evolution from water (Phi = 0.16 upon irradiation at 450 +/- 5 nm) without any aid of electron relay such as methyl viologen.

    DOI: 10.1039/c3nj00790a

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  • Synthesis and Characterization of 2,3,9,10-Tetradendronized Pentacene Reviewed

    Tomoyuki Tajima, Akio Yamakawa, Keitaro Fukuda, Yuuki Hayashi, Masahiko Nakano, Yutaka Takaguchi

    CHEMISTRY LETTERS   41 ( 12 )   1622 - 1624   2012.12

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:CHEMICAL SOC JAPAN  

    A new pentacene dendrimer was synthesized in 81% yield through the aromatization of a dihydropentacene derivative having benzyl ether dendrons at the C2, C3, C9, and C10 positions. The dendrimer is very soluble in various organic solvents such as toluene, benzene, chloroform, dichloromethane, acetone, and ethyl acetate. The half-life of the dendrimer reaches 22.4 min upon photoirradiation in air. Interestingly, regiospecific [4 + 2] cycloaddition reactions proceeded at the central ring of the pentacene.

    DOI: 10.1246/cl.2012.1622

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  • alpha-SUBSTITUTED UNSYMMETRICAL PHTHALOCYANINES WITH ONE THROUGH THREE TTF UNITS AND THEIR OPTICAL AND ELECTROCHEMICAL PROPERTIES Reviewed

    Takeshi Kimura, Nobuhiro Takahashi, Tomoyuki Tajima, Yutaka Takaguchi

    HETEROCYCLES   86 ( 1 )   679 - 686   2012.12

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:PERGAMON-ELSEVIER SCIENCE LTD  

    alpha-Substituted unsymmetrical phthalocyanines fused with one through three TTF units were prepared from mixed 3,6-dioctyloxyphthalonitrile and 3,6-dioctylphthalonitrile bearing a TTF unit. The optical and electrochemical properties of the products were determined by UV-vis spectroscopy and cyclic voltammetry. Mono-TTF-annulated phthalocyanine and iodine produced the electron transfer complex which showed the radical cationic character.

    DOI: 10.3987/COM-12-S(N)18

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  • Proton nuclear magnetic resonance and pattern recognition analysis of liver extracts from rats under different anesthetics Reviewed

    Tomoyuki Tajima, Keiko Hirakawa, Hiroshi Kawaguchi, Atsuhiro Sakamoto

    BMC MEDICAL IMAGING   12   2012.8

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:BIOMED CENTRAL LTD  

    Background: Although general anesthesia is widely used in the surgical arena, the mechanisms by which general anesthetics act remain unclear. We previously described alterations in gene expression ratios in hepatic tissue taken from rats treated with anesthetics. Consequently, it is considered that anesthetics influence liver metabolism. Thus, the goal of this study was to use pattern recognition analysis of proton nuclear magnetic resonance spectra to visualize changes in liver metabolic phenotypes in response to widely used intravenous anesthetics (propofol and dexmedetomidine) and inhalational anesthetics (sevoflurane and isoflurane).
    Methods: Rats were randomized into 13 groups (n = 6 in each group), and each group received one of following agents: propofol, dexmedetomidine, sevoflurane, isoflurane, or no anesthetic (control group). The liver was directly removed from rats immediately after or 24 h or 48 h after a 6-h period of anesthesia. Hydrophilic compounds were extracted from the liver and were analyzed with proton nuclear magnetic resonance spectroscopy. All spectral data were processed and analyzed by principal component analysis for comparison of metabolite profiles.
    Results: Data were visualized by plotting principal component (PC) scores. In the plots, each point represents an individual sample. Each group was clustered separately on the plots, and the PC scores of the propofol group were clearly distinct from those of the control group and other anesthetic groups. The difference in PC scores was more pronounced immediately after completion of anesthesia when compared with 24 or 48 h after completion of anesthesia. Although the effect of intravenous anesthetics on the liver dissipated over time, the effect of inhalational anesthetics persisted.
    Conclusions: Propofol, dexmedetomidine, sevoflurane and isoflurane exert different effects on liver metabolism. In particular, liver metabolism was markedly altered after exposure to propofol. The effect of anesthesia on the liver under propofol or dexmedetomidine resolved rapidly when compared with the effect under sevoflurane or isoflurane.

    DOI: 10.1186/1471-2342-12-28

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  • Factors affecting reproduction in rehabilitant female orangutans: young age at first birth and short inter-birth interval Reviewed

    Noko Kuze, David Dellatore, Graham L. Banes, Peter Pratje, Tomoyuki Tajima, Anne E. Russon

    PRIMATES   53 ( 2 )   181 - 192   2012.4

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:SPRINGER JAPAN KK  

    This study investigated the reproductive parameters of free-ranging rehabilitant female orangutans. We aimed to assess the factors that influence these parameters and provide information that could assist with the management of orangutan reintroduction programs. We analyzed the birth records of free-ranging female rehabilitants at Bukit Lawang, Bukit Tigapuluh, Sepilok, Camp Leakey, Kaja Island, Sungai Wain, and Meratus and compared them with reproductive parameters reported in wild and zoo populations. Females' ages at first birth were 10.6-14.7 years, significantly earlier than those of wild and zoo orangutans. Computed inter-birth intervals (IBIs) calculated by the Kaplan-Meier method were 65.1-90.1 months; the values for Camp Leakey and Bukit Lawang rehabilitants were significantly shorter than those reported for wild Sumatran orangutans. Infant mortality rates were 18-61%; the values for Bukit Lawang and Sepilok were significantly higher than those reported for wild Sumatran and zoo orangutans. In rehabilitants, young ages at first birth and shorter IBIs may result from the high energy intake enabled by provisioning, although the possibility exists that they reflect underestimations of age on arrival at rehabilitation centers. The observed high infant mortality rate may reflect poor mothering skills due to human rearing and/or increased disease transmission. This study demonstrates that accelerated reproductive rates (younger age at first birth and shorter IBI) are common in provisioned rehabilitant females on both Sumatra and Borneo.

    DOI: 10.1007/s10329-011-0285-z

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  • Molecular Structure and Electronic State of the Dibenzo[a,e]pentalene Anion Radical Reviewed

    Masaichi Saito, Yoko Hashimoto, Tomoyuki Tajima, Kazuya Ishimura, Shigeru Nagase, Mao Minoura

    CHEMISTRY-AN ASIAN JOURNAL   7 ( 3 )   480 - 483   2012.3

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

    DOI: 10.1002/asia.201100711

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  • PREPARATION AND OPTICAL AND ELECTROCHEMICAL PROPERTIES OF UNSYMMETRICAL PHTHALOCYANINES WITH ONE OR TWO TTF UNITS Reviewed

    Takeshi Kimura, Nobuhiro Takahashi, Tomoyuki Tajima, Yutaka Takaguchi

    HETEROCYCLES   84 ( 1 )   333 - 337   2012.1

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    Unsymmetrical phthalocyanines with one or two TTF units were obtained by treating mixed 3,6-dioctyltetrathiafluvalenophthalonitrile and 4,5-dioctoxyphthalonitrile with Li in n-hexanol. Their optical and electrochemical properties were examined by UV-vis spectroscopy and cyclic voltammetry.

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  • Synthetic analogues of [Fe4S4(Cys)(3)(His)] in hydrogenases and [Fe4S4(Cys)(4)] in HiPIP derived from all-ferric [Fe4S4{N(SiMe3)(2)}(4)] Reviewed

    Yasuhiro Ohki, Kazuki Tanifuji, Norihiro Yamada, Motosuke Imada, Tomoyuki Tajima, Kazuyuki Tatsumi

    PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA   108 ( 31 )   12635 - 12640   2011.8

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    The all-ferric [Fe4S4](4+) cluster [Fe4S4{N(SiMe3)(2)}(4)] 1 and its one-electron reduced form [1](-) serve as convenient precursors for the synthesis of 3:1-site differentiated [Fe4S4] clusters and high-potential iron-sulfur protein (HiPIP) model clusters. The reaction of 1 with four equivalents (equiv) of the bulky thiol HSDmp (Dmp= 2,6-(mesityl)(2)C6H3, mesityl =2,4,6-Me3C6H2) followed by treatment with tetrahydrofuran (THF) resulted in the isolation of [Fe4S4(SDmp)(3)(THF)(3)] 2. Cluster 2 contains an octahedral iron atom with three THF ligands, and its Fe(S)(3)(O)(3) coordination environment is relevant to that in the active site of substrate-bound aconitase. An analogous reaction of [1](-) with four equiv of HSDmp gave [Fe4S4(SDmp)(4)](-) 3, which models the oxidized form of HiPIP. The THF ligands in 2 can be replaced by tetramethyl-imidazole (Me(4)Im) to give [Fe4S4(SDmp)(3)(Me(4)Im)] 4 modeling the [Fe4S4 (Cys)(3)(His)] cluster in hydrogenases, and its one-electron reduced form [4](-) was synthesized from the reaction of 3 with Me(4)Im. The reversible redox couple between 3 and [3](-) was observed at E-1/2=-820 mV vs. Ag/Ag+, and the corresponding reversible couple for 4 and [4](-) is positively shifted by +440 mV. The cyclic voltammogram of 3 also exhibited a reversible oxidation couple, which indicates generation of the all-ferric [Fe4S4](4+) cluster, [Fe4S4(SDmp)(4)].

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  • Photoreactive Molecule Incorporated within Dendritic Architecture Reviewed

    Yutaka Takaguchi, Tomoyuki Tajima

    JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN   69 ( 6 )   705 - 714   2011.6

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    Dendrimers or dendrons having chromophore at the core or focal point were synthesized, and effects of dendritic substituent on photofunctionality were investigated. We found photoisomerization from allyl alcohol to ketone by the use of dendrimer disulfide as catalyst. Various photooxygenation reactions proceeded by the use of Cd10S16 molecular cluster dendrimer or fullerodendron as photosensitizer of singlet oxygen. Photoinduced charge separation of fullerodendrimers take place with high quantum efficiency in aqueous solution. In the presence of viologen dication and a sacrificial donor, the persistent viologen radical cation was generated. This electron pooling efficiency was obviously enhanced by the use of single-walled carbon nanotube/fullerodendron supramolecular system.

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  • Synthesis of Poly(amidoamine) Dendrimer with a Diphenyl Diselenide Core Reviewed

    Tomoyuki Tajima, Yukie Yamaguchi, Yo-hei Shiomoto, Yutaka Takaguchi

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS   186 ( 1 )   2 - 11   2011

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    We succeeded in the synthesis of a novel poly(amidoamine) dendrimer having diphenyl diselenide at the core. Modification of the dendrimer diselenide by the reaction with glucono--lactone in methanol gave a water-soluble dendrimer diselenide having chiral terminal groups. The structures of dendrimers were satisfactorily confirmed by MAIDI-TOF MS spectrometry, elemental analysis, and NMR spectroscopy. Interestingly, induced circular dichroism (ICD) of the interaction between the diphenyl diselenide core and D-gluconamide periphery of the dendrimer was observed at 300 nm. Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements to view the free supplemental file. GRAPHICAL ABSTRACT[image omitted].

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  • Optically pure fullerodendron formed by diastereoselective Diels-Alder reaction Reviewed

    Nobuhiro Takahashi, Tomoyuki Tajima, Naoki Tsugawa, Yutaka Takaguchi

    TETRAHEDRON   66 ( 39 )   7787 - 7793   2010.9

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    The Diels-Alder reaction between C(60) and anthryl glycodendron, which has D- or L-gluconamides at the terminals, gave a new fullerene glycodendron conjugate. Interestingly, the diastereoselective cycloaddition reaction proceeded upon the treatment of C60 with the anthryl dendron 3. Furthermore, optical pure fullerodendrons (-)-4L and (+)-4D, which were confirmed by (1)H and (13)C NMR spectroscopy, FT-IR, MALDI-TOF mass spectroscopic analysis, were isolated from the mixture of diastereomers. And their absolute configurations were predicted by the use of CD spectra. (C) 2010 Elsevier Ltd. All rights reserved.

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  • 1,5-Bis[2,6-bis(2,4,6-triisopropylphenyl)phenyl]-2,3,4,6,7-pentatellura-1,5-distannabicyclo[3.1.1]heptane Reviewed

    Masaichi Saito, Hizuru Hashimoto, Tomoyuki Tajima

    ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE   66 ( Pt 8 )   M885 - U273   2010.8

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    The title compound, [Sn(2)(C(72)H(98))Te(2)(Te(3))], has a cage-like structure with bulky aryl substituents on the Sn atoms. The molecule sits over a crystallographic twofold axis, and hence the asymmetric unit consists of one half-molecule. Due to the twofold axis, the tritelluride part has a 1:1 disorder. One of the six-membered rings has a boat conformation, whereas the other has a chair conformation. The ditelluradistannane ring has a bent structure, with a dihedral angle of 32.89 (2)degrees between the two Te-Sn-Te planes.

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  • Formation of Pentaorganostannates from Bis(2-bromo-2 '-biphenyl)stannanes and tert-Butyllithium upon Substitution of Alkyl and Aryl Groups on Tin Atoms Reviewed

    Masaichi Saito, Sanae Imaizumi, Tomoyuki Tajima

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY   ( 14 )   2153 - 2157   2010.5

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    The reaction of bis(2-bromo-2'-biphenyl)stannanes 1 with tert-butyllithium in the presence of diaryl- and dialkyldichlorostannanes leads to the extrusion of aryl and alkyl groups on the tin atom, affording 9-stannafluorene derivatives bearing biphenyl groups. The intermediates of the reactions were assigned to the corresponding pentaorganostannates, which were characterized by NMR spectroscopy. Unexpectedly, the dissociation of the aryl and alkyl groups from the tin atoms in intramolecular nucleophilic substitution reactions was preferable to that of chloride ions in intermolecular nucleophilic substitution reactions.

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  • Arching a bay area of triphenyleno[1,12-bcd]thiophene with group 14 functionalities: Synthesis of the first triphenylene derivatives having thiophene and metallafluorene moieties Reviewed

    Masaichi Saito, Tomoharu Tanikawa, Tomoyuki Tajima, Jing Dong Guo, Shigeru Nagase

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   695 ( 7 )   1035 - 1041   2010.4

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    Arching a bay area of triphenyleno[1,12-bcd]thiophene with group 14 functionalities gave the first triphenylene derivatives whose two pairs of bay carbons are connected by two different heteroatom functionalities. Triphenyleno[1,12-bcd:4,5-b'c'd']dithiophene, which had been only accessible through the very severe reaction conditions, was synthesized under the mild reaction conditions. Photophysical properties of newly-obtained heterolotriphenylene derivatives are discussed with theoretical calculations. (C) 2009 Elsevier B. V. All rights reserved.

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  • Nonaggressive interventions by third parties in conflicts among captive Bornean orangutans (Pongo pygmaeus) Reviewed

    Tomoyuki Tajima, Hidetoshi Kurotori

    PRIMATES   51 ( 2 )   179 - 182   2010.4

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    Whereas orangutans are regarded as semisolitary animals in the wild, several studies have reported frequent social interactions, including aggression, among orangutans in captivity. As yet, there is a lack of knowledge about how they cope with aggression. In this report, we provide a number of new observations of interventions by third parties in aggressive interactions within a captive group of Bornean orangutans (Pongo pygmaeus) in the Tama Zoological Park, Japan. We observed that an adult female and a juvenile male orangutan intervened in aggressive interactions. The victim was a newly introduced juvenile female who was unrelated to anyone in the zoo. The ways in which the orangutans intervened were not aggressive, as the interveners simply aimed to separate the opponents, and these interventions did not lead to further aggression in almost every case. Our observations suggest that third parties can play an important role in managing aggressive conflicts among captive orangutans and, under conditions in which orangutans share limited space, nonaggressive interventions by third parties for settling conflicts appear. It is possible that orangutans may actively promote the peaceful coexistence of other individuals.

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  • Dilithioplumbole: A Lead-Bearing Aromatic Cyclopentadienyl Analog Reviewed

    Masaichi Saito, Masafumi Sakaguchi, Tomoyuki Tajima, Kazuya Ishimura, Shigeru Nagase, Masahiko Hada

    SCIENCE   328 ( 5976 )   339 - 342   2010.4

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    Although the concept of aromaticity has long played an important role in carbon chemistry, it has been unclear how applicable the stabilizing framework is to the heaviest elements. Here we report the synthesis of dilithiotetraphenylplumbole by reduction of hexaphenylplumbole. X-ray crystallography revealed a planar structure with no alternation of carbon-carbon bond lengths in the five-membered ring core. Nuclear magnetic resonance spectra and relativistic theoretical calculations show considerable aromatic character in the molecule, thus extending aromaticity to carbon's heaviest congener.

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  • Formation of Zwitterionic Fullerodendron Using a New DBN-Focal Dendron Reviewed

    Yutaka Takaguchi, Maki Hosokawa, Masatoshi Mayahara, Tomoyuki Tajima, Takahiro Sasamori, Norihiro Tokitoh

    SENSORS   10 ( 1 )   613 - 624   2010.1

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    A new poly(amidoamine) dendron having 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) at the focal point was synthesized. Interestingly, formation of zwitterionic fullerodendrons (lambda(max) = 930 nm for C(60) and 795 nm for C(70)) were observed by Vis-NIR spectroscopy upon the reaction of C(60) or C(70) with the DBN-focal dendron. In particular, the C(70) anion was effectively stabilized by the site isolation effect of the dendritic wedge. The half-life of fullerodendron 12b having C(70) anion at the focal point reaches 7,345 min, which is 20 times longer than that of complex between C(60) and pristine DBN. Furthermore, in order to confirm the structure of the zwitterionic complex, fullerodendron 12a was reprecipitated from benzonitrile/1,2,4-trimethylbenzene, and was observed using IR spectroscopy and APPI-MS.

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  • Synthesis and structures of heterasumanenes having different heteroatom functionalities Reviewed

    Masaichi Saito, Tomoharu Tanikawa, Tomoyuki Tajima, Jing Dong Guo, Shigeru Nagase

    TETRAHEDRON LETTERS   51 ( 4 )   672 - 675   2010.1

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    After the protection of two alpha-carbons of the dibenzothiophene moiety in triphenylenothiophene 1 by trimethylsilyl groups, the resulting compound 4 reacted with butyllithium followed by dichlorodimethylsilane to afford 10H-silolo[2',3',4',5':4,5]triphenyleno[1,12-bcd]thiophene 8, which reacted with butyllithium followed by dichlorodimethylsilane to afford novel heterasumanene 11. Using dichlorodimethylstannane instead of dichlorodimethylsilane afforded heterasumanene 12, which is the first example of a heterasumanene having three different heteroatom functionalities. (C) 2009 Elsevier Ltd. All rights reserved.

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  • Synthesis, Structures, and Properties of Plumboles Reviewed

    Masaichi Saito, Masafumi Sakaguchi, Tomoyuki Tajima, Kazuya Ishimura, Shigeru Nagase

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS   185 ( 5-6 )   1068 - 1076   2010

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    Reactions of 1,4-dilithio-1,2,3,4-tetraphenyl-1,3-butadiene with dichlorodiphenylplumbane gave hexaphenylplumbole 1 and spirobiplumbole 2. These structures were determined by X-ray diffraction analysis. Electronic structures of 1 and 2 were discussed by the aid of NMR analysis and theoretical calculations. The compounds 1 and 2 were found to be the first fluorescent organolead compounds.

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  • Synthesis and structure of the dithienostannole anion Reviewed

    Masaichi Saito, Munenori Shiratake, Tomoyuki Tajima, Jing Dong Guo, Shigeru Nagase

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   694 ( 25 )   4056 - 4061   2009.12

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    Novel dithienostannoles were synthesized by the reactions of the corresponding dilithiobithiophenes with dichlorodiphenylstannane. A unique byproduct, 10-membered ring compound was also obtained. Reduction of type A dithienostannole with lithium afforded 2,2'-dilithio-3,3'-bithiophene, while reduction of type B dithienostannole with lithium afforded the corresponding dithienostannole anion. The structure and aromaticity of the dithienostannole anion are also discussed. (C) 2009 Elsevier B. V. All rights reserved.

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  • NOVEL REACTIONS OF STERIC ENCUMBERED 1,4-DILITHIO-1,3-BUTADIENE WITH GROUP 14 ELECTROPHILES: FORMATION AND STRUCTURE OF STABLE DIHYDROXYGERMOLE Reviewed

    Masaichi Saito, Michio Nakamura, Tomoyuki Tajima

    HETEROCYCLES   78 ( 3 )   657 - 668   2009.3

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    Reactions of 1,4-dilithio-1,3-butadiene 1 having bulky silyl ligands at the 1,4-positions with group 14 electrophiles were examined. Reactions of 1,4-dilithio-1,3-butadiene 1 with tetraethoxygermane gave diethoxygermole 5, which was hydrolyzed to give stable dihydroxygermole 16. The X-ray diffraction analysis of dihydroxygermole 16 revealed intermolecular hydrogen bonds. The reaction of I with stannous chloride was also examined.

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  • DECHALCOGENATION OF PENTACHALCOGENADISTANNA-BICYCLO[3.1.1]HEPTANES Reviewed

    Masaichi Saito, Hizuru Hashimoto, Tomoyuki Tajima

    HETEROCYCLES   76 ( 1 )   515 - 520   2008.9

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    Pentathia- and pentaselena-distannabicyclo[3.1.1]heptanes reacted with tributylphosphine to afford tetrathia- and tetraselena- distanna-bicyclo[2.1.1]hexanes, respectively. The novel heterocyclic framework of a tetrathiadistannabicyclo[2.1.1]hexane was demonstrated by X-ray structural analysis. Structures of a series of pentachalcogena and tetrachalcogena derivatives are discussed.

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  • Synthesis and characterization of the first stable stannanetelone Reviewed

    Norihiro Tokitoh, Tomoyuki Tajima, Nobuhiro Takeda, Takahiro Sasamori

    PHOSPHORUS SULFUR AND SILICON AND THE RELATED ELEMENTS   183 ( 4 )   948 - 955   2008.4

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    The first example of a stable stannanetellone was synthesized and isolated by taking advantage of kinetic stabilization afforded by the combination of steric protecting groups, 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris(trimethylsilyl)methyl]phenyl (Bbt) and 2,2 '',4,4 ''-tetraisopropyl-m-terphenyl-2'-yl groups. The structural parameters and spectroscopic data of the isolated stannanetellone were systematically compared with those previously reported for the lighter congeners, i. e., the stannanethione and stannaneselone. Attempted synthesis of a stannanetellone by the reaction of dilithiostannane with tellurium dichloride is also described.

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  • New reactions of a dibenzo[a,e]pentalene Reviewed

    Masaichi Saito, Michio Nakamura, Tomoyuki Tajima

    CHEMISTRY-A EUROPEAN JOURNAL   14 ( 20 )   6062 - 6068   2008

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    Reduction of dibenzo[a,e]pentalene 3 (denoted as dibenzopentalene hereafter) with excess lithium gave dilithium dibenzopentalenide 1. Since oxidation of I with iodine gave 3, redox behavior between 1 and 3 is controllable and reversible. Reaction of 3 with methyllithium gave lithium 5-methyldibenzopehtalenide 5, the formation of which was evidenced by some trapping experiments and X-ray crystallographic analysis. Reactions of 3 with halogens gave 5,10-dihalodibenzopentalenes, 8 and 9. Some optical properties of novel dibenzopentalene derivatives are also demonstrated.

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  • Synthesis, structure and reactions of a trianion equivalent, trilithiostannane Reviewed

    Tomoyuki Tajima, Masatoshi Ikeda, Masaichi Saito, Kazuya Ishimura, Shigeru Nagase

    CHEMICAL COMMUNICATIONS   ( 48 )   6495 - 6497   2008

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    Transmetallation reaction of trisilylstannane ArSn( SiHMe(2))(3) (Ar = 2,6-bis(2,4,6-triisopropylphenyl)phenyl), bearing a bulky substituent on the tin atom, with methyllithium in THF at room temperature gave the first trianion equivalent, trilithiostannane ArSnLi(3), the generation of which was confirmed by trapping experiments with some electrophiles as well as by (119)Sn and (7)Li NMR spectroscopy.

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  • Synthesis and structure of pentaorganostannate having five carbon substituents Reviewed

    Masaichi Saito, Sanae Imaizumi, Tomoyuki Tajima, Kazuya Lshimura, Shigeru Nagase

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   129 ( 36 )   10974 - +   2007.9

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    The reaction of spirostannabifluorene with methyllithium gave lithium pentaorganostannate, which is an intermediate of the transmetalation reaction on the tin atom and the first example of a stable pentaorganostannate having five carbon substituents. The X-ray structural analysis reveals its slightly distorted trigonal bipyramidal structure, the apical bonds of which have a considerable s character. The unique structure of the lithium pentaorganostannate is also discussed by the aid of theoretical calculations.

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  • Synthesis and reactions of a novel bulky aryllithium Reviewed

    Masaichi Saito, Yuta Okuyama, Tomoyuki Tajima, Daichi Kato, Michikazu Yoshioka

    APPLIED ORGANOMETALLIC CHEMISTRY   21 ( 7 )   604 - 611   2007.7

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    A novel bulky aryllithium, 2,6-bis{2,5-bis[bis(trimethylsilyl)methyl]phenyl}phenyllithium (BbspLi), was synthesized. Reactions of BbspLi 5 with Group 14 electrophiles, such as stannous chloride, with carbon tetrachloride or tetrachlorometallanes gave fluorene 6. Reaction of BbspLi with carbon tetrachloride gave benzyl chloride 8, which converted to 6 under acidic conditions. BbspLi 5 isomerized to the corresponding benzyl anion 10, which underwent halophilic reactions with Group 14 electrophiles to give fluorene 6 via the benzyl chloride intermediate 8. Copyright (c) 2007 John Wiley & Sons, Ltd.

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  • 3,5-Bis(trimethylsilyl)triphenyleno[1,12bcd]thiophene Reviewed

    Masaichi Saito, Tomoharu Tanikawa, Tomoyuki Tajima

    ACTA CRYSTALLOGRAPHICA SECTION E-STRUCTURE REPORTS ONLINE   63   O2923 - U2631   2007.6

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    In the title compound, C24H26SSi2, the fused ring system plus the two Si atoms are coplanar, consistent with planar triphenylene but contrary to bowl-shaped triphenyleno[1,12-bcd:4,5-b'c'd':8,9-b '' c '' d '']-trithiophene. The bond alternation pattern of the C-C bonds in the title compound is similar to that found in triphenyleno[1,12-bcd:4,5-b'c'd':8,9-b '' c '' d '']-trithiophene, although the lengths of the C-C bonds around the central and thiophene rings of the title compound are slightly different from the corresponding bonds of triphenyleno[1,12-bcd:4,5-b'c'd':8,9-b '' c '' d '']-trithiophene.

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  • Synthesis and structure of a kinetically stabilized stannanethione Reviewed

    Tomoyuki Tajima, Takahiro Sasamori, Nobuhiro Takeda, Norihiro Tokitoh

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   80 ( 6 )   1202 - 1204   2007.6

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    The X-ray crystallographic analysis of a stable stannanethione, Bbt(Titp)Sn = S, reveals that the tin-sulfur bond distance [2.221(3) angstrom] is ca. 10 % shorter than the normal tin-sulfur single bonds and the tin atom of the stannanethione has a trigonal planar geometry, as do as the carbonyl carbon atoms.

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  • Synthesis and structures of polychalcogenadistannabicyclo[k.l.m]alkanes Reviewed

    Masaichi Saito, Hizuru Hashimoto, Tomoyuki Tajima, Masatoshi Ikeda

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   692 ( 13 )   2729 - 2735   2007.6

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    Reaction of steric encumbered trichlorostannane with disodium sulfide or dilithium selenide gave 2,4-dimercapto-1,3,2,4-dithiadistannetane or tetraselenadistannabicyclo[2.1.1]hexane, respectively. Reactions of steric encumbered trihydrostannane with elemental chalcogens gave pentachalcogenadistannabicyclo[k.1.1]heptanes (k = 2 and 3). The two bridgehead tin atoms of the first polychalcogenadistannabicyclo[k.l.m]alkanes are concluded to have no significant bonding interaction, judging from the longer bond distances than those of the normal tin-tin single bonds. (c) 2007 Elsevier B.V. All rights reserved.

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  • Reduction of phenyl silyl acetylenes with lithium: Unexpected formation of a dilithium dibenzopentalenide Reviewed

    Masaichi Saito, Michio Nakamura, Tomoyuki Tajima, Michikazu Yoshioka

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   46 ( 9 )   1504 - 1507   2007

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  • A kinetically stabilized stannanetellone, a tin-tellurium double-bonded compound Reviewed

    Tomoyuki Tajima, Nobuhiro Takeda, Takahiro Sasamori, Norihiro Tokitoh

    ORGANOMETALLICS   25 ( 15 )   3552 - 3553   2006.7

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    A kinetically stabilized stannanetellone was synthesized by the telluration of an extremely hindered stannylene with (n-Bu)(3)Pd=Te. The structure of the stannanetellone was determined by X-ray crystallographic analysis.

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  • Synthesis of bis(germacyclopropa)benzenes and structures of their annelated benzene rings Reviewed

    T Tajima, T Sasamori, N Takeda, N Tokitoh, K Yoshida, M Nakahara

    ORGANOMETALLICS   25 ( 1 )   230 - 235   2006.1

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    Extremely hindered bis(germacyclopropa)benzenes (3a,b; the IUPAC name is 4,8-digermatricyclo[5.1.0.0(3,5)]octa-1,3(5),6-triene) were synthesized as stable crystalline compounds by the reaction of the corresponding dilithiogermane Tbt(Dip)GeLi2 (8; Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Dip = 2,6-diisopropylphenyl) with 1,2,4,5-tetrabromobenzene. The structures of the two stereoisomeric his(germacyclopropa)benzenes (3a, cis isomer; 3b, trans isomer) were definitively determined by X-ray crystallographic analysis. The central benzene ring of 3a was found to be folded, in contrast to the planar benzene ring of 3b. The X-ray crystallographic analyses of 3a and 3b and the theoretical calculations for some model molecules revealed that the annelated benzene rings have no distinct bond alternation.

    DOI: 10.1021/om0507629

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  • Generation and reactions of overcrowded diaryldilithiostannane and diaryldipotassiostannane Reviewed

    T Tajima, N Takeda, T Sasamori, N Tokitoh

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY   ( 21 )   4291 - 4300   2005.11

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    Exhaustive reduction of an overcrowded dibromostannane bearing two bulky aromatic substituents, Tbt(Dip)SnBr2 {Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Dip = 2,6-diisopropylphenyl}, with an excess amount of lithium naphthalenide in THF at -78 degrees C gave the corresponding dilithiostannane, Tbt(Dip)SnLi2, the generation of which was confirmed by trapping experiments with some electrophiles together with Sn-119 and Li-7 NMR spectroscopy. The diaryldilithiostannane was found to be stable in solution under an inert gas below -25 degrees C. The potassium analogue, Tbt(Dip)SnK2, was also generated by the reduction of the dibromostannane in THF at -78 degrees C by the use of KC8 as a reductant. The reactions of dilithiostannane and dipotassiostannane obtained with o-dibromobenzene did not give a stannacyclopropabenzene derivative but an unexpected cyclization product, a stannacyclobutabenzene derivative, in contrast to the reactions of the corresponding dilithiosilane and dilithiogermane, Tbt(Dip)ELi2 (E = Si, Ge), with o-dibromobenzene leading to the formation of the corresponding metallacyclopropabenzenes as stable crystalline compounds. A preliminary result of the synthesis of a tin-tellurium double-bond compound from the dilithiostannane is also presented. ((c) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005).

    DOI: 10.1002/eijc.200500375

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  • Reactivities of germacyclopropabenzene toward some transition metal carbonyl complexes Reviewed

    T. Tajima, T. Sasaki, T. Sasamori, N. Takeda, N. Tokitoh

    Applied Organometallic Chemistry   19 ( 4 )   570 - 577   2005.4

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    DOI: 10.1002/aoc.810

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  • Thermal reactions of an overcrowded germacyclopropabenzene with group 6 metal hexacarbonyl complexes [M(CO)(6)] (M = Cr, Mo, and W): a novel mode of CO insertion leading to the formation of cyclic germoxycarbene metal complexes Reviewed

    T Tajima, T Sasaki, T Sasamori, N Takeda, N Tokitoh

    CHEMICAL COMMUNICATIONS   ( 4 )   402 - 403   2004.2

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    Thermal reactions of an overcrowded germacyclopropabenzene with hexacarbonyl complexes of group 6 metals resulted in the formation of the corresponding cyclic germoxycarbene complexes, i.e., 1,2-oxagermolan-5-ylidene pentacarbonyl metal complexes, via a novel mode of CO insertion reaction toward cyclopropabenzene derivatives.

    DOI: 10.1039/b314010e

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  • Syntheses and structures of silicon analogues of cyclopropabenzenes Reviewed

    T Tajima, K Hatano, T Sasaki, T Sasamori, N Takeda, N Tokitoh, N Takagi, S Nagase

    JOURNAL OF ORGANOMETALLIC CHEMISTRY   686 ( 1-2 )   118 - 126   2003.11

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    The reactions of an overcrowded diaryldilithiosilane, Tbt(Dip)SiLi2 (Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl; Dip = 2,6-diisopropylphenyl), with o-dibromobenzene and 1,2,4,5-tetrabromobenzene resulted in the synthesis and isolation of the first stable silacyclopropabenzene and bis(silacyclopropa)benzenes (IUPAC name is 4,8-disilatricyclo[5.1.0.0(3,5)]octa-1,3(5),6-triene), respectively. The crystallographic analyses and theoretical calculations revealed that the lengths of the juncture carbon-carbon bonds of the mono- and bis(silacyclopropa)benzenes were marginally in the range of carbon-carbon bond lengths of usual benzene rings. It is shown that this structural feature is attributable to a decrease in the strain energy of silacyclopropabenzenes relative to the corresponding cyclopropabenzenes, and the strain energy is a simple additive function of the number of the fused three-membered rings involving Si atom. (C) 2003 Elsevier B.V. All rights reserved.

    DOI: 10.1016/S0022-328X(03)00446-7

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  • Self-assembly and regioselective photodimerization of anthracene having a dendritic substituent Reviewed

    Y Takaguchi, T Tajima, Y Yanagimoto, S Tsuboi, K Ohta, J Motoyoshiya, H Aoyama

    ORGANIC LETTERS   5 ( 10 )   1677 - 1679   2003.5

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    [GRAPHICS]
    Thermotropic liquid crystallinity can be induced for an anthracene having a dendritic substituent. The photodimerization reaction of an anthracene moiety in the smectic phase proceeded quantitatively and regioselectively.

    DOI: 10.1021/ol0343109

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  • Intra- and intermolecular photochemical properties of poly(amidoamine) dendrons with an anthracene at focal point Reviewed

    M Fujitsuka, O Ito, Y Takaguchi, T Tajima, K Ohta, J Motoyoshiya, H Aoyama

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   76 ( 4 )   743 - 747   2003.4

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    Photophysical and photochemical properties of poly(amidoamine) dendrons containing an anthracene at the focal point have been studied by the steady-state and transient spectroscopic methods in solution. The fluorescence lifetime of the anthracene moiety in the higher generation dendron (G3.5) is slightly shorter than that of the lower generation homologue (G0.5). On the other hand. the triplet lifetime of G3.5 is longer than that of G0.5. The bimolecular rate constants for energy transfer from the triplet states of the anthracene moiety to O-2 (k(O2)) and for T-T annihilation (k(TT)) were almost the same for the anthryl dendrons, G3.5 and G0.5, suggesting that the dendron groups do not hinder the approach of O-2 or the anthracene moiety. Photodimerization of G3.5 took place at a similar rate to G0.5. while the photodissociation rates of these anthracene dimers increase in the order of anthracene > G0.5 > G3.5, suggesting the presence of some attractive forces between dendron wedges.

    DOI: 10.1246/bcsj.76.743

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  • The first examples of stable benzenes fused with two three-membered rings: Synthesis and structures of the two stereoisomers of bis(silacyclopropa)benzenes Reviewed

    T Tajima, K Hatano, T Sasaki, T Sasamori, N Takeda, N Tokitoh

    CHEMISTRY LETTERS   32 ( 3 )   220 - 221   2003.3

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    Two stereoisomers of the first stable bis(silacyclopropa)benzenes (1a, 1b) were successfully synthesized by the reaction of Tbt(Dip)SiLi2 (3) [Tbt = 2,4,6-tris[bis(trimethylsilyl)methyl]phenyl, Dip = 2,6-diisopropylphenyl] with 1,2,4,5-tetrabromobenzene. The molecular structures of 1a and 1b were discussed on the basis of the X-ray structural analyses.

    DOI: 10.1246/cl.2003.220

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  • Photodimerization of anthracene having dendritic substituent within the vaterite crystal of CaCO3 Reviewed

    Y Takaguchi, Y Yanagimoto, T Tajima, K Ohta, J Motoyoshiya, H Aoyama

    CHEMISTRY LETTERS   ( 11 )   1102 - 1103   2002.11

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    Crystallization of CaCO3 in the presence of poly(amidoamine) (PAMAM) dendron containing an anthryl group at the focal point and carboxylate groups at the external surface resulted in the formation of spherical vaterite crystals. Furthermore, photodimerization reaction of anthracene unit proceeded within the vaterite crystals upon irradiation.

    DOI: 10.1246/cl.2002.1102

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  • Reversible binding of C-60 to an anthracene bearing a dendritic poly(amidoamine) substituent to give a water-soluble fullerodendrimer Reviewed

    Y Takaguchi, T Tajima, K Ohta, J Motoyoshiya, H Aoyama, T Wakahara, T Akasaka, M Fujitsuka, O Ito

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   41 ( 5 )   817 - +   2002

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    DOI: 10.1002/1521-3773(20020301)41:5<817::aid-anie817>3.0.co;2-r

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  • Reversible binding of C-60 to an anthracene bearing a dendritic poly(amidoamine) substituent to give a water-soluble fullerodendrimer Reviewed

    Y Takaguchi, T Tajima, K Ohta, J Motoyoshiya, H Aoyama, T Wakahara, T Akasaka, M Fujitsuka, O Ito

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   41 ( 5 )   817 - +   2002

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    DOI: 10.1002/1521-3773(20020301)41:5<817::AID-ANIE817>3.0.CO;2-R

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  • Synthesis, characterization and liquid crystal organization of a poly(amide amine) dendron having anthracene at the focal point

    Takaguchi Yutaka, Tajima Tomoyuki, Ohta Kazuchika, Motoyoshiya Jiro, Aoyama Hiromu

    Proceedings of Japanese Liquid Crystal Society Annual meeting   2001   479 - 480   2001

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    As a class of new materials, dendrimers have, in recent years, generated a great deal of interest within the scientific community. In particular, there is an increasing focus on developing applications for photoresponsive dendrimers. Recently, we have described dechalcogenation reaction of dendrimer dichalcogenides upon irradiation and a new photoreactive anthracenyl dendron undergoes a reversible photocyclization to form a dendrimer.^<1,2> Interestingly, a poly(amide amine) dendron having anthracene at the focal point undergoes reversible photodimerization within it's liquid-crystalline state. Investigation of thermal behavior of the LC dendron by means of polarizing optical microscopy, differential scanning calorimetry, and X-ray diffraction experiments reveals smectic-type mesophase.

    DOI: 10.11538/ekitou.2001.0_479

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  • Photoresponsive dendrimers: Syntheses and characterizations of anthracenes bearing dendritic substituents Reviewed

    Y Takaguchi, T Tajima, K Ohta, J Motoyoshiya, H Aoyama

    CHEMISTRY LETTERS   ( 12 )   1388 - 1389   2000.12

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    A new photoreactive anthracenyl dendron undergoes a reversible photocyclization to form a dendrimer.

    DOI: 10.1246/cl.2000.1388

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Books

  • 光吸収材料としてのSWCNTs

    ( Role: Sole author)

    CanAppleニュース(カーボン・エネルギーコントロール社会協議会) 2021,194号.  2021.4 

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    Total pages:1   Language:Japanese Book type:Textbook, survey, introduction

  • 再生可能エネルギーによる水素製造

    柴田 善朗, 石原 顕光, 太田 健一郎, 児玉 竜也, 木村 元昭, 加納 純也, 堂脇 清志, 平田 好洋, 鮫島 宗一郎, 下之薗 太郎, 中島田 豊, 石原 達己, 松本 広重, 曽根 理嗣, 杉山 正和, 泉 康雄, 佐山 和弘, 野地 智康, 近藤 政晴, 神 哲郎, 丹後 佑斗, 村上 範武, 石本 寛伍, 田嶋 智之, 高口 豊, 北島 正治, 櫻井 英博, 井上 和仁, 増川 一, 三宅 淳, 比護 拓馬, 小河 脩平, 関根 泰, 井口 昌幸, 姫田 雄一郎, 川波 肇, 花田 信子( Role: Joint author)

    S&T出版  2016.9  ( ISBN:4907002580

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MISC

  • Synthesis and Structures of Sterically Encumbered Group 14 Monolithio Compounds and Unexpected Differences in Their Reactivity

    Lucian-Cristian Pop, Nobuaki Kurokawa, Hiroaki Ebata, Katsuya Tomizawa, Tomoyuki Tajima, Masaichi Saito

    EUROPEAN JOURNAL OF INORGANIC CHEMISTRY   ( 43 )   4969 - 4975   2017.11

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    Group 14 monolithio compounds with sterically encumbered terphenyl ligands, ArM14(SiHMe2)(2)Li [M-14 = Si, Ge, Sn; Ar = 2,6-bis(2,6-diisopropylphenyl)phenyl and 2,6-bis(2,4,6-triisopropylphenyl)phenyl], were prepared by transmetalation reactions of ArM14(SiHMe2)(3) with methyllithium, the structures of which were established by X-ray diffraction analysis. The monolithiosilanes and monolithiogermanes reacted with iodomethane and trichlorophosphane to afford the corresponding monomethylated and dichlorophosphane-substituted derivatives, respectively. However, surprisingly, the reactions of monolithiostannanes with iodomethane and trichlorophosphane provided trimethylstannane and trichlorostannane, respectively.

    DOI: 10.1002/ejic.201700945

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  • Synthesis of a poly(amidoamine) dendrimer having a 1,10-bis(decyloxy) decane core and its use in fabrication of carbon nanotube/calcium carbonate hybrids through biomimetic mineralization

    Shunichi Nishimura, Tomoyuki Tajima, Tatsuki Hasegawa, Tomoaki Tanaka, Yutaka Takaguchi, Yuya Oaki, Hiroaki Imai

    CANADIAN JOURNAL OF CHEMISTRY   95 ( 9 )   935 - 941   2017.9

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    A new dendritic dispersant of carbon nanotubes (CNTs) was synthesized and applied for the noncovalent functionalization of single-walled carbon nanotubes (SWCNTs) and multi-walled carbon nanotubes (MWCNTs). The 1,10-bis(decyloxy) decane core of the poly(amidoamine) dendrimer strongly adhered to the sidewalls of CNTs to form CNT/dendrimer supramolecular nanocomposites having many carboxyl groups (-COOH) on the surface. Then, crystallization of calcium carbonate (CaCO3) by the CO2 diffusion technique in aqueous environments using the CNT/dendrimer supramolecular nanocomposites as scaffolds afforded monodisperse spherical CNT/CaCO3 nanohybrids consisting of CNTs and calcite nanocrystals. The morphologies of the SWCNT/CaCO3 hybrids and MWCNT/CaCO3 hybrids were almost the same.

    DOI: 10.1139/cjc-2017-0022

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  • Ligand Exchange Reaction of (Me4N)(4)[Cd10S4(SPh)(16)] with Diphenyl Diselenide

    Tomoyuki Tajima, Shoko Yamamoto, Yuta Sakamoto, Shoji Takagi, Toshitaka Nakaya, Yutaka Takaguchi, Asako Igashira-Kamiyama, Nobuto Yoshinari, Takumi Konno

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   90 ( 4 )   384 - 386   2017.4

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    The reaction of (Me4N)(4)[Cd10S4(SPh)(16)] (1) with diphenyl diselenide (2) in propionitrile afforded a molecular cluster, (Me4N)(4)[Cd10S4(SePh)(16)] (3), the structure of which was determined by X-ray crystallography. Ligand exchange proceeded in a heterogeneous reaction system, and the use of a less polar solvent appeared to be crucial for the synthesis of 3 to prevent degradation of the Cd10S4Se16 cluster core.

    DOI: 10.1246/bcsj.20160395

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  • Self-Assembly and Fluorescence Properties of [60]Fullerene-Pentacene Monoadducts

    Kentaro Kubo, Tomoyuki Tajima, Hitoshi Shirai, Takuya Nishihama, Yutaka Takaguchi

    CHEMISTRYSELECT   2 ( 8 )   2452 - 2456   2017.3

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    The highly soluble [60]fullerene-pentacene monoadducts 2a and 2b were synthesized by a Diels-Alder reaction between [60]fullerene and pentacene derivatives. The single-crystal X-ray diffraction analysis of 2a revealed an attractive intermolecular interaction between [60]fullerene moiety of one molecule and the pentacene arms of an adjacent molecule, resulting in the formation of head-to-tail dimers in solution. This self-association behavior of 2a and 2b was also observed by (HNMR)-H-1 and fluorescence spectroscopy in chloroform. Both the excitation and emission wavelengths can be modulated via the concentration of 2a and 2b.

    DOI: 10.1002/slct.201602074

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  • SWCNT Photocatalyst for Hydrogen Production from Water upon Photoexcitation of (8,3) SWCNT at 680-nm Light

    Noritake Murakami, Yuto Tango, Hideaki Miyake, Tomoyuki Tajima, Yuta Nishina, Wataru Kurashige, Yuichi Negishi, Yutaka Takaguchi

    SCIENTIFIC REPORTS   7   46 - 53   2017.3

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    Single-walled carbon nanotubes (SWCNTs) are potentially strong optical absorbers with tunable absorption bands depending on their chiral indices (n, m). Their application for solar energy conversion is difficult because of the large binding energy (&gt; 100 meV) of electron-hole pairs, known as excitons, produced by optical absorption. Recent development of photovoltaic devices based on SWCNTs as light-absorbing components have shown that the creation of heterojunctions by pairing chirality-controlled SWCNTs with C-60 is the key for high power conversion efficiency. In contrast to thin film devices, photocatalytic reactions in a dispersion/solution system triggered by the photoexcitation of SWCNTs have never been reported due to the difficulty of the construction of a well-ordered surface on SWCNTs. Here, we show a clear-cut example of a SWCNT photocatalyst producing H-2 from water. Self-organization of a fullerodendron on the SWCNT core affords water-dispersible coaxial nanowires possessing SWCNT/C-60 heterojunctions, of which a dendron shell can act as support of a co-catalyst for H-2 evolution. Because the band offset between the LUMO levels of (8, 3) SWCNT and C-60 satisfactorily exceeds the exciton binding energy to allow efficient exciton dissociation, the (8, 3) SWCNT/fullerodendron coaxial photocatalyst shows H-2-evolving activity (QY = 0.015) upon 680-nm illumination, which is E-22 absorption of (8, 3) SWCNT.

    DOI: 10.1038/srep43445

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  • Synthesis and Light-absorption Characteristics of Thiophene Derivatives Bearing Ferrocenylthiocarbonyl Groups

    Hideaki Miyake, Tomoyuki Tajima, Yutaka Takaguchi

    CHEMISTRY LETTERS   46 ( 1 )   48 - 50   2017.1

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    Thiophene-based dyes bearing two ferrocenylcarbonyl groups were obtained from a short synthesis involving direct arylations of the thiophene rings. A subsequent thionation of the carbonyl groups resulted in the formation of new thiophene-based dyes bearing two ferrocenylthiocarbonyl groups. These dyes absorb in a wide range of the visible spectrum due to their p-p* and d-p* transitions, and show a remarkable red-shift of the absorption band relative to their carbonyl analogues without increasing the molecular size.

    DOI: 10.1246/cl.160866

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  • Incorporating a TiOx shell in single-walled carbon nanotube/fullerodendron coaxial nanowires: increasing the photocatalytic evolution of H-2 from water under irradiation with visible light

    K. Kurniawan, T. Tajima, Y. Kubo, H. Miyake, W. Kurashige, Y. Negishi, Y. Takaguchi

    RSC ADVANCES   7 ( 50 )   31767 - 31770   2017

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    A custom-tailored single-walled carbon nanotube (SWCNT) photocatalyst with an electron-extracting TiOx shell, i.e., a SWCNT/fullerodendron/TiOx coaxial nanowire, has been fabricated. Due to the presence of the TiOx shell, the SWCNT/fullerodendron/TiOx coaxial nanowire shows an enhanced photocatalytic activity (Phi = 0.47) for the evolution of hydrogen from water under irradiation with visible light (lambda = 450 nm).

    DOI: 10.1039/c7ra05412b

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  • Synthesis and Photoproperties of Edge-functionalized Zeolite-templated Carbon with Bromine or Carbazole Groups

    Haruko Goto, Tomoyuki Tajima, Kazumasa Kobayashi, Yutaka Takaguchi, Khanin Nueangnoraj, Hirotomo Nishihara

    CHEMISTRY LETTERS   45 ( 6 )   601 - 603   2016.6

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    We succeeded in synthesizing edge-brominated zeolite-templated carbon (ZTC-Br) as the key intermediate of edge-functionalization of ZTC via an electrophilic aromatic substitution reaction using dibromoisocyanuric acid. ZTC-Br was easily converted into carbazole-modified ZTC (ZTC-Cz) using Suzuki-Miyaura coupling. Interestingly, solvent-dependent changes of the fluorescence intensity of ZTC-Cz owing to its swelling shrinking behavior were observed.

    DOI: 10.1246/cl.160123

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  • Synthesis and Photoproperties of Edge-functionalized Zeolite-templated Carbon with Bromine or Carbazole Groups

    Haruko Goto, Tomoyuki Tajima, Kazumasa Kobayashi, Yutaka Takaguchi, Khanin Nueangnoraj, Hirotomo Nishihara

    CHEMISTRY LETTERS   45 ( 6 )   601 - 603   2016.6

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    We succeeded in synthesizing edge-brominated zeolite-templated carbon (ZTC-Br) as the key intermediate of edge-functionalization of ZTC via an electrophilic aromatic substitution reaction using dibromoisocyanuric acid. ZTC-Br was easily converted into carbazole-modified ZTC (ZTC-Cz) using Suzuki-Miyaura coupling. Interestingly, solvent-dependent changes of the fluorescence intensity of ZTC-Cz owing to its swelling shrinking behavior were observed.

    DOI: 10.1246/cl.160123

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  • Synthesis and Photoproperties of Edge-functionalized Zeolite-templated Carbon with Bromine or Carbazole Groups

    Haruko Goto, Tomoyuki Tajima, Kazumasa Kobayashi, Yutaka Takaguchi, Khanin Nueangnoraj, Hirotomo Nishihara

    CHEMISTRY LETTERS   45 ( 6 )   601 - 603   2016.6

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    We succeeded in synthesizing edge-brominated zeolite-templated carbon (ZTC-Br) as the key intermediate of edge-functionalization of ZTC via an electrophilic aromatic substitution reaction using dibromoisocyanuric acid. ZTC-Br was easily converted into carbazole-modified ZTC (ZTC-Cz) using Suzuki-Miyaura coupling. Interestingly, solvent-dependent changes of the fluorescence intensity of ZTC-Cz owing to its swelling shrinking behavior were observed.

    DOI: 10.1246/cl.160123

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  • Synthesis and Crystal Structure of a [70]Fullerene-Pentacene Monoadduct

    Hitoshi Shirai, Tomoyuki Tajima, Kentaro Kubo, Takuya Nishihama, Hideaki Miyake, Yutaka Takaguchi

    BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN   89 ( 4 )   437 - 443   2016.4

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    We succeeded in the first isolation of a single pure regioisomer of a C-70-acene monoadduct. 1,9-Diels-Alder monoadducts of C-70 with pentacene derivatives were obtained by not only the Diels-Alder reaction but also a one-pot reaction using stable dihydropentacene derivatives, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and C-70. The X-ray crystallographic study of a single pure regioisomer 2b confirmed positions of the linkage between C-70 and acenes for the first time, and revealed unique columnar stacks.

    DOI: 10.1246/bcsj.20150378

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  • Spectroscopic Characterization of Nanohybrids Consisting of Single-walled Carbon Nanotubes and Fullerodendron

    Hironori Suzuki, Yoko Iizumi, Masayoshi Tange, Soon-Kil Joung, Akihiro Furube, Takaaki Wada, Tomoyuki Tajima, Yutaka Takaguchi, Toshiya Okazaki

    FULLERENES NANOTUBES AND CARBON NANOSTRUCTURES   22 ( 1-3 )   75 - 87   2014.1

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    Hydrogen gas, which can be used in fuel cells to generate electricity, is considered the ultimate clean energy source. Recently, it was reported that a photo-induced electron transfer system consisting of single-walled carbon nanotubes (SWCNTs) and fullerodendrons shows photo-catalytic activity with a very high quantum yield for splitting water under visible light irradiation. However, the mechanism of high efficiency hydrogen generation is not yet clearly understood. We report here the spectroscopic characterizations of the SWCNT-fullerodendron composites. The results indicate two important fundamental properties of the composite system. First, fullerodendrons preferentially interact with the semiconducting SWCNTs instead of with their metallic counterparts. Second, the photo-induced electron transfer process from the C-60 moiety of fullerodendrons to SWCNTs occurs more efficiently with an increasing tube diameter.

    DOI: 10.1080/1536383X.2013.794340

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  • Spectroscopic Characterization of Nanohybrids Consisting of Single-walled Carbon Nanotubes and Fullerodendron

    Hironori Suzuki, Yoko Iizumi, Masayoshi Tange, Soon-Kil Joung, Akihiro Furube, Takaaki Wada, Tomoyuki Tajima, Yutaka Takaguchi, Toshiya Okazaki

    FULLERENES NANOTUBES AND CARBON NANOSTRUCTURES   22 ( 1-3 )   75 - 87   2014.1

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    Hydrogen gas, which can be used in fuel cells to generate electricity, is considered the ultimate clean energy source. Recently, it was reported that a photo-induced electron transfer system consisting of single-walled carbon nanotubes (SWCNTs) and fullerodendrons shows photo-catalytic activity with a very high quantum yield for splitting water under visible light irradiation. However, the mechanism of high efficiency hydrogen generation is not yet clearly understood. We report here the spectroscopic characterizations of the SWCNT-fullerodendron composites. The results indicate two important fundamental properties of the composite system. First, fullerodendrons preferentially interact with the semiconducting SWCNTs instead of with their metallic counterparts. Second, the photo-induced electron transfer process from the C-60 moiety of fullerodendrons to SWCNTs occurs more efficiently with an increasing tube diameter.

    DOI: 10.1080/1536383X.2013.794340

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  • Synthesis and Characterization of 2,3,9,10-Tetradendronized Pentacene

    Tomoyuki Tajima, Akio Yamakawa, Keitaro Fukuda, Yuuki Hayashi, Masahiko Nakano, Yutaka Takaguchi

    CHEMISTRY LETTERS   41 ( 12 )   1622 - 1624   2012.12

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    A new pentacene dendrimer was synthesized in 81% yield through the aromatization of a dihydropentacene derivative having benzyl ether dendrons at the C2, C3, C9, and C10 positions. The dendrimer is very soluble in various organic solvents such as toluene, benzene, chloroform, dichloromethane, acetone, and ethyl acetate. The half-life of the dendrimer reaches 22.4 min upon photoirradiation in air. Interestingly, regiospecific [4 + 2] cycloaddition reactions proceeded at the central ring of the pentacene.

    DOI: 10.1246/cl.2012.1622

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  • Synthesis and Characterization of 2,3,9,10-Tetradendronized Pentacene

    Tomoyuki Tajima, Akio Yamakawa, Keitaro Fukuda, Yuuki Hayashi, Masahiko Nakano, Yutaka Takaguchi

    CHEMISTRY LETTERS   41 ( 12 )   1622 - 1624   2012.12

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    A new pentacene dendrimer was synthesized in 81% yield through the aromatization of a dihydropentacene derivative having benzyl ether dendrons at the C2, C3, C9, and C10 positions. The dendrimer is very soluble in various organic solvents such as toluene, benzene, chloroform, dichloromethane, acetone, and ethyl acetate. The half-life of the dendrimer reaches 22.4 min upon photoirradiation in air. Interestingly, regiospecific [4 + 2] cycloaddition reactions proceeded at the central ring of the pentacene.

    DOI: 10.1246/cl.2012.1622

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  • Fabrication of novel core-shell microspheres consisting of single-walled carbon nanotubes and CaCO3 through biomimetic mineralization

    Tomoyuki Tajima, Akira Tsutsui, Tatsuo Fujii, Jun Takada, Yutaka Takaguchi

    POLYMER JOURNAL   44 ( 6 )   620 - 624   2012.6

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    Calcium carbonate (CaCO3) in the presence of single-walled carbon nanotube (SWCNT) /fullerodendron supramolecular nanocomposites was crystallized with a CO2 diffusion method under ambient conditions and in aqueous environments to produce monodisperse spherical SWCNT/CaCO3 hybrids with a core-shell structure. The crystals nucleate at the carboxyl groups on the surface of the SWCNT/fullerodendron supramolecular nanocomposites grow around a spherical scaffold consisting of the SWCNTs, and finally form spherical calcite crystals embedded with and covered by the SWCNTs. Owing to of the phase transition from vaterite to calcite through a solvent-mediated process, the morphology of the microspheres is unique; the shell is primarily composed of calcite crystals of CaCO3, and a greater amount of SWCNTs is embedded in the core moiety. Polymer Journal (2012) 44, 620-624; doi:10.1038/pj.2012.36; published online 18 April 2012

    DOI: 10.1038/pj.2012.36

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  • Fabrication of novel core-shell microspheres consisting of single-walled carbon nanotubes and CaCO3 through biomimetic mineralization

    Tomoyuki Tajima, Akira Tsutsui, Tatsuo Fujii, Jun Takada, Yutaka Takaguchi

    POLYMER JOURNAL   44 ( 6 )   620 - 624   2012.6

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    Calcium carbonate (CaCO3) in the presence of single-walled carbon nanotube (SWCNT) /fullerodendron supramolecular nanocomposites was crystallized with a CO2 diffusion method under ambient conditions and in aqueous environments to produce monodisperse spherical SWCNT/CaCO3 hybrids with a core-shell structure. The crystals nucleate at the carboxyl groups on the surface of the SWCNT/fullerodendron supramolecular nanocomposites grow around a spherical scaffold consisting of the SWCNTs, and finally form spherical calcite crystals embedded with and covered by the SWCNTs. Owing to of the phase transition from vaterite to calcite through a solvent-mediated process, the morphology of the microspheres is unique; the shell is primarily composed of calcite crystals of CaCO3, and a greater amount of SWCNTs is embedded in the core moiety. Polymer Journal (2012) 44, 620-624; doi:10.1038/pj.2012.36; published online 18 April 2012

    DOI: 10.1038/pj.2012.36

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  • 配位子交換反応を利用した(Me4N)4[Cd10S4(SePh)16]クラスター分子の合成

    坂本裕太, 田嶋智之, 吉成信人, 井頭麻子, 今野巧, 高口豊

    日本化学会講演予稿集   92nd ( 4 )   2012

  • Photosensitized Hydrogen Evolution from Water Using a Single-Walled Carbon Nanotube/Fullerodendron/SiO2 Coaxial Nanohybrid

    Tomoyuki Tajima, Wakako Sakata, Takaaki Wada, Akira Tsutsui, Shunsuke Nishimoto, Michihiro Miyake, Yutaka Takaguchi

    ADVANCED MATERIALS   23 ( 48 )   5750 - +   2011.12

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    A coaxial nanohybrid consisting of a single- walled carbon nanotube (SWCNT), fullerodendron, and SiO(2) shows higheffi ciency light- driven hydrogen evolution from water. Upon visible light irradiation, SWCNT/ fullerodendron/SiO(2) coaxial nano hybrid shows hydrogen evolution activity in the presence of methyl viologen (MV(2+)), benzyldihydronicotinamide (BNAH), and a colloidal polyvinyl alcohol(PVA)-Pt.

    DOI: 10.1002/adma.201103472

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  • Photosensitized Hydrogen Evolution from Water Using a Single-Walled Carbon Nanotube/Fullerodendron/SiO2 Coaxial Nanohybrid

    Tomoyuki Tajima, Wakako Sakata, Takaaki Wada, Akira Tsutsui, Shunsuke Nishimoto, Michihiro Miyake, Yutaka Takaguchi

    ADVANCED MATERIALS   23 ( 48 )   5750 - +   2011.12

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    A coaxial nanohybrid consisting of a single- walled carbon nanotube (SWCNT), fullerodendron, and SiO(2) shows higheffi ciency light- driven hydrogen evolution from water. Upon visible light irradiation, SWCNT/ fullerodendron/SiO(2) coaxial nano hybrid shows hydrogen evolution activity in the presence of methyl viologen (MV(2+)), benzyldihydronicotinamide (BNAH), and a colloidal polyvinyl alcohol(PVA)-Pt.

    DOI: 10.1002/adma.201103472

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  • New reactions of a dibenzo[a,e]pentalene

    Masaichi Saito, Michio Nakamura, Tomoyuki Tajima

    CHEMISTRY-A EUROPEAN JOURNAL   14 ( 20 )   6062 - 6068   2008

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    Reduction of dibenzo[a,e]pentalene 3 (denoted as dibenzopentalene hereafter) with excess lithium gave dilithium dibenzopentalenide 1. Since oxidation of I with iodine gave 3, redox behavior between 1 and 3 is controllable and reversible. Reaction of 3 with methyllithium gave lithium 5-methyldibenzopehtalenide 5, the formation of which was evidenced by some trapping experiments and X-ray crystallographic analysis. Reactions of 3 with halogens gave 5,10-dihalodibenzopentalenes, 8 and 9. Some optical properties of novel dibenzopentalene derivatives are also demonstrated.

    DOI: 10.1002/chem.200800451

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  • 速度論的に安定化されたスタンナンチオンおよびスタンナンテロンの合成、構造、反応性 Reviewed

    田嶋智之, 武田亘弘, 笹森貴裕, 時任宣博

    日本化学会第86回春季年会 ,船橋市   2006.3

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  • 安定なスズ?テルル二重結合化合物の合成、構造、および反応性(poster) Reviewed

    田嶋 智之, 田嶋 智之, 笹森 貴裕, 武田 亘弘, 時任 宣博

    第10回ケイ素化学協会シンポジウム ,広島県佐伯郡   2005.10

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  • スズ‐テルル二重結合化合物の速度論的安定化とそれを用いたスズおよびテルルを含む新規環状化合物の合成 Reviewed

    田嶋智之, 笹森貴裕, 武田亘弘, 時任宣博

    複素環化学討論会講演要旨集   35th   285 - 286   2005.10

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  • 速度論的安定化の手法を用いたスズ-テルル二重結合化合物の合成 Reviewed

    田嶋智之, 田嶋 智之, 武田 亘弘, 笹森 貴裕, 時任 宣博

    第85日本化学会春季年会 ,横浜市   2005.3

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  • ビス(メタラシクロプロパ)ベンゼンの合成と構造 Reviewed

    田嶋智之, 田嶋 智之, 幡野 健, 佐々木 貴代, 武田 亘弘, 笹森 貴裕, 吉田 健, 中原 勝, 時任 宣博

    第85日本化学会春季年会 ,横浜市   2005.3

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  • Stable Bis(metallacyclopropa)benzenes of Heavier Group 14 Elements (poster) Reviewed

    T. Tajima, Tomoyuki Tajima, Nobuhiro Takeda, Takahiro Sasamori, Norihiro Tokitoh

    The 4th International Symposium of the Kyoto COE Project "Elements Science" ,京都   2005.1

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  • 含ゲルマニウム高歪み三員環化合物、ビス(ゲルマシクロプロパ)ベンゼンの合成と構造(poster) Reviewed

    田嶋智之, 田嶋 智之, 笹森 貴裕, 武田 亘弘, 時任 宣博

    第9回ケイ素化学協会シンポジウム ,港区、東京   2004.10

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  • 高周期14 族元素を含むメタラシクロプロパベンゼン類の合成と性質 Reviewed

    田嶋智之, 田嶋智之, 武田亘弘, 笹森貴裕, 時任宣博

    第51回有機金属化学討論会 ,東京   2004.10

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  • Generation and Reactions of Overcrowded Dimetallastannane Derivatives Reviewed

    N. Tokitoh, Tomoyuki Tajima, Nobuhiro Takeda, Takahiro Sasamori, Norihiro Tokitoh

    THE 7th IUPAC INTERNATIONAL CONFERENCE ON HETEROATOM CHEMISTRY (ICHAC-7) ,Shanghai, China   2004.8

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  • Reactions of an overcrowded Germacyclopropabenzene with Metal Carbonyl Comolexes (poster) Reviewed

    T. Tajima, kyoto Un, T. Tajima, T. Sasaki, T. Sasamori, N. Takeda, N. Tokitoh

    XI International Conference On the Coordination and Organometallic Chemistry Of Germanium, Tin and Lead ,Santa Fe, New Mexico   2004.6

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  • かさ高い置換基を持つジリチオスタンナンと二塩化テルルとの反応 Reviewed

    田嶋智之, 田嶋智之, 武田亘弘, 笹森貴裕, 時任宣博

    第84日本化学会春季年会 ,西宮、兵庫   2004.3

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  • かさ高い置換基を有する新規スズジアニオン種の性質とその特性を活かした新規含スズ化合物の合成 Reviewed

    田嶋智之, 田嶋智之, 笹森貴裕, 武田亘弘, 時任宣博

    第30回ヘテロ原子化学討論会 ,富山   2003.12

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  • かさ高い置換基を持つスズジアニオンの発生とその反応性(poster) Reviewed

    田嶋智之, 田嶋智之, 武田亘弘, 笹森貴裕, 時任宣博

    第8回ケイ素化学協会シンポジウム ,京都   2003.10

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  • 速度論的に安定化されたゲルマシクロプロパベンゼンの反応性 Reviewed

    田嶋智之, 田嶋智之, 武田亘弘, 時任宣博

    第83日本化学会春季年会 ,東京都新宿区   2003.3

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  • The First Stable Metallacyclopropabenzenes Reviewed

    T. Tajima, T. Tajima, N. Takeda, N. Tokitoh

    The first Trilateral Workshop on Organic Chemistry ,Taipei   2003.1

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  • Kinetically stabilized tintellurium doublebond compound: Synthesis, structure and reactivities(poster) Reviewed

    T. Tajima, yoto Uni, T. Tajima, N. Takeda, T. Sasamori, N. Tokitoh

    2005 International Chemical Congress of Pacific Basin Societies (Pacifichem 2005) ,Honolulu, Hawaii, USA   2000.12

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Industrial property rights

  • 細胞内導入機能を有するホウ素を含むデンドリマー

    道上 宏之, 福永 麻美, 松井 秀樹, 高口 豊, 田嶋 智之, 石本 寛伍, 大津 裕貴

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    Applicant:国立大学法人 岡山大学

    Application no:特願2017-038462  Date applied:2017.3.1

    Announcement no:特開2018-145107  Date announced:2018.9.20

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  • ハロゲン化された炭素シート及びその製造方法

    高口 豊, 田嶋 智之, 小林 和正, 和田 卓聡

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    Applicant:国立大学法人 岡山大学

    Application no:JP2014068553  Date applied:2014.7.11

    Announcement no:WO2015-005470  Date announced:2015.1.15

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  • コアシェル型カーボンナノチューブ複合材料及びその製造方法

    高口 豊, 田嶋 智之, 笹田 由香里

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    Applicant:国立大学法人 岡山大学

    Application no:特願2014-048235  Date applied:2014.3.11

    Announcement no:特開2015-171965  Date announced:2015.10.1

    Patent/Registration no:特許第6225399号  Date issued:2017.10.20

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  • コアシェル型カーボンナノチューブ複合材料及びその製造方法

    高口 豊, 田嶋 智之, 笹田 由香里

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    Applicant:国立大学法人 岡山大学

    Application no:特願2014-048235  Date applied:2014.3.11

    Announcement no:特開2015-171965  Date announced:2015.10.1

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  • ヘキサチオペンタセン化合物及びその製造方法、並びにそれを含むゲル

    高口 豊, 田嶋 智之, 西濱 拓也, 林 勇樹

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    Applicant:国立大学法人 岡山大学

    Application no:特願2013-153089  Date applied:2013.7.23

    Announcement no:特開2015-020998  Date announced:2015.2.2

    Patent/Registration no:特許第6179011号  Date issued:2017.7.28

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  • ヘキサチオペンタセン化合物及びその製造方法、並びにそれを含むゲル

    高口 豊, 田嶋 智之, 西濱 拓也, 林 勇樹

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    Applicant:国立大学法人 岡山大学

    Application no:特願2013-153089  Date applied:2013.7.23

    Announcement no:特開2015-020998  Date announced:2015.2.2

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  • 酸化物の製造方法

    高口 豊, 田嶋 智之, 大澤 侑史, 和田 卓聡

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    Applicant:国立大学法人 岡山大学

    Application no:特願2012-094458  Date applied:2012.4.18

    Announcement no:特開2013-220980  Date announced:2013.10.28

    Patent/Registration no:特許第6097490号  Date issued:2017.2.24

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  • 酸化物の製造方法

    高口 豊, 田嶋 智之, 大澤 侑史, 和田 卓聡

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    Applicant:国立大学法人 岡山大学

    Application no:特願2012-094458  Date applied:2012.4.18

    Announcement no:特開2013-220980  Date announced:2013.10.28

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  • グラフェンナノリボン及びグラフェンナノリボンの化学修飾方法

    高口 豊, 田嶋 智之, 福間 智彦

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    Applicant:国立大学法人 岡山大学

    Application no:特願2012-012684  Date applied:2012.1.25

    Announcement no:特開2013-151387  Date announced:2013.8.8

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  • ヘキサチアペンタセン化合物及びその製造方法、並びにそれからなる光触媒

    高口 豊, 田嶋 智之, 山川 晃生

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    Applicant:国立大学法人 岡山大学

    Application no:特願2010-136445  Date applied:2010.6.15

    Announcement no:特開2012-001463  Date announced:2012.1.5

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  • ヘキサチアペンタセン化合物及びその製造方法、並びにそれからなる光触媒

    高口 豊, 田嶋 智之, 山川 晃生

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    Applicant:国立大学法人 岡山大学

    Application no:特願2010-136445  Date applied:2010.6.15

    Announcement no:特開2012-001463  Date announced:2012.1.5

    Patent/Registration no:特許第5652856号  Date issued:2014.11.28

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Awards

  • 岡山大学SDGs推進表彰(President Award)奨励賞

    2021.3   岡山大学  

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    Country:Japan

  • 岡山工学振興会科学技術賞受賞

    2010.6   岡山工学振興会  

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    Award type:Award from publisher, newspaper, foundation, etc.  Country:Japan

Research Projects

  • ナノ・バイオ融合によるエネルギー集積・高度利用研究拠点形成

    2021.10 - 2022.03

    岡山大学  令和3年度岡山大学次世代研究拠点形成支援事業 次世代育成グループ 

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\500000

  • ナノ構造集積化による希少金属を用いない太陽光エネルギー変換・CO2フリー水素製造技術開発

    2021.06 - 2022.03

    岡山県  令和3年度特別電源所在県科学技術振興事業 

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\8400000

  • ナノ同軸ワイヤー構造のヘテロ界面理解に基づくカーボンナノチューブ光触媒の高活性化

    Grant number:20K05266  2020.04 - 2023.03

    日本学術振興会  科学研究費助成事業 基盤研究(C)  基盤研究(C)

    田嶋 智之

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    Grant amount:\4290000 ( Direct expense: \3300000 、 Indirect expense:\990000 )

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  • Dendritic molecular glue for fabrlication of CNT/inorganic hybrids

    Grant number:16K05895  2016.04 - 2019.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C)  Grant-in-Aid for Scientific Research (C)

    Tajima Tomoyuki, Takaguchi Yutaka

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    Grant amount:\4940000 ( Direct expense: \3800000 、 Indirect expense:\1140000 )

    Multi-walled carbon nanotube (MWCNT)/dendrimer sheet scaffolds, i.e., dendrimers attached to the surface of MWCNT buckypaper, were fabricated, and a hydroxyapatite (HAp) coating prepared on dendrimer-modified buckypaper using an alternate soaking process (ASP) is described. The amount of the HAp that is retained on the surface of the MWCNT/dendrimer sheet scaffolds depends on the modification method; i.e., surface modification performed after the formation of the buckypaper is much more effective in producing MWCNT/HAp hybrid materials than surface modification prior to the formation of the buckypaper. Moreover, biomimetic crystallization of calcium phosphate on buckypaper in simulated body fluid (SBF) was carried out. TEM analysis of the resulting MWCNT/dendrimer sheet scaffolds revealed that the MWCNT backbone was covered with scaly crystals.

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  • Development of CNT-photocatalyst having coaxial nanowire heterojunction

    Grant number:15H03519  2015.04 - 2018.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (B)  Grant-in-Aid for Scientific Research (B)

    Takaguchi Yutaka, TAJIMA Tomoyuki

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    Grant amount:\17810000 ( Direct expense: \13700000 、 Indirect expense:\4110000 )

    A novel category of H2-evolving photocatalysts based on semiconducting SWCNTs (s-SWCNTs) for the photocatalytic overall water splitting is described. These CNT-photocatalysts shows H2-evolving activity under visible and even near-IR illumination since s-SWCNTs act as light absorbers.

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  • Molecular Technology based on Diels-Alder reaction of C70 with acenes

    Grant number:25410041  2013.04 - 2016.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C)  Grant-in-Aid for Scientific Research (C)

    Tajima Tomoyuki, TAKAGUCHI YUTAKA

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    Grant amount:\5200000 ( Direct expense: \4000000 、 Indirect expense:\1200000 )

    Diels-Alder reaction of fullerenes with acenes is among the most studied addition reactions. Although [60]fullerene-acene reactions using scenes have been reported, there are only a few examples of the reaction of acenes with C70. We succeeded in the first isolation of a single pure regioisomer of a C70-acene monoadduct. 1,9-Diels-Alder monoadducts of C70 with pentacene derivatives were obtained by not only the Diels-Alder reaction but also a one-pot reaction using stable dihydropentacene derivatives, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), and C70. The X-ray crystallographic study of a single pure regioisomer confirmed positions of the linkage between C70 and acenes for the first time, and revealed unique columnar stacks.

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  • Synthesis of hypervalent sulfur atoms annelated with a acene and it's development to functional materials

    Grant number:23750041  2011 - 2012

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Young Scientists (B)  Grant-in-Aid for Young Scientists (B)

    TAJIMA Tomoyuki

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    Grant amount:\4680000 ( Direct expense: \3600000 、 Indirect expense:\1080000 )

    Dendrimer with insoluble chromophore have attracted considerable attention because of the flexibility of molecular design for functional materials. We have reported the synthesis of dendron-functionalized fullerene and cadmium chalcogenide. They are soluble in various solvents and act as effective photosensitizers to generate singlet oxygen.Meanwhile, hexathiopentacene has been studied as an active material in OFETs because of its high hole transport mobility. However, hexathiopentacene is insoluble in organic solvents, Hence the properties of the hexathiopentacene in solution are still unclear, i.e., NMR, UV-Vis, and fluorescence spectra of the solution of hexathiopentacene at room temperature have never been reported. Here we present the synthesis of hexathiopentacene dendrimer together with photooxygenation reaction using hexathiopentacene dendrimer as a photosensitizer of singlet oxygen.

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  • Control of the meso-architecture using self-assembly of the organic semiconductor having dendritic substituents

    Grant number:21510103  2009 - 2011

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Scientific Research (C)  Grant-in-Aid for Scientific Research (C)

    TAKAGUCHI Yutaka, TAJIMA Tomoyuki

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    Grant amount:\4680000 ( Direct expense: \3600000 、 Indirect expense:\1080000 )

    In order to control the meso-architecture of self-assembled semiconducting materials, several new dendrimers have been synthesized. For instance, a fullerodendron having sugar moieties at the terminals, DBN-focal dendrons and their fullerene adducts, and a dendrimer having diphenyl diselenide at the core. Interestingly, fullerodendrons are self-assembled on the surface of single-walled carbon nanotubes(SWCNTs) to form the SWCNT/fullerodendron supramolecular nanocomposite that have nicely ordered photofunctional interface generating charge separated state via photoinduced electron transfer process. Furthermore, the supramolecular nanocomposite was covered by SiO_2 to produce the SWCNT/fullerodendron/SiO_2 coaxial nanohybrid that can be used for the photocatalyst for water splitting. It is notable that the quantum yield of H2 generation reaches to 31% upon visible light irradiation.

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  • Development of novel key reagent for synthesis of multiple bond of heavier group main group elements.

    Grant number:21750043  2009 - 2010

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Young Scientists (B)  Grant-in-Aid for Young Scientists (B)

    TAJIMA Tomoyuki, TAKAGUCHI Yutaka

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    Grant amount:\4550000 ( Direct expense: \3500000 、 Indirect expense:\1050000 )

    The author wishes to describe control of reactivity of tri- and tetraanions containing group 14 atom in the mild condition. When a chemical reaction is to be carried out selectively at one (two or three) site in a multifunctional compound, other reactive sites must be temporarily blocked. I design a new type of element, which has a several protective groups on the atom. A number of anion is easy to control depend on the kind of reagents or trigger groups on the element. We can easy to create new four bonds on the element. The strategy might be applicable for synthesis of more intricate doubly-bonded systems such as heaver analogues of vinyllithium and 1,1-dilithio-dimetalene containing group 14 elements.

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  • The Chemistry of Unsaturated Compounds of Heavier Main Group Elements : Pursuit of Novel Properties

    Grant number:17GS0207  2005 - 2009

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research Grant-in-Aid for Creative Scientific Research  Grant-in-Aid for Creative Scientific Research

    TOKITOH Norihiro, SASAMORI Takahiro, MATSUDA Kazunari, NAGASE Shigeru, FURUKAWA Yukio, MIZUHATA Yoshiyuki, TAJIMA Tomoyuki, NAGAHORA Noriyoshi, TAKEDA Nobuhiro, TSUJI Hayato, SATO Naoki

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    Grant amount:\532350000 ( Direct expense: \409500000 、 Indirect expense:\122850000 )

    Unsaturated compounds between the second row elements such as carbon and oxygen has played an important role in the function of organic compounds. In order to open the new chemistry of unsaturated compounds, we focused our attention on multiple-bond compounds between heavier elements such as silicon and phosphorus as novel functional materials. As a result, several numbers of novel unsaturated compounds between heavier elements have been successfully synthesized by utilizing kinetic stabilization and we have revealed their functions on the basis of element chemistry.

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  • 嵩高い置換基を持つジリチオメタランを用いた新規高周期14族元素化学種の合成と性質

    Grant number:04J00754  2004 - 2005

    日本学術振興会  科学研究費助成事業 特別研究員奨励費  特別研究員奨励費

    田嶋 智之

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    Grant amount:\1900000 ( Direct expense: \1900000 )

    近年、高周期14族元素ジアニオン種を用いて様々な新規化学種が合成されている。申請者の所属研究室においても、独自に開発した優れた立体保護基である2,4,6-トリス[ビス(トリメチルシリル)メチル]フェニル基(Tbt基)を有するジリチオシラン、およびジリチオゲルマンとo-ジブロモベンゼンとの反応により、三員環内にケイ素及びゲルマニウムを有するメタラシクロプロパベンゼンの合成に初めて成功している。
    本研究では、ゲルマシクロプロパベンゼンと各種試剤との反応を行ったところ、高歪みを有する三員環部位での反応が進行し、様々な環拡大化合物を得た。特に6族金属ヘキサカルボニル錯体との熱反応では、TiやZrのベンザイン錯体で報告されている様なヘキサカルボニル錯体のC=O結合がゲルマシクロプロパベンゼンのC-Ge結合に挿入したFischer型カルベン錯体が生成することを明らかとし、炭化水素化合物類縁体であるシクロブロパベンゼンとは異なる反応性を見い出した。
    一方、更に高周期14族元素であるスズにおいては、ジアニオン種の確かな発生例はこれまで報告がなかった。本研究では、Tbt基を有するジブロモスタンナンに対し過剰量のリチウムナフタレニドをTHF中-78℃で作用させることにより、ジリチオスタンナンの発生に成功した。ジリチオスタンナンの発生は、各種捕捉剤(重塩酸、重水、ヨウ化メチル等)との反応により確認するとともに、THF中-80℃での^<119>Sn NMRの測定により-362ppmにスズジアニオン種に由来するシグナルを観測することに成功した。THF中、ジリチオスタンナンは-25℃まで安定に存在し、これまで発生に成功しているジリチオシランおよびジリチオゲルマンとは異なる安定性も見い出した。この研究結果は、第51回有機金属化学討論会にて口頭発表し、欧文雑誌へ論文投稿した。

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