Updated on 2024/03/25

写真a

 
TANAKA Kentaro
 
Organization
Graduate School of Science Professor
Graduate School
Graduate School of Science
Undergraduate School
School of Science
Title
Professor

Degree 1

  1. Doctor of Engineering ( 1995.3   Tokyo Institute of Technology ) 

Research Interests 7

  1. Catalyst

  2. Molecular Device

  3. Liquid-Crystal

  4. Biopolymer

  5. Self-Assembly

  6. Metal Complex

  7. Supramolecular Chemistry

Research Areas 6

  1. Nanotechnology/Materials / Inorganic/coordination chemistry  / Coordination Chemistry

  2. Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry  / Supramolecular Chemistry

  3. Nanotechnology/Materials / Nanomaterials  / Nanoporous Liquid Crystals

  4. Nanotechnology/Materials / Organic functional materials

  5. Nanotechnology/Materials / Inorganic/coordination chemistry

  6. Nanotechnology/Materials / Structural organic chemistry and physical organic chemistry

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Current Research Project and SDGs 4

  1. ナノ細孔性液晶による分子組織場、分子反応場の構築

  2. 金属錯体精密分子組織による新しい分子反応場、分子情報場の構築

  3. 金属錯体組織型高性能触媒

  4. 生体高分子をモチーフとした高次機能分子組織の構築

Research History 12

  1. Nagoya University   Graduate School of Science   Professor

    2022.4

  2. Nagoya University   Administrative Support Organizations Academic Research & Industry-Academia-Government Collaboration   Vice Director

    2018.4 - 2020.3

  3. Kyoto University

    2017.4 - 2018.3

  4. Nagoya University   Presidential Advisor   Presidencial Advisor

    2015.4 - 2020.3

  5. Nagoya University   Graduate School of Science Division of Material Science   Professor

    2007.4

  6. Nagoya University   Graduate School of Science, Department of Chemistry   Professor

    2007.4 - 2022.3

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    Country:Japan

  7. The University of Tokyo   Graduate School of Science, Department of Chemistry   Associate Professor

    2002.7 - 2007.3

  8. The University of Tokyo   Graduate School of Science, Department of Chemistry   Assistant

    1999.6 - 2002.7

  9. Okazaki National Research Institutes   Institute for Molecular Science   Assistant

    1995.12 - 1999.5

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    Country:Japan

  10. Okazaki National Research Institutes   Institute for Molecular Science   Assistant Professor

    1995.12 - 1999.5

  11. Japan Society for Promotion of Science   Postdoctoral Fellow

    1995.7 - 1995.10

  12. University of California, Irvine   Department of Chemistry   Postdoctoral Fellow

    1995.4 - 1995.11

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Education 3

  1. Tokyo Institute of Technology   Graduate School of Bioscience and Bioengineering   Doctoral course

    1992.4 - 1995.3

  2. Tokyo Institute of Technology   Graduate School of Science and Engineering   Master course

    1990.4 - 1992.3

  3. Tokyo Institute of Technology   School of Engineering   Department of Polymer Science

    1986.4 - 1990.3

Professional Memberships 12

  1. The Chemical Society of Japan

  2. Japan Society of Coordination Chemistry

  3. The Society of Polymer Science, Japan

  4. ナノ学会   理事

  5. 分析化学会

  6. The Institute of Electrical Engineers of Japan

  7. ナノ学会

  8. 分析化学会

  9. The Chemical Society of Japan

  10. Japan Society of Coordination Chemistry

  11. The Institute of Electrical Engineers of Japan

  12. The Society of Polymer Science, Japan

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Committee Memberships 17

  1. ナノ学会   理事  

    2021.5   

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    Committee type:Academic society

  2. 錯体化学会   事務局長  

    2019.9   

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    Committee type:Academic society

  3. 錯体化学会   副会長・理事  

    2017.9 - 2019.9   

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    Committee type:Academic society

  4. 錯体化学会   将来計画委員会委員長  

    2016.9 - 2017.9   

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    Committee type:Academic society

  5. 錯体化学会   理事  

    2014.9 - 2016.9   

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    Committee type:Academic society

  6. 高分子学会   東海支部幹事  

    2013.4   

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    Committee type:Academic society

  7. 日本化学会   錯体・有機金属ディビジョン幹事  

    2012.4 - 2016.3   

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    Committee type:Academic society

  8. 日本化学会   生体機能関連化学・バイオテクノロジーディビジョン幹事  

    2012.4 - 2016.3   

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    Committee type:Academic society

  9. 錯体化学会   理事  

    2011.9 - 2013.9   

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    Committee type:Academic society

  10. 日本化学会   代表正会員  

    2013.4 - 3017.3   

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    Committee type:Academic society

  11. 錯体化学会   国際交流委員会委員  

    2009.9 - 2018.9   

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    Committee type:Academic society

  12. 錯体化学会   将来計画委員会委員  

    2009.9 - 2011.9   

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    Committee type:Academic society

  13. 財団法人科学技術交流財団   企画運営委員  

    2008.4 - 2012.3   

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    Committee type:Other

  14. ナノ学会   学会誌編集委員  

    2008.4 - 2010.3   

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    Committee type:Academic society

  15. 日本化学会   東海支部常任幹事  

    2008.4 - 2010.3   

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    Committee type:Academic society

  16. 日本表面科学会   学会誌編集委員  

    2005.4 - 2008.3   

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    Committee type:Academic society

  17. 日本化学会   生体機能関連科学部会若手の会代表幹事  

    2001.4 - 2002.3   

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    Committee type:Academic society

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Awards 7

  1. 文部科学大臣表彰若手科学者賞

    2006.4   文部科学省  

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    Country:Japan

  2. 錯体化学会研究奨励賞

    2003.9   錯体化学会  

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    Award type:International academic award (Japan or overseas)  Country:Japan

  3. 日本液晶学会論文賞A部門

    2020.9   日本液晶学会  

    河野 慎一郎, 宗宮 伸弥, 中谷 真人, 尾上 順, 田中 健太郎

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    Award type:Honored in official journal of a scientific society, scientific journal 

  4. Asian Core Program Lectureship Award

    2009.12   Asian Core Program   Programmable Assembly of Metal Complexes

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    Award type:Award from international society, conference, symposium, etc.  Country:Taiwan, Province of China

  5. 文部科学大臣表彰若手科学者賞

    2006.4   文部科学省  

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    Country:Japan

  6. 錯体化学会研究奨励賞

    2003.9   錯体化学会  

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    Country:Japan

  7. 日本化学会生体機能関連化学部会 部会講演賞

    2001.9   日本化学会生体機能関連化学部会  

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    Country:Japan

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Papers 142

  1. Continuous Nanospace in Nanoporous Liquid Crystal Investigated by 129Xe NMR Spectroscopy Reviewed

    Shin-ichiro Kawano, Hiroaki Yoshimizu, Kentaro Tanaka

    Angewandte Chemie International Edition   Vol. 63   page: e2023165   2023.11

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    Continuous nanopores within fluid materials could be used for novel chemical events such as the accommodation of guest molecules, unique arrays of the entrapped molecules, and chemical reactions in a dynamic molecular assembly. Columnar liquid crystals composed of a one‐dimensionally stacked assembly of shape‐persistent macrocycles form nanochannels owing to the intrinsic nanospace in the column. However, the existence of substantial nanoporosity has not been confirmed experimentally thus far. In this study, for the first time in the literature, we confirmed the presence of discrete and spatiotemporally continuous voids in a liquid‐crystalline material. In 129Xe NMR spectroscopy of liquid crystalline columnar assembly of imine‐bridged shape‐persistent macrocycles under Xe atmosphere, the NMR signals of the Xe atoms entrapped in the liquid‐crystalline macrocycle depended on the gas pressure and phase‐transition temperatures. These results indicate that the encapsulation of Xe gas molecules within the discrete and oriented nanospaces of nanoporous liquid crystals is different from the homogeneous dissolution of the solute in an ordinary solution.

    DOI: 10.1002/anie.202316523

  2. Thermally Stable Array of Discrete C<sub>60</sub>s on a Two-Dimensional Crystalline Adlayer of Macrocycles both in Vacuo and under Ambient Pressure Reviewed

    Shin-ichiro Kawano, Masato Nakaya, Masaaki Saitow, Atsuki Ishiguro, Takeshi Yanai, Jun Onoe, Kentaro Tanaka

    Journal of the American Chemical Society   Vol. 144 ( 15 ) page: 6749 - 6758   2022.4

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/jacs.1c13610

  3. Inorganic–Organic Framework Constructed by the Intercalation of a Double-Decker Porphyrin Metal Complex into Clay Nanosheets and Its Efficient Dye Adsorption Ability Reviewed

    Y. Yamada, T. Nishino, Ayako Hashimoto, Y. Toyoda, H. Yoshikawa, K. Tanaka

    ACS Applied Optical Materials   Vol. 2   page: 405 - 413   2024.2

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (international conference proceedings)  

    DOI: /10.1021/acsaom.3c00444

  4. Calamitic Liquid Crystals for Reversible Light‐modulated Phase Regulation based on Arylazopyrazole Photoswitches Reviewed International coauthorship

    Hoan Quan Tran, Shinichiro Kawano, Rebecca E. Thielemann, Kentaro Tanaka, Bart Jan Ravoo

    Chemistry – A European Journal   Vol. 30   page: e202304061   2023.11

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    The design of responsive liquid crystals enables a diversity of technological applications. Especially photochromic liquid crystals gained a lot of interest in recent years due to the excellent spatiotemporal control of their phase transitions. In this work we present calamitic light responsive mesogens based on a library of arylazopyrazole photoswitches. These compounds show liquid‐crystalline behavior as shown by differential scanning calorimetry, grazing incidence X‐ray diffraction and polarized optical microscopy. UV‐vis spectroscopy and NMR analysis confirmed the excellent photophysical properties in solution and thin film. Additionally, polarized optical microscopy studies of the pristine compounds show reversible phase transition upon irradiation with light. Moreover, as a dopant in the commercially available liquid crystal 4‐cyano‐4'‐pentylbiphenyl (5CB), the temperature range was reduced to ambient temperatures while preserving the excellent photophysical properties. Remarkably this co‐assembled system shows reversible liquid‐crystalline to isotropic phase transition upon irradiation with light of different wavelengths. The spatiotemporal control of the phase transition of the liquid crystals offers opportunities in the development of optical devices.

    DOI: 10.1002/chem.202302958

  5. Kinetically-Locked Metallomacrocycle for Host-Guest Chemistry with Bulky Anions Reviewed

    Shinichiro Kawano, Takahiro Harada, Ako Sasaki, Kentaro Tanaka

    European Journal of Inorganic Chemistry   Vol. 26   page: e20220592   2023.2

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: https://doi.org/10.1002/ejic.202200592

  6. Evaluation of CH4 Oxidation Activity of High-Valent Iron-Oxo Species of A µ-Nitride-Bridged Heterodimer of Iron Porphycene and Iron Phthalocyanine Reviewed

    Catalysis Science and Technology   Vol. 13   page: 1725 - 1734   2023.1

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: /10.1039/D2CY01980A

  7. Stacking of a Cofacially Stacked Iron Phthalocyanine Dimer on Graphite Achieved High Catalytic CH4 Oxidation Activity Comparable to That of pMMO Reviewed

    Yasuyuki Yamada, Kentaro Morita, Takuya Sugiura, Yuka Toyoda, Nozomi Mihara, Masanari Nagasaka, Hikaru Takaya, Kiyohisa Tanaka, Takanori Koitaya, Naoki Nakatani, Hiroko Ariga-Miwa, Satoru Takakusagi, Yutaka Hitomi, Toshiji Kudo, Yuta Tsuji, Kazunari Yoshizawa, Kentaro Tanaka

    JACS Au     2023.1

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/jacsau.2c00618

  8. Synthesis of Isomeric Tb3+–Phthalocyanine Double–Decker Complexes Depending on the Difference in the Direction of Coordination Plane and Their Magnetic Properties Reviewed International coauthorship

    Yasuyuki Yamada, Hiroaki Nakajima, Chisa Kobayashi, Yoshiaki Shuku, Kunio Awaga, Shigehisa Akine, Kentaro Tanaka

    Chemistry - A European Journal   Vol. 29 ( 1 ) page: e202203272   2023.1

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  9. Unraveling the reasons behind lead phthalocyanine acting as a good absorber for near-infrared sensitive devices Reviewed

    Masahiro Kato, Hayato Yoshizawa, Masato Nakaya, Yasutaka Kitagawa, Koichi Okamoto, Tomoaki Yamada, Masahito Yoshino, Kentaro Tanaka, Jun Onoe

    Scientific Reports   Vol. 12 ( 1 ) page: 8810   2022.12

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Springer Science and Business Media LLC  

    Abstract

    Lead phthalocyanine (PbPc) is well known to be used as a good near-infrared (NIR) light absorber for organic solar cells (OSCs) and photodetectors. The monoclinic and triclinic phases have been understood to absorb the visible and NIR regions, respectively, so far. In the present study, we demonstrated from the absorption spectra and theoretical analysis that the visible band considerably originates from not only the monoclinic but also the amorphous and triclinic phases, and revealed the exciton dynamics in the PbPc film from static/time-resolved photoluminescence (PL), which are first reported. By comparing the external quantum efficiency between PbPc- and ZnPc-based OSCs in relation to their structure, morphology, and optical (absorption and PL) characteristics, we unraveled the reasons behind the PbPc film used as a good absorber for NIR-sensitive devices.

    DOI: 10.1038/s41598-022-12990-z

    Other Link: https://www.nature.com/articles/s41598-022-12990-z

  10. Synthesis of Isomeric Tb3+-Phthalocyanine Double-Decker Complexes Depending on the Difference in the Direction of Coordination Plane and Their Magnetic Properties Reviewed

    Yasuyuki Yamada, Hiroaki Nakajima, Chisa Kobayashi, Yoshiaki Shuku, Kunio Awaga, Shigehisa Akine, Kentaro Tanaka

    CHEMISTRY-A EUROPEAN JOURNAL     2022.12

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:WILEY-V C H VERLAG GMBH  

    A C-4h symmetrically substituted phthalocyanine, 1,8,15,22-tertrakis(2,4-dimethylpent-3-oxy)phthalocyanine (H(2)TdMPPc), was used to synthesize Tb3+-phthalocyanine double-decker complexes ([Tb(TdMPPc)(2)]s). Because H(2)TdMPPc has C-4h symmetry, S,S, R,R, and meso isomers of [Tb(TdMPPc)(2)] were obtained depending on the difference in the direction of the coordination plane of two C-4h-type phthalocyanines with respect to a central Tb3+ ion. We investigated the physical properties of these [Tb(TdMPPc)(2)] isomers, including their single-ion magnetic properties, and found that the spin-reversal energy barrier (U-eff) of the meso isomer was apparently higher than that of the enantiomers. Detailed crystal structural analyses indicated that the meso isomer has a more symmetrical structure than do the enantiomers, thereby suggesting that the higher U-eff of the meso isomer originated from the more highly symmetrical structure.

    DOI: 10.1002/chem.202203272

    Web of Science

  11. Significant Effect of the Flexibility of Bridging Alkyl Chains on the Proximity of Stacked Porphyrin and Phthalocyanine Conjugated with a Fourfold Rotaxane Linkage Reviewed

    Yasuyuki Yamada, Hayato Iida, Shinya Shibano, Nozomi Mihara, Tatsuhisa Kato, Kentaro Tanaka

    Chemistry – A European Journal   Vol. 28 ( 37 ) page: e202200819   2022.7

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Wiley  

    DOI: 10.1002/chem.202200819

    Other Link: https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202200819

  12. Mesogenic discrete metallofoldamer for columnar liquid crystal Reviewed

    Shin-ichiro Kawano, Kazutaka Narita, Yuka Ikemoto, Ako Sasaki, Kentaro Tanaka

    Chemical Communications   Vol. 58 ( 20 ) page: 3274 - 3277   2022.2

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    DOI: https://doi.org/10.1039/D2CC00310D

  13. Metalloporphyrins substituted with N-carbazolyl groups quadruply at meso positions Reviewed

    Shin-ichiro Kawano, Sae Kawada, Atsuya Matsubuchi, Kentaro Tanaka

    Journal of Porphyrins and Phthalocyanines   Vol. 26 ( 2 ) page: 140 - 146   2022.2

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    DOI: https://doi.org/10.1142/S1088424621501170

  14. Direct catalytic benzene hydroxylation under mild reaction conditions by using a monocationic μ-nitrido-bridged iron phthalocyanine dimer with 16 peripheral methyl groups Reviewed International coauthorship

    Yasuyuki Yamada, Chee-Ming Teoh, Yuka Toyoda, Kentaro Tanaka

    New Journal of Chemistry   Vol. 46 ( 3 ) page: 955 - 958   2022.1

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    DOI: https://doi.org/10.1039/D1NJ05369H

  15. Synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer and its methane oxidation activity Invited Reviewed

    Yasuyuki Yamada, Yusuke Miwa, Yuka Toyoda, Tomoo Yamaguchi, Shigehisa Akine, Kentaro Tanaka

    Dalton Transactions   Vol. 50 ( 45 ) page: 16775 - 16781   2021.12

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    DOI: https://doi.org/10.1039/D1DT02922C

  16. Close-Stacking of Iron-Oxo-Based Double-Decker Complex on Graphite Surface Achieved High Catalytic CH4 Oxidation Activity Comparable to that of Methane Monooxygenases Reviewed

    Yasuyuki Yamada, Kentaro Morita, Takuya Sugiura, Yuka Toyoda, Nozomi Mihara, Masanari Nagasaka, Hikaru Takaya, Kiyohisa Tanaka, Takanori Koitaya, Naoki Nakatani, Hiroko Ariga-Miwa, Satoru Takakusagi, Yutaka Hitomi, Toshiji Kudo, Yuta Tsuji, Kazunari Yoshizawa, Kentaro Tanaka

        2021.6

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:American Chemical Society (ACS)  

    Herein, we report that the close-stacking of a double-decker-type dinuclear iron phthalocyanine complex on a graphite surface is effective for achieving high methane oxidation activity, comparable to those of certain MMOs, in an aqueous solution.

    DOI: 10.26434/chemrxiv.14728860.v1

  17. A Light‐Harvesting/Charge‐Separation Model with Energy Gradient Made of Assemblies of meta ‐Pyridyl Zinc Porphyrins Reviewed International coauthorship International journal

    Joe Otsuki, Takumi Okumura, Kosuke Sugawa, Shin‐ichiro Kawano, Kentaro Tanaka, Takehiro Hirao, Takeharu Haino, Yu Jin Lee, Seongsoo Kang, Dongho Kim

    Chemistry – A European Journal   Vol. 27 ( 12 ) page: 4053 - 4063   2021.2

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

    DOI: 10.1002/chem.202003327

    Other Link: https://onlinelibrary.wiley.com/doi/full-xml/10.1002/chem.202003327

  18. Synthesis of Bis{meso-Tetrakis(4-N-alkylpyridiniumyl)porphyrinato}cerium and Its Redox Switching Behavior Invited Reviewed International journal

    Toshio Nishino, Yasuyuki Yamada, Ayumi Yamamoto, Kentaro Tanaka

    Molecules   Vol. 26 ( 4 ) page: 790 - 790   2021.2

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:MDPI AG  

    A novel double-decker porphyrin complex, bis{meso-tetrakis(4-N-alkylpyridiniumyl)porphyrinato}cerium, was prepared. Electrochemical measurements revealed that this complex exhibited reversible redox waves corresponding to a 1e– redox reaction of the cerium center. Treating the complex alternately with an oxidant and a reductant resulted in the reversible redox switching between the oxidized and reduced states in an organic solvent.

    DOI: 10.3390/molecules26040790

  19. High catalytic methane oxidation activity of monocationic μ-nitrido-bridged iron phthalocyanine dimer with sixteen methyl groups Reviewed International journal

    Yasuyuki Yamada, Jyunichi Kura, Yuka Toyoda, Kentaro Tanaka

    Dalton Transactions   Vol. 50 ( 19 ) page: 6718 - 6724   2021

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

    <p>High catalytic methane oxidation activity of a μ-nitrido-bridged iron phthalocyanine dimer was achieved by introducing 16 electron-donating methyl groups onto the phthalocyanine rings.</p>

    DOI: 10.1039/d1dt00941a

  20. Synthesis of a monocationic μ-nitrido-bridged iron porphycene dimer and its methane oxidation activity Reviewed

    Yasuyuki Yamada, Yusuke Miwa, Yuka Toyoda, Tomoo Yamaguchi, Shigehisa Akine, Kentaro Tanaka

    Dalton Transactions   Vol. 50 ( 45 ) page: 16775 - 16781   2021

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

    Herein, we synthesized a monocationic μ-nitrido-bridged iron porphycene dimer, a structural analogue of a monocationic μ-nitrido-bridged iron phthalocyanine dimer, which is known as one of the most potent molecule-based catalysts for methane oxidation.

    DOI: 10.1039/d1dt02922c

  21. Structure and dynamics of a chiral cubanoid complex composed of lithium and salphen Reviewed International journal

    Shin-ichiro Kawano, Kyohei Tomita, Kentaro Tanaka

    Inorganica Chimica Acta   Vol. 512   page: 119894 - 119894   2020.11

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Elsevier BV  

    DOI: 10.1016/j.ica.2020.119894

  22. Development of functional molecular assemblies based on programmable construction of face-to-face assemblies of metallo-porphyrinoids Invited Reviewed International journal

    Yasuyuki Yamada, Kentaro Tanaka

    Journal of Inclusion Phenomena and Macrocyclic Chemistry   Vol. 96 ( 3-4 ) page: 197 - 213   2020.4

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Springer Science and Business Media LLC  

    DOI: 10.1007/s10847-019-00969-9

    Other Link: http://link.springer.com/article/10.1007/s10847-019-00969-9/fulltext.html

  23. μ-Nitrido-bridged iron phthalocyanine dimer bearing eight peripheral 12-crown-4 units and its methane oxidation activity Reviewed International journal

    Yasuyuki Yamada, Jyunichi Kura, Yuka Toyoda, Kentaro Tanaka

    New Journal of Chemistry   Vol. 44 ( 44 ) page: 19179 - 19183   2020

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:Royal Society of Chemistry (RSC)  

    <p>A novel μ-nitrido-bridged iron phthalocyanine dimer with eight peripheral 12-crown-4 units was synthesized and its methane oxidation activity was investigated.</p>

    DOI: 10.1039/d0nj04601a

  24. Liquid-crystalline Metallomacrocycles Composed of Bis(hydroxypyridono)toluene Ligand and Cu2+ Ions. Reviewed International journal

    Shin-Ichiro Kawano, Kohei Ideta, Tomohiko Banno, Kentaro Tanaka

    Chemistry, an Asian journal   Vol. 14 ( 23 ) page: 4415 - 4419   2019.12

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    A series of π-extended chelating scaffolds incorporating two hydroxypyridone moieties were synthesized. X-ray crystallographic analysis revealed that a bis(hydroxypyridono)toluene ligand possessed a unique π-extended structure and exhibited efficient phase segregation from the aliphatic chains attached at the heterocyclic nitrogen. The bis-bidentate ligand formed a metal-coordination-induced macrocycle with Cu2+ ions. During the complexation, a spectral change in the visible region was induced. Furthermore, the successful development of a liquid crystal of the metallomacrocycle with appropriate side chains was achieved. Examples of liquid-crystalline macrocycles formed via metal-mediated self-assembly are still rare. Among them, the macrocycle described in this paper showed an obvious hexagonal columnar phase reflecting the three-fold symmetric planar structure of the mesogenic metal complex.

    DOI: 10.1002/asia.201901323

    PubMed

  25. Catalytic methane oxidation by a supramolecular conjugate based on a mu-nitrido-bridged iron porphyrinoid dimer Reviewed International journal

    Yamada, Yasuyuki, Morita, Kentaro, Mihara, Nozomi, Igawa, Kazunobu, Tomooka, Katsuhiko, Tanaka, Kentaro

    NEW JOURNAL OF CHEMISTRY   Vol. 43 ( 29 ) page: 11477 - 11482   2019.8

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:ROYAL SOC CHEMISTRY  

    Catalytic methane oxidation was conducted using a mu-nitrido-bridged dinuclear iron complex of a fourfold rotaxane heterodimer of a porphyrin and a phthalocyanine. Extension of the mu-stacked structure of the four-fold rotaxane-based mu-nitrido-bridged iron porphyrinoid dimer by supramolecular complexation with an additional tetraanionic porphyrin apparently increased the methane conversion ability.

    DOI: 10.1039/c9nj02210d

    Web of Science

  26. Improved synthesis of monocationic mu-nitrido-bridged iron phthalocyanine dimer with no peripheral substituents Reviewed International journal

    Yamada Yasuyuki, Sugiura Takuya, Morita Kentaro, Ariga-Miwa Hiroko, Tanaka Kentaro

    INORGANICA CHIMICA ACTA   Vol. 489   page: 160 - 163   2019.4

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    Authorship:Last author, Corresponding author   Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELSEVIER SCIENCE SA  

    mu-Nitrido-bridged iron phthalocyanine dimers have attracted considerable attention because of their catalytic ability in alkane oxidation. However, clear and practical synthetic procedures for the simplest mu-nitrido-bridged iron phthalocyanine dimer with no peripheral substituents have not been reported because of its low solubility. In this study, we report improved synthesis and spectroscopic identification of the monocationic species of mu-nitrido-bridged iron phthalocyanine dimers that has no peripheral substituent groups. We observed that the use of iodine as an oxidant for the mu-nitrido-bridged iron phthalocyanine dimer prevents over-oxidation. Pyridine can dissolve its 1e(-)-oxidized monocationic species, which was characterized by H-1 NMR, C-13 NMR, IR, and UV spectroscopy as well as cyclic voltammetry.

    DOI: 10.1016/j.ica.2019.02.021

    Web of Science

  27. Near-infrared absorption by intramolecular charge-transfer transition in 5,10,15,20-tetra(N-carbazolyl)porphyrin through protonation Reviewed International journal

    Kawano Shin-ichiro, Kawada Sae, Kitagawa Yasutaka, Teramoto Rena, Nakano Masayoshi, Tanaka Kentaro

    CHEMICAL COMMUNICATIONS   Vol. 55 ( 20 ) page: 2992 - 2995   2019.3

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    DOI: 10.1039/c8cc09667h

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  28. Site-Selective Supramolecular Complexation Activates Catalytic Ethane Oxidation by a Nitrido-Bridged Iron Porphyrinoid Dimer Reviewed International journal

    Nozomi Mihara, Yasuyuki Yamada, Hikaru Takaya, Yasutaka Kitagawa, Kazunobu Igawa, Katsuhiko Tomooka, Hiroshi Fujii, Kentaro Tanaka

    Chemistry - A European Journal   Vol. 25 ( 13 ) page: 3369 - 3375   2019.3

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    © 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Development of supramolecular methods to further activate a highly reactive intermediate is a fascinating strategy to create novel potent catalysts for activation of inert chemicals. Herein, a supramolecular approach to enhance the oxidizing ability of a high-valent oxo species of a nitrido-bridged iron porphyrinoid dimer that is a known potent molecular catalyst for light alkane oxidation is reported. For this purpose, a nitrido-bridged dinuclear iron complex of porphyrin-phthalocyanine heterodimer 3 5+ , which is connected through a fourfold rotaxane, was prepared. Heterodimer 3 5+ catalyzed ethane oxidation in the presence of H 2 O 2 at a relatively low temperature. The site-selective complexation of 3 5+ with an additional anionic porphyrin (TPPS 4− ) through π–π stacking and electrostatic interactions afforded a stable 1:1 complex. It was demonstrated that the supramolecular post-synthetic modification of 3 5+ enhances its catalytic activity efficiently. Moreover, supramolecular conjugates achieved higher catalytic ethane oxidation activity than nitrido-bridged iron phthalocyanine dimer, which is the most potent iron-oxo-based molecular catalyst for light-alkane oxidation reported so far. Electrochemical measurements proved that the electronic perturbation from TPPS 4− to 3 5+ enhanced the catalytic activity.

    DOI: 10.1002/chem.201805580

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    PubMed

  29. Specific and Oriented Encapsulation of Fullerene C70 into a Supramolecular Double-Decker Cage Composed of Shape-Persistent Macrocycles Reviewed International journal

    Kawano Shin-ichiro, Fukushima Tomoaki, Tanaka Kentaro

    ANGEWNDTE CHEMIE-INTERNATIONAL EDITION   Vol. 57 ( 45 ) page: 14827 - 14831   2018.11

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    DOI: 10.1002/anie.201809167

    Web of Science

  30. Liquid-crystalline Phthalocyanine with Short Intercolumnar Distance and Variation of the Liquid Crystallinity Induced by Square-planar Metal Ions Reviewed International journal

    Kawano Shin-ichiro, Yamada Yasuyuki, Shu Rongfang, Ishihara Yu, Tanaka Kentaro

    CHEMISTRY LETTERS   Vol. 47 ( 10 ) page: 1262 - 1264   2018.10

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    DOI: 10.1246/cl.180591

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  31. Programmable arrangement of metal ions in a cofacially stacked assembly of porphyrinoids toward molecular tags Reviewed

    Mihara Nozomi, Yamada Yasuyuki, Furukawa Ko, Kato Tatsuhisa, Tanaka Kentaro

    DALTON TRANSACTIONS   Vol. 47 ( 20 ) page: 7044-7049   2018.5

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    DOI: 10.1039/c8dt01334a

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  32. Columnar Liquid-Crystalline Macrocycles Synthesized via Metal Ion-Assisted Self-Assembly Reviewed

    Kawano Shin-ichiro, Murai Takafumi, Harada Takahiro, Tanaka Kentaro

    INORGANIC CHEMISTRY   Vol. 57 ( 7 ) page: 3913-3919   2018.4

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/acs.inorgchem.8b00046

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  33. Columnar Liquid Crystals from a Giant Macrocycle Mesogen Reviewed

    Kawano Shin-ichiro, Kato Masahiro, Soumiya Shinya, Nakaya Masato, Onoe Jun, Tanaka Kentaro

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 57 ( 1 ) page: 167-171   2018.1

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/anie.201709542

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  34. Intramolecular strong electronic coupling in a discretely H-aggregated phthalocyanine dimer connected with a rigid linker

    Yasuyuki Yamada, Yasuyuki Yamada, Yasuyuki Yamada, Katsuhiko Nawate, Tomoaki Maeno, Kentaro Tanaka

    Chemical Communications   Vol. 54   page: 8226-8228   2018.1

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    © 2018 The Royal Society of Chemistry. Preparation of an accurate assembly of phthalocyanines is rather difficult because of the high aggregation property of phthalocyanines. In this study, a novel discrete phthalocyanine dimer was prepared in which the relative configuration of each component was tightly and accurately fixed in an H-aggregate form by a rigid U-shaped linker. Electrochemical measurements showed that there were strong intramolecular electronic interactions between the two phthalocyanines.

    DOI: 10.1039/c8cc04335c

    Scopus

  35. Dynamic Molecular Invasion into a Multiply Interlocked Catenane Reviewed

    Yamada Yasuyuki, Itoh Ryohei, Ogino Sayaka, Kato Tatsuhisa, Tanaka Kentaro

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 56 ( 45 ) page: 14124-14129   2017.11

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/ange.201708248

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  36. Electronic perturbation of supramolecular conjugates of porphyrins and phthalocyanines Reviewed

    Mihara Nozomi, Yamada Yasuyuki, Akine Shigehisa, Sugimoto Kunihisa, Tanaka Kentaro

    CHEMICAL COMMUNICATIONS   Vol. 53 ( 14 ) page: 2230-2232   2017.2

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1039/c6cc09590a

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  37. Programmable Arrangement of Heterometal Ions in a Supramolecular Array of Porphyrin and Phthalocyanine Reviewed

    Nozomi Mihara, Yasuyuki Yamada, and Kentaro Tanaka

    Bull. Chem. Soc. Jpn.   Vol. 90   page: 427-435   2017

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1246/bcsj.20160423

  38. Solid-State NMR Study of Dynamic Properties of a Columnar Liquid Crystalline Macrocycle Reviewed

    Shin-ichiro Kjawano and Kentaro Tanaka

    Bull. Chem. Soc. Jpn.   Vol. 90   page: 826–830   2017

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    DOI: 10.1246/bcsj.20170047

  39. Oxygen Reduction to Water by Cofacial Dimer of Fe(III)porphyrin and Fe(III)phthalocyanine Linked via Highly Flexible Four-fold Rotaxane Reviewed

    Nozomi Mihara, Yasuyuki Yamada, Hikaru Takaya, Yasutaka Kitagawa, Shin Aoyama, Kazunobu Igawa, Katsuhiko Tomooka, and Kentaro Tanaka

    Chem. Eur. J.   Vol. 23   page: 7508-7514   2017

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    DOI: 10.1002/chem.201700082

  40. Electronic Perturbation of Supramolecular Conjugates of Porphyrins and Phthalocyanines Reviewed

    Nozomi Mihara, Yasuyuki Yamada, Shigehisa Akine, Kunihisa Sugimoto and Kentaro Tanaka

      Vol. 53   page: 2230-2232   2017

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    DOI: 10.1039/C6CC09590A

  41. Frontispiece: Metal-Ion-Induced Switch of Liquid-Crystalline Orientation of Metallomacrocycles

    Shin ichiro Kawano, Takashi Hamazaki, Atsushi Suzuki, Kenshin Kurahashi, Kentaro Tanaka

    Chemistry - A European Journal   Vol. 22   page: 15674   2016.10

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/chem.201504864

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  42. Inside Cover: Assembly of Multi-Phthalocyanines on a Porphyrin Template by Fourfold Rotaxane Formation (Chem. Eur. J. 35/2016)

    Yasuyuki Yamada, Yasuyuki Yamada, Tatsuhisa Kato, Kentaro Tanaka

    Chemistry - A European Journal   Vol. 22   page: 12202   2016.8

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/chem.201602993

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  43. Kinetically "Locked" Metallomacrocycle Reviewed

    Toshio Nishino, Yasuyuki Yamada, Shigeyuki Akine, Kunihisa Sugimoto and Kentaro Tanaka

    Dalton Trans.   Vol. 45   page: 3831-3837   2016

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    DOI: 10.1039/c5dt04635a

  44. Self-Assembled Synthesis and Liquid Crystalline Property of Metallomacrocycle Composed of Naphthalenedihydroxamate and Cu2+ Ions Reviewed

    Shin-ichiro Kawano, Hiroshi Inada, and Kentaro Tanaka

    Chem. Lett.   Vol. 45   page: 1105-1107   2016

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    DOI: 10.1246/cl.160577

  45. Metal-Ion-Induced Switch of Liquid Crystalline Orientation of Metallomacrocycles Reviewed

    Shin-ichiro Kawano, Takashi Hamazaki, Atsushi Suzuki, Kenshin Kurahashi, and Kentaro Tanaka

    Chem. Eur. J.   Vol. 22   page: 15674-15683   2016

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1002/chem.201601941

  46. Assembly of Multi-Phthalocyanines on a Porphyrin Template via Fourfold Rotaxane Formation Reviewed

    Yasuyuki Yamada, Tatsuhisa Kato, and Kentaro Tanaka

    Chem. Eur. J.   Vol. 22   page: 12371-12380   2016

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    DOI: 10.1002/chem.201601768

  47. Crystalline Two-dimensional Nanosheet Composed of Tetraanionic Porphyrins and Tetracationic Metallomacrocycles Reviewed

    Toshio Nishino, Yasuyuki Yamada, and Kentaro Tanaka

    J. Porphyrins and Phthalocyanines   Vol. 20   page: 694-699   2016

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    DOI: 10.1142/S1088424616500590

  48. Stacked Pairing of Anionic Porphyrins on a Tetracationic Macrocyclic Template Reviewed

    Toshio Nishino, Yasuyuki Yamada, and Kentaro Tanaka

    Chem. Lett.   Vol. 45   page: 356-358   2016

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    DOI: 10.1246/cl.151185

  49. Columnar Liquid-Crystalline Metallomacrocycles Reviewed

    Sinichito Kawano, Yukari Ishida, Kentaro Tanaka

    Journal of American Chemical Society   Vol. 137   page: 2295-2302   2015.2

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    DOI: 10.1021/ja510585u

  50. Metal-Induced Dynamic Conformational and Fluorescence Switch of Quinone-Appended Zn-Porphyrin Reviewed

    Yasuyuki Yamada, Kosuke Hiraga, Kentaro Tanaka

    Journal of Porphyrins and Phthalocyanines   Vol. 19   page: 334-351   2015

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1142/S1088424615500169

  51. Crystal Structures of Stacked Ionic Assemblies of Tetracationic and Tetraanionic Porphyrins Reviewed

    Yamada Yamada, Satoru Matsumoto, Kazushi Yamada, Toshio Nishino, Nozomi Mihara, Kunihiko Sugimoto, Kentaro Tanaka

    Chemistry Letters   Vol. 43   page: 1377-1379   2014.8

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    DOI: 10.1246/cl.140392

  52. Coordination Oligomers and Polymers of an Oxazole-Appended Zinc Chlorophyll Derivative Reviewed

    Y. Shinozaki, I. Yoshikawa, K. Araki, K. Ohara, K. Yamaguchi, S. Kawano, K. Tanaka, Y. Araki, T. Wada, J. Otsuki

    Chemistry Letters   Vol. 43   page: 862-864   2014.6

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    DOI: 10.1246/cl.140135

  53. Triply Stacked Heterogeneous Array of Porphyrins and Phthalocyanine through Stepwise Formation of a Fourfold Rotaxane and an Ionic Complex Reviewed

    Yasuyuki Yamada, Nozomi Mihara, Shinya Shibano, Kunihiro Sugimoto, Kentaro Tanaka

    Journal of American Chemical Society   Vol. 135   page: 11505-11508   2013.8

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    DOI: 10.1021/ja405963t

  54. Metal-Induced Structural Switching of a Folded Quinone-Sandwiched Porphyrin Reviewed

    Yasuyuki Yamada Kentaro Tanaka

    J. Inorg. Organomet. Polym.   Vol. 23   page: 180-185   2013.6

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    Authorship:Lead author   Language:English   Publishing type:Research paper (scientific journal)  

    DOI: 10.1007/s10904-012-9726-4

  55. Double Helices of a Pyridine-Appended Zinc Chlorophyll Derivative Reviewed

    Y. Shinozaki, G. Richards, K. Ogawa, A. Yamano, K. Ohara, K. Yamaguchi, S. Kawano, K. Tanaka, Y. Araki, T. Wada, J. Otsuki

    Journal of American Chemical Society   Vol. 135   page: 5262–5265   2013.4

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    DOI: 10.1021/ja400493e

  56. Synthesis of a Hetero-Dinuclear Metal Complex in a Porphyrin/Phthalocyanine Four-Fold Rotaxane Reviewed

    Yasuyuki Yamada, Nozomi Mihara, Kentaro Tanaka

    Dalton Transaction   Vol. 42   page: 15873-15876   2013

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    DOI: 10.1039/C3DT51043C

  57. Repetitive Stepwise Rotaxane Formation toward Programmable Molecular Arraying Reviewed

    Yauyuki Yamada, Masaaki Okada, Kentaro Tanaka

    Chemical Communications   Vol. 49   page: 11053-11055   2013

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    DOI: 10.1039/C3CC46859C

  58. Synthesis of a hetero-dinuclear metal complex in a porphyrin/phthalocyanine four-fold rotaxane Reviewed

    Yamada Yasuyuki, Mihara Nozomi, Tanaka Kentaro

    DALTON TRANSACTIONS   Vol. 42 ( 45 ) page: 15873-15876   2013

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    DOI: 10.1039/c3dt51043c

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  59. Repetitive stepwise rotaxane formation toward programmable molecular arrays Reviewed

    Yamada Yasuyuki, Okada Masa-aki, Tanaka Kentaro

    CHEMICAL COMMUNICATIONS   Vol. 49 ( 94 ) page: 11053-11055   2013

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    DOI: 10.1039/c3cc46859c

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  60. Harmony of π-π Stacking Interaction and Metal Complexation to Generate Molecular Functional Emergence Invited Reviewed

    Yamada Yasuyuki, Tanaka Kentaro

    Bull. Jpn. Soc. Coord. Chem.   Vol. 62   page: 12 - 22   2013

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    In this review, we focus on the integrated assemblies of metal complexes and their functional emergence generated by the synergy effects of π-π stacking interaction and metal complexation. Programmable construction of integrated molecular assemblies is the best measure for bringing out the emergent functions which can be evolved from the intermolecular communications of functional molecular components. Combination of π-π stacking interaction and metal complexation allows not only to reinforce the mutual interactions but also to generate the emergent intermolecular communications. This review introduces the recent studies including the synergy effects on electrical, magnetic, catalytic and molecular recognition functions in soft, crystalline and single molecular materials.

    DOI: 10.4019/bjscc.62.12

    Other Link: https://jlc.jst.go.jp/DN/JALC/10031164206?from=CiNii

  61. Room-Temperature Single Molecular Memory Reviewed

    S. Kano, Y. Yamada, K. Tanaka, Y. Majima

    App. Phys. Lett.   Vol. 100   page: 053101(1-3)   2012.1

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    DOI: 10.1063/1.3679127

  62. Switchable Intermolecular Communication in a Four-Fold Rotaxane Reviewed

    Yasuyuki Yamada, Mitsuyoshi Okamoto, Ko Furukawa, Tatsuhisa Kato, Kentaro Tanaka

    Angewandte Chimie International Edition   Vol. 51   page: 709–713   2012

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    DOI: 10.1002/anie.201107104

  63. Direct Conductance Measurement of Individual Metallo-DNA Duplexes within Single-Molecule Break Junctions Reviewed

    S. Liu, G. H. Clever, Y. Takezawa, M. Kaneko, K. Tanaka, X. Guo, M. Shionoya

    Angewandte Chemie International Edition   Vol. 50   page: 9048-9052   2011

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    DOI: 10.1002/anie.201102980

  64. Discrete Self-Assembly of Iron(III) Ions inside Triple-Stranded Artificial DNA Reviewed

    Y. Takezawa, W. Maeda, K. Tanaka, and M. Shionoya

    Angew. Chem. Int. Ed.   Vol. 48   page: 1081-1084   2009

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  65. Discrete Self-Assembly of Iron(III) Ions inside Triple-Stranded Artificial DNA Reviewed

    Takezawa Yusuke, Maeda Wakana, Tanaka Kentaro, Shionoya Mitsuhiko

    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION   Vol. 48 ( 6 ) page: 1081-1084   2009

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    DOI: 10.1002/anie.200804654

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  66. Soft metal-mediated base pairing with novel synthetic nucleosides possessing an O,S-donor ligand Reviewed

    Takezawa Yusuke, Tanaka Kentaro, Yori Maiko, Tashiro Shohei, Shiro Motoo, Shionoya Mitsuhiko

    JOURNAL OF ORGANIC CHEMISTRY   Vol. 73 ( 16 ) page: 6092-6098   2008.8

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    DOI: 10.1021/jo800587d

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  67. Ni(II)-Mediated self-assembly of artificial beta-dipeptides forming a macrocyclic tetranuclear complex with interior spaces for in-line molecular arrangement Reviewed

    Miyake Ryosuke, Tashiro Shohei, Shiro Motoo, Tanaka Kentaro, Shionoya Mitsuhiko

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 130 ( 17 ) page: 5646-+   2008.4

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    DOI: 10.1021/ja8009555

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  68. A close-packed, highly insulating organic thin monolayer on Si(111) Reviewed

    Tanaka Kentaro, Tanaka Taishi, Hasegawa Takeshi, Shionoya Mitsuhiko

    CHEMISTRY LETTERS   Vol. 37 ( 4 ) page: 440-441   2008.4

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    DOI: 10.1246/cl.2008.440

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  69. A Closed-packed, Highly-insulating Organic Thin Monolayer on Si(111) Reviewed

    K. Tanaka, T. Tanaka, T. Hasegawa, and M. Shionoya

    Chem. Lett.   Vol. 37   page: 440-441   2008

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  70. バイオインスパイアードなテンプレートを用いた精密分子組織の構築 Invited

    田中健太郎

    液晶   Vol. 13   page: 33-41   2008

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  71. Soft Metal-Mediated Base Pairing with Novel Synthetic Nucleosides Possessing an O,S-Donor Ligand Reviewed

    Y. Takezawa, K. Tanaka, M. Yori, S. Tashiro, M. Shiro, and M. Shionoya

    J. Org. Chem.   Vol. 73   page: 6092-6098   2008

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  72. Ni(II)-Mediated Self-Assembly of Artificial β-Dipeptides Forming a Macrocyclic Tetranuclear Complex with Interior Spaces for In-Line Molecular Arrangement Reviewed

    R. Miyake, S. Tashiro, M. Shiro, K. Tanaka, and M. Shionoya

    J. Am. Chem. Soc.   Vol. 130   page: 5646-5647   2008

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  73. Synthesis of a macrocyclic tetranuclear Ni(II) complex possessing functional holes from artificial beta-dipeptides Reviewed

    Miyake Ryosuke, Tashiro Shohei, Shiro Motoo, Tanaka Kentaro, Shionoya Mitsuhiko

    YAKUGAKU ZASSHI-JOURNAL OF THE PHARMACEUTICAL SOCIETY OF JAPAN   Vol. 128   page: 74   2008

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  74. Discrete self-assembly of iron (III) ions inside triple-stranded artificial DNA Reviewed

    Takezawa Yusuke, Kaneko Motoo, Maeda Wakana, Clever Guido H., Tanaka Kentaro, Shionoya Mitsuhiko

    YAKUGAKU ZASSHI-JOURNAL OF THE PHARMACEUTICAL SOCIETY OF JAPAN   Vol. 128   page: 78   2008

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  75. Synthesis of a metal-salen base pair for the assembly of programmed metal arrays inside DNA Reviewed

    Clever Guido H., Tanaka Kentaro, Takezawa Yusuke, Kaul Corinna, Carell Thomas, Shionoya Mitsuhiko

    YAKUGAKU ZASSHI-JOURNAL OF THE PHARMACEUTICAL SOCIETY OF JAPAN   Vol. 128   page: 67   2008

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  76. A template-directed synthetic approach to halogen-bridged mixed-valence platinum complexes on artificial peptides in solution Reviewed

    Tanaka Kentaro, Kaneko Kenji, Watanabe Yusuke, Shionoya Mitsuhiko

    DALTON TRANSACTIONS   ( 46 ) page: 5369-5371   2007.12

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    DOI: 10.1039/b711804j

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  77. Programmable metal assembly on bio-inspired templates Reviewed

    Tanaka Kentaro, Shionoya Mitsuhiko

    COORDINATION CHEMISTRY REVIEWS   Vol. 251 ( 21-24 ) page: 2732-2742   2007.11

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    DOI: 10.1016/j.ccr.2007.08.018

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  78. Programmable self-assembly of metal ions inside artificial DNA duplexes (vol 1, pg 190, 2006) Reviewed

    Tanaka Kentaro, Clever Guido H., Takezawa Yusuke, Yamada Yasuyuki, Kaul Corinna, Shionoya Mitsuhiko, Carell Thomas

    NATURE NANOTECHNOLOGY   Vol. 2 ( 1 ) page: 63   2007.1

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    DOI: 10.1038/nnano.2006.182

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  79. A template-directed synthetic approach to halogen-bridged mixed-valence platinum complexes on artificial peptides in solution Reviewed

    Kentaro Tanaka, Kenji Kaneko, Yusuke Watanabe and Mitsuhiko Shionoya

    Dalton Transactions   Vol. 2007   page: 5369-5371   2007

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    A template-directed synthetic approach to halogen-bridged mixed-valence platinum complexes has been performed in organic media using, for instance, a synthetic peptide bearing two bis(ethylenediamine)-based Pt(IV) complexes with two axial bromide anionic ligands,5 [1a(Pt(IV)Br2 (en))2 ](RSO3 )4 , and a [Pt(II)(en)2 ](RSO3 )2 complex (R = (C12 H25 OCH2 )2 CHO(CH2 )3 -).

  80. 生体高分子に学ぶ“ものづくり”-金属イオンの精密配列化 Invited

    田中健太郎

    超分子研究会アニュアルレビュー   Vol. 28   page: 2-3   2007

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  81. Programmable metal assembly on bio-inspired templates Invited Reviewed

    Kentaro Tanaka and Mitsuhiko Shionoya

    Coordination Chemistry Reviews   Vol. 251   page: 1731-2742   2007

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    This review highlights precisely controlled assembly of metal complexes on DNA templates towards functionalized materials including our recent research progress

  82. Programmed metal arrays by means of designable biological macromolecules

    Kentaro Tanaka, Kentaro Tanaka, Tokomo Okada, Mitsuhiko Shionoya

    Redox Systems Under Nano-Space Control     page: 155-165   2006.12

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    9.4 Conclusion: In this study, we demonstrate that biopolymers such as DNA and peptides can be precisely redesigned and reconstructed as templates for homogeneous or even heterogeneous assembly of metal ions in a programmable manner by chemically modiyfing their building blocks. This bottom-up strategy based on biorelated molecules would generate not only a new structuralmotif formetal clusters in the biomolecules but also a metal-triggered information-transfer system. © 2006 Springer-Verlag Berlin Heidelberg.

    DOI: 10.1007/3-540-29580-1_9

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  83. Programmable self-assembly of metal ions inside artificial DNA duplexes Reviewed

    Tanaka Kentaro, Clever Guido H., Takezawa Yusuke, Yamada Yasuyuki, Kaul Corinna, Shionoya Mitsuhiko, Carell Thomas

    NATURE NANOTECHNOLOGY   Vol. 1 ( 3 ) page: 190-U5   2006.12

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    DOI: 10.1038/nnano.2006.141

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  84. Bio-inspired programmable self-assembly on DNA templates Reviewed

    Tanaka Kentaro, Shionoya Mitsuhiko

    CHEMISTRY LETTERS   Vol. 35 ( 7 ) page: 694-699   2006.7

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    DOI: 10.1246/cl.2006.694

    Web of Science

  85. Toward a protecting-group-free halogen-metal exchange reaction: Practical, chemoselective metalation of functionalized aromatic halides using dianion-type zincate, (Bu4ZnLi2)-Bu-t Reviewed

    Uchiyama Masanobu, Furuyama Taniyuki, Kobayashi Minoru, Matsumoto Yotaro, Tanaka Kentaro

    JOURNAL OF THE AMERICAN CHEMICAL SOCIETY   Vol. 128 ( 26 ) page: 8404-8405   2006.7

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    DOI: 10.1021/ja058246x

    Web of Science

  86. Bio-Inspired Programmable Self-Assembly on DNA Templates Invited

    K. Tanaka and M. Shionoya

    Chem. Lett.   Vol. 35   page: 694-699   2006

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    Besides the biological importance of DNA as storage of genetic information, DNA is a smart molecule to assemble functional units since it is possible to use sequences of nucleobases to encode molecular assembled systems in a predetermined fashion over a wide range in size. This review highlights recent advance in precise control of molecular assembly on DNA templates directed towards functionalized materials.

  87. *Programmable Self-Asembly of Metal Ions Inside Artificial DNA Duplexes Reviewed

    K. Tanaka, G. Clever, Y. Takezawa, Y. Yamada, C. Kaul, M. Shionoya, and T. Carell

    Nature Nanotech.   Vol. 1   page: 190-194   2006

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  88. Toward a Protecting-Group-Free Halogen-Metal Exchange Reaction:Practical, Chemoselective Metalation of Functionalized Aromatic HalidesUsing Dianion-type Zincate, tBu4ZnLi2 Reviewed

    Masanobu Uchiyama, Taniyuki Furuyama, Minoru Kobayashi, Yotaro Matsumoto, and Kentaro Tanaka

    J. Am. Chem. Soc.   Vol. 128   page: 8404-8405   2006

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    A versatile preparation method for aromatic zincate compounds through a halogen-zinc exchange reaction using dilithium tetra-tert-butylzincate (tBu4ZnLi2) has been developed. This reagent permits efficient preparation of highly functionalized aromatic zincates, particularly, those with electrophilic functional groups, such as ester, amide, alcohol, and phenol. Halogen-zinc exchange reactions followed by electrophilic trapping (with allyl bromide or benzaldehyde) proved to be a powerful tool for C-C bond formation on functionalized aromatic rings. The functionalized aromatic zincate intermediate was also found to undergo copper- and palladium-catalyzed C-C bond-forming reactions with good yields and high chemoselectivity.

  89. Molecular orientation of organic monolayers on Si(111)

    Taishi Tanaka, Kentaro Tanaka, Kentaro Tanaka, Hiroyuki Kakuda, Takeshi Hasegawa, Takeshi Hasegawa, Mitsuhiko Shionoya

    Polymer Preprints, Japan   Vol. 54   page: 3329-3330   2005.12

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    Alkenes form self-assembled monolayers on a hydrogen-terminated Si(111) surface via hydrosilylation of defines. Since the monolayers are attached onto the substrate covalently through direct Si-C bonding, the molecular orientation of the monolayer is strongly influenced by compatibility between the crystal structure of Si(111) surface and the molecular structure of the olefin. In this study, we examined the formation of various monolayers and their molecular orientations on Si(111).

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  90. Heterogeneous metal arrays into artificial metallo-DNAs as templates International journal

    Kentaro Tanaka, Kentaro Tanaka, Yusuke Takezawa, Takuya Agata, Atsushi Katagiri, Tatsuhisa Kato, Mitsuhiko Shionoya

    Polymer Preprints, Japan   Vol. 54   page: 5126 - 5127   2005.12

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    Besides the biological importance of DNA as storage of genetic information, the fundamental and canonical structure of duplex DNA can be regarded as a template for the bio-inspired molecular architectures to develop new functions. DNA has an attractive system to assemble functional building blocks, because automated synthesizers can routinely make oligomers with desired lengths and sequences. Replacement of hydrogen-bonded base pairing of DNA by metal-mediated base pairing could lead to &quot;metallo-DNA&quot; in which metal ions are aligned along the helix axis in a controllable fashion (Chart 1). We report here the de novo designed heterogeneous metal array in artificial metallo-DNA. To heterogeneously array metal ions in double helices, d(5′-GHPHC-3′)2, d(5′-GHHPHHC-3′)2, and d(5′-GHVHC- 3′)2were synthesized, where H is a hydroxypyridone-bearing nucleotide forming a square planar complex with a Cu2+ion, P is a pyridine-bearing nucleotide forming a linear complex with an Ag+or an Hg2+ion, and V is an abasic site. Stepwise photometric titration experiments of Cu2+and subsequent Hg2+to the duplexes and electrospray ionization mass spectroscopy clearly demonstrated the quantitative and site-selective formation of Cu2+-Hg2+-Cu2+, Cu2+-Cu2+-Hg2+-Cu2+-Cu2+and Cu2+- Cu2+arrays in the centers of the duplexes, respectively (Fig. 2).

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  91. Analysis of hydrogen-terminated Si(1 1 1) surface by infrared multiple-angle incidence resolution spectroscopy

    Hiroyuki Kakuda, Takeshi Hasegawa, Takeshi Hasegawa, Taishi Tanaka, Kentaro Tanaka, Kentaro Tanaka, Mitsuhiko Shionoya

    Chemical Physics Letters   Vol. 415   page: 172-175   2005.10

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    The infrared multiple-angle incidence resolution spectroscopy (MAIRS) has been employed to analyze the hydrogen-terminated Si(1 1 1) 1 × 1-H surface. The new technique of infrared MAIRS provides two absorption spectra simultaneously on an identical sample, which separately reveal the surface-parallel and surface-normal vibration spectra. It has been exhibited in the present study that the infrared MAIRS technique is powerful to discuss some infrared key bands in terms of molecular orientation concerned with Si-H vibrational modes on the Si(1 1 1) 1 × 1-H surface with the use of the two spectra. © 2005 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.cplett.2005.09.017

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  92. Heterogeneous assembly of silver(I) and calcium(II) ions accompanying a dimer formation of cyclo(L-Ala-L-Met)3. Reviewed

    Okada T, Tanaka K, Shiro M, Shionoya M

    Chemical communications (Cambridge, England)   ( 11 ) page: 1484-1486   2005.3

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    DOI: 10.1039/b415567j

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  93. Analysis of Hydrogen-Terminated Si(111) Surface by Infrared Multiple-Angle Incidence Resolution Spectroscopy Reviewed

    Hiroyuki Kakuda, Takeshi Hasegawa, Taishi Tanaka, Kentaro Tanaka, and Mitsuhiko Shionoya

    Chem. Phys. Lett.   Vol. 415   page: 172-175   2005

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  94. Heterogeneous Assembly of Silver(I) and Calcium(II) Ions Accompanying a Dimer Formation of cyclo(L-Ala- L -Met)3 Reviewed

    T. Okada, K. Tanaka, M. Shiro, and M. Shionoya

    Chem. Commun.   Vol. 2005   page: 1484/1486   2005

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    Heterogeneous assembly of three Ag+ and one Ca2+ ion has
    been accomplished in a dimeric structure of cyclic hexapeptides,
    cyclo(L-Ala-L-Met)3.

  95. Artificial metallo-DNA: a bio-inspired approach to metal array programming. Reviewed

    Shionoya M, Tanaka K

    Current opinion in chemical biology   Vol. 8 ( 6 ) page: 592-597   2004.12

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    DOI: 10.1016/j.cbpa.2004.09.006

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  96. [Artificial metallo-DNA: arraying metal ions using DNA]. Reviewed

    Shionoya M, Tanaka K

    Tanpakushitsu kakusan koso. Protein, nucleic acid, enzyme   Vol. 49 ( 10 ) page: 1438-1443   2004.8

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  97. Interaction of plastocyanin with oligopeptides: effect of lysine distribution within the peptide. Reviewed

    Hirota S, Okumura H, Arie S, Tanaka K, Shionoya M, Takabe T, Funasaki N, Watanabe Y

    Journal of inorganic biochemistry   Vol. 98 ( 5 ) page: 849-855   2004.5

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    DOI: 10.1016/j.jinorgbio.2003.10.022

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  98. Artificial metallo-DNA: Structural control of DNA and nano-assembly of metal complexes

    Kentaro Tanaka, Mitsuhiko Shionoya

    Yuki Gosei Kagaku Kyokaishi/Journal of Synthetic Organic Chemistry   Vol. 62   page: 508-513   2004.1

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    DNA has a structural basis for the "bottom-up" fabrication of functionalized molecular building blocks. In particular, the replacement of hydrogen-bonded DNA base pairing for alternative one would lead to a novel tool for re-engineering DNA. Recently, we have synthesized a series of artificial nucleosides bearing metal ligands instead of natural nucleobases and demonstrated that metal complexation between the nucleosides effectively drives base pairing. This review describes our recent approaches to metal-based strategy directed towards self-assembled metal arrays within DNA as well as towards structural control of DNA. This strategy provides a new method for self-assembled metal arrays in a predesigned fashioji, leading possibly to metal-based molecular devices such as molecular magnets and wires.

    DOI: 10.5059/yukigoseikyokaishi.62.508

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  99. 金属錯体型人工DNA Invited

    塩谷光彦, 田中健太郎

    蛋白質核酸酵素   Vol. 49   page: 1438-1443   2004

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  100. 金属錯体型人工DNA:DNA構造制御と金属錯体ナノ集積化 Invited

    田中健太郎, 塩谷光彦

    有機合成化学協会誌   Vol. 8   page: 592-579   2004

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  101. Interaction of plastocyanin with oligopeptides: effect of lysine distribution within the peptide Reviewed

    Shun Hirota, Hisano Okumura, Sachiko Arie, Kentaro Tanaka, Mitsuhiko Shionoya, Teruhiro Takabe, Noriaki Funasaki, amd Yoshihito Watanabe

    Journal of Inorganic Biochemistry   Vol. 98   page: 849-855   2004

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    We synthesized and purified four oligopeptides containing four lysines (KKKK, GKKGGKK, KKGGGKK, and KGKGKGK) as models for the plastocyanin (PC) interacting site of cytochrome f. These peptides competitively inhibited electron transfer between cytochrome c and PC. The inhibitory effect increased as the peptide concentrations were increased. The association constants between PC and the peptides did not differ significantly (3500-5100 M

  102. Artificial Metallo-DNA: A Bio-Inspired Approach to Metal Array Programming Invited Reviewed

    M. Shionoya and K. Tanaka

    Curr. Opin. Chem. Biol.   Vol. 8   page: 592-579   2004

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    The structure of DNA is such that the multi-array of functionalized units with desired numbers and sequences within the DNA is possible. In particular, to replace DNA bases, which are biologically important elements for gene expression, by alternative bases would provide powerful tools for programming molecular arrays in a pre-designed manner. This review focuses on recent chemical approaches to
    self-assembled metal arrays within DNA with metal-mediated base pairing.

  103. Role of a non-natural beta-C-nucleotide unit in DNA as a template for DNA and RNA syntheses and as a substrate for nucleolytic digestion. Reviewed

    Aketani S, Tanaka K, Yamamoto K, Ishihama A, Cao H, Tengeiji A, Shionoya M

    European journal of pharmaceutical sciences : official journal of the European Federation for Pharmaceutical Sciences   Vol. 20 ( 1 ) page: 43-51   2003.9

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  104. A discrete self-assembled metal array in artificial DNA. Reviewed

    Tanaka K, Tengeiji A, Kato T, Toyama N, Shionoya M

    Science (New York, N.Y.)   Vol. 299 ( 5610 ) page: 1212-1213   2003.2

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    DOI: 10.1126/science.1080587

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  105. Artificial nucleosides possessing metal binding sites at the 3'- and 5'-positions of the deoxyribose moieties. Reviewed

    Chiba JY, Tanaka K, Ohshiro Y, Miyake R, Hiraoka S, Shiro M, Shionoya M

    The Journal of organic chemistry   Vol. 68 ( 2 ) page: 331-338   2003.1

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    DOI: 10.1021/jo026026l

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  106. Artificial Metallo-DNA: Structural Control and Discrete Metal Assembly Reviewed

    K. Tanaka, Y. Yamada, A. Tengeiji, T. Kato, N. Toyama, Y. Takezawa, M. Yori, M. Shiro, and M. Shionoya

    Nucleic Acids Research Supplement   Vol. 3   page: 121-122   2003

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  107. Artificial Nucleosides Possessing Metal Binding Sites at the 3'- and 5'-Positions of the Deoxyribose Moieties Reviewed

    J. Chiba, K. Tanaka, Y. Ohshiro, R. Miyake, M. Shiro, and M. Shionoya

    J. Org. Chem.   Vol. 68   page: 331-338   2003

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  108. Role of a Non-natural β-C-Nucleotide Unit in DNA as a Template for DNA and RNA Syntheses and as a Substrate for Nucleolytic Digestion Reviewed

    S. Aketani, K. Tanaka, K. Yamamoto, A. Ishihama, H. Cao, A. Tengeiji, and M. Shionoya

    Eur. J. Pharm. Sci.   Vol. 20   page: 43-51   2003

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  109. Artificial metallo-DNA: structural control and discrete metal assembly. Reviewed

    Tanaka K, Yamada Y, Tengeiji A, Kato T, Toyama N, Takezawa Y, Yori M, Shiro M, Shionoya M

    Nucleic acids research. Supplement (2001)   ( 3 ) page: 121-122   2003

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  110. Syntheses and structure-activity relationships of nonnatural beta-C-nucleoside 5'-triphosphates bearing an aromatic nucleobase with phenolic hydroxy groups: inhibitory activities against DNA polymerases. Reviewed

    Aketani S, Tanaka K, Yamamoto K, Ishihama A, Cao H, Tengeiji A, Hiraoka S, Shiro M, Shionoya M

    Journal of medicinal chemistry   Vol. 45 ( 25 ) page: 5594-5603   2002.12

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  111. Efficient incorporation of a copper hydroxypyridone base pair in DNA. Reviewed

    Tanaka K, Tengeiji A, Kato T, Toyama N, Shiro M, Shionoya M

    Journal of the American Chemical Society   Vol. 124 ( 42 ) page: 12494-12498   2002.10

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  112. Formation of silver(I)-mediated DNA duplex and triplex through an alternative base pair of pyridine nucleobases. Reviewed

    Tanaka K, Yamada Y, Shionoya M

    Journal of the American Chemical Society   Vol. 124 ( 30 ) page: 8802-8803   2002.7

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  113. Syntheses of nucleic acid mimics designed for metal-induced strand formation on DNA

    Akihiko Hatano, Kentaro Tanaka, Motoo Shiro, Mitsuhiko Shionoya

    Tetrahedron   Vol. 58   page: 2965-2972   2002.4

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    This paper describes design and syntheses of a new class of chelator-type nucleic acid mimics. Four nucleic acid mimics 7, 11, 15, 17 possess a nucleobase and two ethylenediamine moieties for intermolecular metal coordination. We expected that chelator-type nucleic acid mimics formed a strand in the presence of metal ion and then interacted with a single-stranded DNA. Efficient synthetic routes leading to the four nucleic acid analogues have been achieved via the key intermediate compound 5 which was derived from 3,5-dimethylphenol in five steps. Compound 7 was treated with zinc nitrate and Zn complex 8 was isolated as crystals.1H NMR study of Zn complex 8 in D2O showed the single-strand formation. Job plots showed that mixture of (dT)70with Zn complex 8 at 5°C reached a minimum absorbance at a mole ratio of 2:1, and the hypochromic effect showed the π-π stacking interaction between the nucleobases. Thermal denaturation study at 2:1 mole ratio of complexes between (dT)70and Zn complex 8 showed melting point at 27°C. © 2002 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0040-4020(02)00203-X

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  114. Toward nano-assembly of metals through engineered DNAs

    Kentaro Tanaka, Motoyuki Tasaka, Honghua Cao, Mitsuhiko Shionoya

    Supramolecular Chemistry   Vol. 14   page: 255-261   2002.1

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    DOI: 10.1080/10610270290026167

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  115. Formation of Silver(I)-Mediated DNA Duplex and Triplex through an Alternative Base Pair of Pyridine Nucleobases Reviewed

    K. Tanaka, Y. Yamada, and M. Shionoya

    J. Am. Chem. Soc.   Vol. 124   page: 8802-8803   2002

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  116. Towards Nano-Assembly of Metals with Engineered DNAs Reviewed

    K. Tanaka, M. Tasaka, H. Cao, and M. Shionoya

    Supramol. Chem.   Vol. 14   page: 255-261   2002

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  117. Syntheses of Nucleic Acid Mimics Designed for Metal-Induced Strand Formation on DNA Reviewed

    A. Hatano, K. Tanaka, M. Shiro and M. Shionoya

    Tetrahedron   Vol. 58   page: 2965-2972   2002

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  118. Synthesis and Structure-Activity Relationships of Nonnatural β-C-Nucleoside Triphosphates Bearing an Aromatic Nucleobase with Phenolic Hydroxyl Groups: Inhibitory Activities against DNA Polymerases Reviewed

    S. Aketani, K. Tanaka, K. Yamamoto, A. Ishihama, H. Cao, A. Tengeiji, S. Hiraoka, M. Shiro, and M. Shionoya

    J. Med. Chem.   Vol. 25   page: 5594-5603   2002

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  119. Spontaneously resolved chiral interpenetrating 3-D nets with two different zinc coordination polymers [7]

    M. Sasa, K. Tanaka, X. H. Bu, M. Shiro, M. Shionoya

    Journal of the American Chemical Society   Vol. 123   page: 10750-10751   2001.10

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    DOI: 10.1021/ja0116324

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  120. Nickel-mediated alcoholysis reaction of carbon-nitrogen triple bond: Structural characterization of an unprecedented moisture stable imido ester with an E-configuration

    Xian He Bu, Miao Du, Kentaro Tanaka, Mitsuhiko Shionoya, Motoo Shiro

    Inorganic Chemistry Communications   Vol. 4   page: 150-152   2001.4

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    The X-ray structural characterization of a moisture stable imido ester with an E-configuration, obtained from the nickel(II)-mediated alcoholysis reaction of the nitrile group of a newly synthesized 6,7-dicyano-2,3-di(2-pyridyl) pyrazine compound (L), is reported. © 2001 Elsevier Science B.V.

    DOI: 10.1016/S1387-7003(01)00147-2

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  121. Novel organic crystals as candidates for frequency up-converted materials: Syntheses and crystal structures of two Tröger's bases

    X. H. Bu, M. Du, L. J. Zhao, K. Tanaka, M. Shionoya, M. Shiro

    Journal of Chemical Research - Part S     page: 243-245   2001.1

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    The syntheses and crystal structures of two novel Tröger's bases as candidates for frequency up-coverted organic materials are reported.

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  122. Spontaneously Resolved Chiral Interpenetrating 3-D Nets with Two Different Zinc Coordination Polymers Reviewed

    M. Sasa, K. Tanaka, M. Shiro, X.-H. Bu, and M. Shionoya

    J. Am. Chem. Soc.   Vol. 123   page: 10750-10751   2001

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  123. A Palladium-Mediated DNA Base Pair of a beta-C-Nucleoside Possessing a 2-Aminophenol as the Nucleobase Reviewed

    M. Tasaka, K. Tanaka, M. Shiro, and M. Shionoya

    Supramol. Chem.   Vol. 13   page: 671-675   2001

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    DOI: 10.1080/10610270108027496

  124. An approach to metal-assisted DNA base pairing: Novel β-C-nucleosides with a 2-aminophenol or a catechol as the nucleobase International journal

    Kentaro Tanaka, Motoyuki Tasaka, Honghua Cao, Mitsuhiko Shionoya

    European Journal of Pharmaceutical Sciences   Vol. 13 ( 1 ) page: 77 - 83   2001

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    The metal-chelating β-C-nucleoside having a phenylenediamine moiety as the nucleobase was previously found to form a stable 2:1 complex with a Pd2+ ion in aqueous media, where hydrogen bonding is replaced by metal coordination in the base pairing, thereby creating a novel hybridization motif in duplex DNA. In this regard, we have further designed two types of artificial β-C-nucleosides possessing a metal-chelating site (a 2-aminophenol or a catechol) as the nucleobase moiety. These artificial nucleosides are directed toward controlling the net charges of the metal-assisted base pairs. This paper describes convenient syntheses of the artificial nucleosides bearing a 2-aminophenol or a catechol moiety. Each nucleoside was directly synthesized through 2′-deoxy derivative via a Friedel-Crafts coupling reaction as the key step between the aromatic ring and ribose moiety, whereas the nucleoside having a phenylenediamine moiety was prepared in rather longer steps through an RNA type intermediate followed by the removal of 2′-hydroxyl group. © 2001 Elsevier Science B.V.

    DOI: 10.1016/S0928-0987(00)00210-4

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  125. A novel polymeric Ag(I) complex consisting of two three-dimensional networks which are enantiometric and interpenetrating

    X. H. Bu, K. Biradha, T. Yamaguchi, M. Nishimura, T. Ito, K. Tanaka, M. Shionoya

    Chemical Communications     page: 1953-1954   2000.10

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    One-pot reaction of AgNO3and a large aromatic bridging ligand, diquinoxalino[2,3-a:2',3'-c]phenazine, which has three bidentate coordination sites, afforded a Ag(I) complex consisting of two independent three-dimensional (3D) networks which are enantiometric and interpenetrating.

    DOI: 10.1039/b003183f

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  126. Synthetic incorporation of metal complexes into nucleic acids and peptides directed toward functionalized molecules

    M. Shionoya, K. Tanaka

    Bulletin of the Chemical Society of Japan   Vol. 73   page: 1945-1954   2000.9

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    Novel synthetic approaches for incorporation of metal complexes into nucleic acids and peptides are described. First, novel artificial β-C-nucleosides bearing a chelator nucleobase (2-aminophenol, catechol, or o-phenylenediamine) have been synthesized. These artificial nucleobases were introduced for alternative base pairing through metal coordination instead of the hydrogen bonding in natural DNA.1HNMR and mass spectral studies clearly showed that o-phenylenediamine-type nucleoside forms a stable 2: 1 square-planar complex with a Pd(II) ion, providing an alternative DNA base pairing through metal complexation. Secondly, an efficient strategy for the liquid-phase synthesis of cyclic metallopeptides having a repeating Gly-L-Cys(terpyPt(II)) sequence, cyclo[-Gly-L-Cys(terpyPt(II))-](n)Cl(n) (n = 3, 4), has been developed. These cyclic metallopeptides were obtained by cyclization of the corresponding linear peptides, H2[-Gly-L-Cys(terpyPt(II))-](n)OH-(CF3CO2)(n+1) (n = 3, 4), in moderate yields. The former cyclic hexapeptide was found to act as a positively charged anion receptor. This synthetic approach would provide a powerful tool for arraying metal centers on cyclopeptide frameworks.

    DOI: 10.1246/bcsj.73.1945

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  127. A spontaneously resolved chiral molecular box: A cyclic tetranuclear Zn(II) complex with DPTZ (DPTZ = 3,6-di-2-pyridyl-1,2,4,5-tetrazine)

    Xian He Bu, Xian He Bu, Xian He Bu, Hiromasa Morishita, Kentaro Tanaka, Kumar Biradha, Sanae Furusho, Mitsuhiko Shionoya

    Chemical Communications     page: 971-972   2000.6

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    A quantitative synthesis of a novel cyclic tetranuclear Zn(II) complex with 3,6-di-2-pyridyl-1,2,4,5-tetrazine (DPTZ), which was spontaneously resolved as chiral crystals, has been developed.

    DOI: 10.1039/a909742b

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  128. An alternative base-pairing of catechol-bearing nucleosides by borate formation

    Honghua Cao, Kentaro Tanaka, Mitsuhiko Shionoya

    Chemical and Pharmaceutical Bulletin   Vol. 48   page: 1745-1748   2000.1

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    A chelator-type β-C-nucteoside having a catechol ligand as the nucleobase was found to form a stable 2 : 1 complex with trimethyl borate, which was characterized by1H-NMR and etectrospray ionization time-of-flight (ESI-TOF) mass speetroseopies. Both phosphoramidite and phosphotriester derivatives of this nueleoside were also prepared as synthetic precursors for DNA oligomer syntheses.

    DOI: 10.1248/cpb.48.1745

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  129. Self-assembly of chelator-type nucleic acid mimics into a single-stranded ZnIIcoordination polymer

    Akihiko Hatano, Kentaro Tanaka, Motoo Shiro, Mitsuhiko Shionoya

    Chemistry Letters     page: 822-823   2000.1

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    The synthesis of a "chelator-type" adenine mimic, which has two metal binding sites, and its ZnII-assisted self-assembly into a single-stranded coordination polymer are described. The UV absorption changes of a 1 : 1 mixture of the ZnIIcomplex and a single-stranded DNA oligomer (dT)70showed the temperature-dependent hyperchromic effect in an analogous manner as thermal denaturation processes of natural DNA duplexes.

    DOI: 10.1246/cl.2000.822

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  130. Cyclic metallopeptides, cyclo[Gly-L-Cys(terpyPt(II))](n)Cl(n)

    Kentaro Tanaka, Kentaro Tanaka, Kazuki Shigemori, Mitsuhiko Shionoya, Mitsuhiko Shionoya

    Chemical Communications     page: 2475-2476   1999.12

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    An efficient strategy for the liquid-phase synthesis of cyclic metallopeptides, cyclo[Gly-L-Cys(terpyPt(II))](n)Cl(n) (n = 3, 4), has been developed, which could provide a powerful tool for arraying metal centers on cyclopeptide frameworks.

    DOI: 10.1039/a906144d

    Scopus

  131. Synthesis of a novel nucleoside for alternative DNA base pairing through metal complexation

    Kentaro Tanaka, Mitsuhiko Shionoya, Mitsuhiko Shionoya

    Journal of Organic Chemistry   Vol. 64   page: 5002-5003   1999.7

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/jo990326u

    Scopus

  132. Artificial DNAs with metal-assisted base pairs.

    K. Tanaka, H. Cao, M. Tasaka, M. Shionoya

    Nucleic acids symposium series     page: 111-112   1999.1

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    Publishing type:Research paper (scientific journal)  

    Two types of artificial beta-C-nucleosides, 2 and 3, were newly synthesized, which possess a metal chelating site (2-aminophenol and catechol, respectively) at the nucleobase moiety. These nucleosides are expected to form metal-assisted base pairs in oligonucleotides and thereby to control high-order structures and functions of DNAs.

    Scopus

    PubMed

  133. Anisotropic electric conductivity in an aligned DNA cast film

    Y. Okahata, T. Kobayashi, K. Tanaka, M. Shimomura

    Journal of the American Chemical Society   Vol. 120   page: 6165-6166   1998.1

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1021/ja980165w

    Scopus

  134. DNA-aligned cast film and its anisotropic electron conductivity International journal

    Y. Okahata, T. Kobayashi, H. Nakayama, K. Tanaka

    Supramolecular Science   Vol. 5 ( 3-4 ) page: 317 - 320   1998

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

    A DNA-lipid cast film was prepared, in which counter cations of DNA phosphates were replaced by cationic amphiphiles. The film is transparent, physically strong, and water-insoluble. DNA strands could be aligned in one direction by stretching the film. The aligned-DNA film showed a large anisotropic and ohmic electric current (10-5 S cm-1, A⊥/A = 104) along DNA strands in the film.

    DOI: 10.1016/S0968-5677(98)00025-X

    Scopus

  135. Oriented thin films of a DNA-lipid complex

    Yoshio Okahata, Kentaro Tanaka

    Thin Solid Films   Vol. 284-285   page: 6-8   1996.9

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    Publishing type:Research paper (scientific journal)  

    Organic thin films in which DNA double strands aligned in one direction were prepared by two methods: 1) polyion complexes of DNA anions and cationic amphiphiles was prepared and the organic solution of the DNA-lipid complex was cast and the obtained transparent film was stretched in one direction, and 2) DNA anions were solubilized in subphase with intercalated dyes and were transferred with cationic lipid monolayers by vertical dipping method. DNA strands could be aligned along stretching direction in the cast film and along dipping direction in the LB film. The orientation of DNA strands in the thin films were confirmed by X-ray diffraction and polarized absorption spectra.

    DOI: 10.1016/S0040-6090(96)08830-X

    Scopus

  136. Orientation of DNA double strands in a Langmuir-Blodgett film

    Yoshio Okahata, Takuya Kobayashi, Kentaro Tanaka

    Langmuir   Vol. 12   page: 1326-1330   1996.3

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    Publishing type:Research paper (scientific journal)  

    A cationic amphiphile monolayer was spread on a subphase containing DNA double strands and intercalating dyes, and the polyion complex DNA/dye/cationic monolayer was transferred to a substrate by the vertical dipping method. It was confirmed by X-ray diffraction patterns and polarized absorption spectra that the dye-intercalated DNA strands were aligned along the dipping direction in the LB film. DNA strands are not aligned in the LB film without intercalating dye molecules. When the DNA-lipid monolayers were deposited by a horizontal lifting method instead of a vertical dipping method, DNA strands were randomly oriented in the film. The orientation of DNAs was decreased when the monolayer packing was decreased by using a low surface pressure or an expanded monolayer. Thus, the rigid, dye-intercalated DNA strands could be oriented during the vertical dipping process.

    Scopus

  137. A DNA-lipid complex in organic media and formation of an aligned cast film

    K. Tanaka, Y. Okahata

    Journal of the American Chemical Society   Vol. 118   page: 10679-10683   1996.1

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    Publishing type:Research paper (scientific journal)  

    A novel DNA-lipid complex is prepared by replacing sodium counter cations by cationic amphiphilic lipids (1). The DNA-lipid complex is insoluble in aqueous solutions, but is soluble in most orgamc media such as benzene, ethanol, and chloroform. The DNA-lipid complex was confirmed to form double helical strands even in organic media, and the internal conformation of DNA strands could be reversibly changed from B-form to C-form in the organic solution (CHCl3/EtOH = 4:1) by changing the water content. A self-standing, water-insoluble DNA-lipid (1) film was prepared by casting from the organic solution and could be stretched to produce oriented DNA strands with their axes aligned along the stretching direction. The film can be impregnated with the drug ethidium bromide in the aqueous solution. The linear dichroism characteristics of the drug-DNA film show that the DNA strands are well oriented and the ethidium molecules are intercalated, as they are in normal aqueous solutions.

    DOI: 10.1021/ja9617855

    Scopus

  138. Evaluation of a Transfer Process for Langmuir-Blodgett Films by Means of a Quartz-Crystal Microbalance

    Yoshio Okahata, Katsuhiko Ariga, Kentaro Tanaka

    Thin Films   Vol. 20   page: 317-329   1995.1

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    Publishing type:Research paper (scientific journal)  

    DOI: 10.1016/B978-0-12-523485-6.50021-3

    Scopus

  139. Quartz Crystal Microbalance and UV-Vis Absorption Study of Q-State CdS Particle Formation in Cadmium Arachidate Langmuir-Blodgett Films

    Robert S. Urquhart, D. Neil Furlong, Herman Mansur, Herman Mansur, Franz Grieser, Franz Grieser, Kentaro Tanaka, Kentaro Tanaka, Yoshio Okahata, Yoshio Okahata

    Langmuir   Vol. 10   page: 899-904   1994.3

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    Publishing type:Research paper (scientific journal)  

    The formation of Q-state CdS particles in cadmium arachidate (CdAr) Langmuir-Blodgett films has been monitored using the quartz crystal microbalance (QCM) and UV-vis absorption measurements. QCM studies showed that the mass uptake of different thickness CdAr films on exposure to hydrogen sulfide was consistent with that expected for the quantitative conversion of Cd2+ ions in the films to CdS and the corresponding conversion of CdAr to arachidic acid. UV-vis absorbance measurements showed an optical blue shift typical of particles between 2 and 3 nm in diameter. Complimentary electron microscopic studies showed a polydisperse size distribution of CdS particles. The most common particle size observed in the electron micrographs was found to be close to the particle size determined from the optical properties of the semiconductor particles. There was a linear relationship between the mass uptake of a film on H2S exposure and changes in its absorption properties due to Q-state particle formation. The linear relationship was used to calculate the optical extinction coefficient of the Q-state particles in the film. Mass uptake measurements on CdAr films extensively exposed to H2S gas showed that the arachidic acid molecules left after Q-state particle formation could be quantitatively converted to CdAr by immersing the film in a stirred aqueous solution containing cadmium chloride. Subsequent reexposure of the film to H2S increased the mole fraction of CdS in the film. © 1994, American Chemical Society. All rights reserved.

    DOI: 10.1021/la00015a047

    Scopus

  140. Size-quantised cadmium sulfide particles in Langmuir-Blodgett films: Film thermal stability

    D. Neil Furlong, Robert Urquhart, Franz Grieser, Franz Grieser, Kentaro Tanaka, Kentaro Tanaka, Yoshio Okahata, Yoshio Okahata

    Journal of the Chemical Society, Faraday Transactions   Vol. 89   page: 2031-2035   1993.12

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    Publishing type:Research paper (scientific journal)  

    The fabrication of particles in Langmuir-Blodgett films of cadmium icosanoate and nonacosa-10,12-diynoate is followed using a quartz crystal microbalance. The mass changes accompanying the exposure of the film to hydrogen sulfide are consistent with a chemical reaction in the film which also produces the acid form of the surfactant. Film thermal stability is greatly reduced after the particles are formed, a result also consistent with formation of the more volatile acid form. The extent of film removal by heating/outgassing suggests that particles are capped by adsorbed icosano or diynoic acid. It is likely that this capping plays a role in particle growth control.

    DOI: 10.1039/FT9938902031

    Scopus

  141. GROWTH OF CDS PARTICLES IN CADMIUM ARACHIDATE FILMS - MONITORING BY SURFACE-PLASMON RESONANCE, UV-VISIBLE ABSORPTION-SPECTROSCOPY, AND QUARTZ-CRYSTAL MICROGRAVIMETRY International journal

    NJ GEDDES, RS URQUHART, DN FURLONG, CR LAWRENCE, K TANAKA, Y OKAHATA

    JOURNAL OF PHYSICAL CHEMISTRY   Vol. 97 ( 51 ) page: 13767 - 13772   1993.12

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

    The growth of Q-state CdS particles during exposure of Langmuir-Blodgett films of cadmium arachidate to hydrogen sulfide has been monitored by surface plasmon resonance (SPR), UV-visible absorption, and quartz crystal microbalance (QCM) measurements. The growth kinetic profile, expressed in terms of increasing refractive index (SPR), absorption or mass increase (QCM), was the same when films were gassed under similar conditions. Microgravimetry showed the quantitative conversion of Cd2+ to CdS in such systems; UV-visible absorption exhibited the blue shift typical of Q-state particles of 2-3-nm diameter. SPR reflectance curves obtained after H2S treatment were initially fitted assuming that either the film thickness or the real component of the relative permittivity (epsilon(r)) was constant during Q-state particle formation. Film thickness changes (assuming epsilon(r) was constant) were similar to those previously reported. Relative permittivity changes, determined assuming the film thickness was constant, indicated that for thinner films (i.e., fewer than about 10 layers) effects such as film breakup during particle;formation and HS exposure to the gold surface of the SPR crystal were important. The change in epsilon(r) for a 20-layer cadmium arachidate film after-extensive gassing was calculated using Maxwell-Garnett theory. Use of this value in the fitting routine indicated that the film thickness change during particle formation was 0.13 nm/layer or 4.9%.

    DOI: 10.1021/j100153a054

    Web of Science

    Scopus

  142. Evaluation of a horizontal lifting method of Langmuir-Blodgett films using a quartz-crystal microbalance

    Y. Okahata, K. Ariga, K. Tanaka

    Thin Solid Films   Vol. 210-211   page: 702-706   1992.4

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    Publishing type:Research paper (scientific journal)  

    A quartz-crystal microbalance (QCM) was employed as a substrate for a horizontal lifting method of various LB films, in which the QCM plate was touched to monolayers on a subphase and lifted horizontally. The transferred mass of monolayers on the QCM could be measured directly at a nanogram level from a frequency decrease of the QCM plate: two monolayers were deposited each cycle (Y-type, transfer ratio 2). The QCM method gave more precise transfer information than the conventional method using the moving area of the barrier on the trough. It was found by the QCM method that Y-type horizontal lifting methods could be widely applied for most monolayers to form well-layered LB films, compared with the conventional vertical dipping method. © 1992.

    DOI: 10.1016/0040-6090(92)90379-P

    Scopus

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Books 24

  1. 理科年表 2024

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2023.11  ( ISBN:978-4-621-30857-8

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    Total pages:1216   Language:Japanese Book type:Dictionary, encyclopedia

  2. 理科年表 2023

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2022.11  ( ISBN:978-4-621-30561-4

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    Total pages:1174   Language:Japanese Book type:Dictionary, encyclopedia

  3. フロンティア・ナノ金属錯体化学

    山下正廣・小西克明・秋吉亮平・芥川智行・有賀克彦・井口弘章・伊藤肇・内田さやか・加藤恵一・川脇徳久・河野慎一郎・日下心平・米田忠弘・澤田知久・陳旻究・七分勇勝・鈴木康介・高石慎也・高野慎二郎・田所誠・田中健太郎・佃達哉・中西亮・中村貴義・根岸雄一・芳賀正明・速水真也・福嶋貴・牧浦理恵・松田亮太郎・山内美穂・山林奨・吉田健文 ( Role: Joint author ,  金属錯体ソフトマテリアル)

    三共出版  2022.7  ( ISBN:4782708017

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    Total pages:435   Responsible for pages:25   Language:Japanese Book type:Scholarly book

  4. 理科年表 2022

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2021.11  ( ISBN:978-4-621-30561-4

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    Total pages:1174   Language:Japanese Book type:Dictionary, encyclopedia

  5. 化学便覧 基礎編 改訂6版

    日本化学会 編( Role: Contributor ,  4.2節「無機化合物・錯体・有機金属・生物無機錯体・超分子化合物の性質」)

    丸善出版  2021.1  ( ISBN:978-4-621-30521-8

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    Total pages:1543   Language:Japanese Book type:Dictionary, encyclopedia

  6. 理科年表 2021

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2020.11  ( ISBN:978-4-621-30561-4

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    Total pages:1174   Language:Japanese Book type:Dictionary, encyclopedia

  7. 理科年表 2020

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2019.11  ( ISBN:978-4621304259

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    Total pages:1162   Language:Japanese Book type:Dictionary, encyclopedia

  8. 錯体化合物辞典

    錯体化学会 編( Role: Contributor)

    朝倉書店  2019.10  ( ISBN:978-4-254-14105-4

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    Total pages:1000   Language:Japanese Book type:Dictionary, encyclopedia

  9. 理科年表 2019

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2018.11  ( ISBN:978-4621303313

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    Total pages:1130   Language:Japanese Book type:Dictionary, encyclopedia

  10. 理科年表 平成30年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2017.11  ( ISBN:978-4621302170

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    Total pages:1118   Language:Japanese Book type:Dictionary, encyclopedia

  11. 理科年表 平成29年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2016.11  ( ISBN:978-4621300954

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    Total pages:1104   Language:Japanese Book type:Dictionary, encyclopedia

  12. 理科年表 平成28年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2015.11  ( ISBN:978-4621089668

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    Total pages:1098   Language:Japanese Book type:Dictionary, encyclopedia

  13. 理科年表 平成27年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2014.11  ( ISBN:978-4621088890

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    Total pages:1092   Language:Japanese Book type:Dictionary, encyclopedia

  14. 理科年表 平成26年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2013.11  ( ISBN:978-4621087381

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    Total pages:1081   Language:Japanese Book type:Dictionary, encyclopedia

  15. 理科年表 平成25年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2012.11  ( ISBN:978-4621086063

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    Total pages:1136   Language:Japanese Book type:Dictionary, encyclopedia

  16. 理科年表 平成24年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2011.11  ( ISBN:978-4621084380

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    Total pages:1072   Language:Japanese Book type:Dictionary, encyclopedia

  17. 理科年表 平成23年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2010.11  ( ISBN:978-4621082928

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    Total pages:1064   Language:Japanese Book type:Dictionary, encyclopedia

  18. 理科年表 平成22年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2009.11  ( ISBN:978-4621081907

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    Total pages:1064   Language:Japanese Book type:Dictionary, encyclopedia

  19. 超分子金属錯体

    ( Role: Contributor ,  DNAを用いた超分子金属錯体)

    三共出版  2009.10  ( ISBN:978-4-7827-0608-4

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    Total pages:413   Language:Japanese Book type:Textbook, survey, introduction

  20. 超分子サイエンス&ナノテクノロジー —基礎からイノベーションまで—

    ( Role: Contributor ,  金属錯体型人工DNAを利用した金属錯体の精密集積)

    エヌ・ティー・エス  2009.5  ( ISBN:978-4-86043-309-3

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    Total pages:1340   Language:Japanese Book type:Textbook, survey, introduction

  21. 理科年表 平成21年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2008.11  ( ISBN:978-4621080467

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    Total pages:1064   Language:Japanese Book type:Dictionary, encyclopedia

  22. 理科年表 平成20年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2007.11  ( ISBN:978-4621079027

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    Total pages:1060   Language:Japanese Book type:Dictionary, encyclopedia

  23. 理科年表 平成19年

    国立天文台 編纂( Role: Contributor ,  高分子化合物 石油製品の比重と沸点)

    丸善出版  2006.11  ( ISBN:978-4621077641

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    Total pages:1056   Language:Japanese Book type:Dictionary, encyclopedia

  24. 図解 高分子新素材のすべて

    ( Role: Contributor ,  DNAの中に金属イオンを並べる)

    工業調査会  2005.5  ( ISBN:4-7693-4189-X

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    Total pages:257   Language:Japanese Book type:General book, introductory book for general audience

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MISC 6

  1. 超分子会合体形成反応を利用した窒素架橋鉄ポルフィリノイド二核錯体型エタン酸化触媒の活性化

    山田泰之, 三原のぞみ, 森田健太郎, 高谷光, 北河康隆, 井川和宣, 友岡克彦, 田中健太郎

    ホスト-ゲスト・超分子化学シンポジウム講演要旨集   Vol. 16th   2018

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  2. 4重ロタキサン構造で連結した鉄ポルフィリン・鉄フタロシアニンヘテロ二量体を利用した電気化学的酸素還元反応

    山田泰之, 三原のぞみ, 高谷光, 北河康隆, 青山慎, 井川和宣, 友岡克彦, 田中健太郎

    電気化学会大会講演要旨集(CD-ROM)   Vol. 84th   2017

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  3. 超分子的に連結したポルフィリン・フタロシアニンスタッキング型鉄二核錯体オキソ種によるメタン酸化活性評価

    森田健太郎, 山田泰之, 三原のぞみ, 高谷光, 北河康隆, 井川和宣, 友岡克彦, 田中健太郎

    錯体化学会討論会講演要旨集   Vol. 67th   2017

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  4. Synthesis of an oxygen-bridged dinuclear complex composed of Fe-porphyrin and Fe-phthalocyanine inside a fourfold rotaxane International journal

    MIHARA Nozomi, YAMADA Yasuyuki, IGAWA Kazunobu, KASHIWAGI Ken, TOMOOKA Katsuhiko, TANAKA Kentaro

    日本化学会講演予稿集   Vol. 95th ( 2 ) page: 547   2015.3

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    Language:English  

    J-GLOBAL

  5. Programmed arraying of metal complexes in a supramolecular system: Stacked assembly of porphyrin and phthalocyanine Invited International journal

    Tanaka, K, Yamada, Y

    Spring-8 Research Frontiers     page: 68 - 69   2013

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    Language:English   Publishing type:Article, review, commentary, editorial, etc. (bulletin of university, research institution)  

  6. Structural change of plastocyanin. Molecular interaction and protein folding International journal

    S Hirota, N Funasaki, Y Fujimoto, H Okumura, N Katagiri, Y Watanabe, J Choi, M Terazima, S Arie, K Tanaka, M Shionoya, T Okajima, T Takabe

    JOURNAL OF INORGANIC BIOCHEMISTRY   Vol. 96 ( 1 ) page: 32 - 32   2003.7

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    Language:English   Publishing type:Research paper, summary (international conference)   Publisher:ELSEVIER SCIENCE INC  

    Web of Science

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Presentations 29

  1. Capturing of Fullerenes with Metal Complexes with Macrocycles Invited International conference

    Kentaro Tanaka

    13th Japan-China Joint Symposium on Metal Cluster Compounds  2024.3.6 

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    Event date: 2024.3

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Venue:Tokyo   Country:Japan  

  2. Capturing of Fullerenes with Macrocyclic Metal Complexes Invited International conference

    Kentaro Tanaka

    The 9th Asian Conference on Coordination Chemistry (ACCC9), 

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    Event date: 2024.2

    Language:English   Presentation type:Oral presentation (keynote)  

    Venue:Bangkok   Country:Thailand  

  3. Intermolecular Communications in Supramolecular Conjugates of porphyrinoides Invited International conference

    Kentaro Tanaka

    The 2nd Asian Conference of Porphyrins & Phthalocyanines and Related Materials  2023.12.4  Hong Kong Baptist University

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    Event date: 2023.12

    Language:English   Presentation type:Oral presentation (invited, special)  

    Venue:Hong Kong Baptist University   Country:Hong Kong  

  4. Molecular Capturing of Fullerenes with Macrocyclic Metal Complexes Invited International conference

    Kentaro Tanaka

    2023 International IRCCS-ILR-IRTG Symposium on “New Horizons of Molecular Functions”  2023.12.1  Nagoya University IRCCS-ILR-IRTG

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    Event date: 2023.12

    Language:English   Presentation type:Oral presentation (invited, special)  

    Venue:Nagoya University   Country:Japan  

  5. Nano Spaces Generated in Supramolecular Assemblies Invited International conference

    Kentaro Tanaka

    Nankai Mini-Symposium on Advanced Functional Materials  2023.10.6 

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    Event date: 2023.10

    Language:English   Presentation type:Oral presentation (keynote)  

    Venue:Nankai University (China)   Country:China  

  6. Highly oriented nanotubular arrays of macrocyclic metal complexes reversibly induced by ethanol adsorption

    Shin- ichiro KAWANO, Hiroki FUNABASHI, Tsubasa KIUCHI, Yuka IKEMOTO, Kohei NEGITA, Shinpei KUSAKA, Ryotaro MATSUDA, Kentaro TANAKA

    2023.9.22 

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    Event date: 2023.9

    Language:English   Presentation type:Oral presentation (general)  

  7. Molecular Capturing of Fullerenes with Macrocyclic Metal Complexes Invited International conference

    Kentaro Tanaka

    INTERNATIONAL CONGRESS ON PURE & APPLIED CHEMISTRY (ICPAC) BALI 2023  2023.9.15 

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    Event date: 2023.9

    Language:English   Presentation type:Oral presentation (invited, special)  

  8. 組織化した分子から生まれる新機能 Invited

    田中健太郎

    錯体化学若手研究会 「錯体化学若手の会夏の学校2023」  2023.8.4  錯体化学若手研究会

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    Event date: 2023.8

    Language:Japanese   Presentation type:Public lecture, seminar, tutorial, course, or other speech  

  9. 分子ピットによるC60の2次元配列

    田中健太郎, 河野慎一郎, 中谷真人, 尾上 順

    光・量子デバイス研究会「機能性材料の創出とSGDsへの応用」  2023.7.16  電気学会SDGsに向けた革新的機能性材料創出に関する光・量子ビーム応用技術調査専門委員会

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    Event date: 2023.7

    Language:Japanese   Presentation type:Oral presentation (general)  

  10. カラムナー液晶性大環状白金(II)ジアセチリド錯体の合成

    植松凌我、河野慎一郎、田中健太郎

    第 8 回 D-マテリアルズ分野融合研究会  2023.4.22 

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    Event date: 2023.4

    Language:English   Presentation type:Oral presentation (general)  

  11. 液晶巨大環状化合物のナノ空間を用いたゲスト分子の配向組織化

    出口淳仁、河野慎一郎、田中健太郎

    第 8 回 D-マテリアルズ分野融合研究会  2023.4.22 

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    Event date: 2023.4

    Language:English   Presentation type:Oral presentation (general)  

  12. アミンペンダント鉄ポルフィリン触媒を利用した高効率光化学 CO2 還 元

    杉村遼哉、山田泰之、田中健太郎

    第 8 回 D-マテリアルズ分野融合研究会  2023.4.22 

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    Event date: 2023.4

    Language:English   Presentation type:Oral presentation (general)  

  13. テトラ(N‒カルバゾリル)ポルフィリン を基にした含窒素π拡張型縮環 ポルフィリン の合成

    松永涼、河野慎一郎、田中健太郎

    第 8 回 D-マテリアルズ分野融合研究会  2023.4.22 

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    Event date: 2023.4

    Language:English   Presentation type:Oral presentation (general)  

  14. μ‒窒素架橋鉄フタロシアニン二量体型メタン酸化触媒上での疎水性反 応場の構築

    宇野佳樹、山田泰之、田中健太郎

    第 8 回 D-マテリアルズ分野融合研究会  2023.4.22 

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    Event date: 2023.4

    Language:English   Presentation type:Oral presentation (general)  

  15. Hierarchical Organization of Metal Complexes International conference

    7th Japan-China Joint Symposium on Metal Cluster Compounds 

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    Event date: 2008.10

    Language:English   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  16. プログラムに基づく金属錯体の階層的組織化

    田中健太郎

    第58回錯体化学討論会 シンポジウム「高分子で魅せる錯体化学」 

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    Event date: 2008.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  17. 生体分子にヒントをもらう“ものづくり”

    田中健太郎

    第88回日本化学会春季年会 特別企画講演「生体機能の理解と制御を目指した生命化学の最前線」 

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    Event date: 2008.3

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  18. 金属錯体の階層的集積プログラミング

    第88回日本化学会春季年会 特別講演「金属錯体によるイノベーション-配位空間から融合分野への新展開」 

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    Event date: 2008.3

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  19. バイオインスパイアード精密分子組織の構築

    田中健太郎

    第4回電気学会バイオマイクロシステム研究会 

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    Event date: 2008.2

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  20. 生体高分子で金属錯体の自己組織化をプログラムする

    田中健太郎

    第57回錯体化学討論会 シンポジウム「金属イオンを含む新しい生体分子の創製と実践的活用」 

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    Event date: 2007.9

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  21. Programmable Meal Array in DNA Duplex International conference

    13th International Conference on Biological Inorganic Chemistry (ICBIC13) 

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    Event date: 2007.8

    Language:English   Presentation type:Oral presentation (invited, special)  

    Besides the biological importance of DNA as storage of genetic information, DNA acts as a smart molecule for programmable self-assembly since it is possible to encode molecular assembled systems using sequences of nucleobases in a designable fashion. We have recently reported a novel metal-mediated base-pairing motif in DNA duplex as an approach based on the replacement of hydrogen-bonded base pairs by metal-mediated ones. 1-3 Herein, we describe discrete metal arrays under the precise programmi

  22. Bio-inspired Programmable Metal Array International conference

    41st IUPAC World Chemistry Congress 

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    Event date: 2007.8

    Language:English   Presentation type:Oral presentation (general)  

    We describe programmable metal arrays under the precise control of “element", “number", “composition" and “sequence" without any distribution via self-assembly into artificial DNAs.

  23. バイオ分子を使って金属錯体の機能をプログラムする

    田中健太郎

    分子研シンポジウム2007 

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    Event date: 2007.6

    Language:Japanese   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  24. Programmable Discrete 1D Array of Metal Complexes on Bio-Inspired Templates

    One-Dimensional Nanostructures for Nanoarchitectonics (ODNN2007) 

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    Event date: 2007.3

    Language:English   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  25. Programmable Self-Assembly of Metal Ions in Artificial DNA International conference

    2006 Osaka Univ./LANL Joint International Workshop on "The Nanoelectronics and Dynamics of DNA 

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    Event date: 2006.8

    Language:English   Presentation type:Oral presentation (invited, special)  

  26. Functional Metal Array in Artificial DNA

    First International Symposium on Chemistry of Coordination Space (ISCCS 2005) 

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    Event date: 2005.11

    Language:English   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  27. Functional Metal Array on Bio-Inspired Templates

    Tokyo Summer School of Frontier Chemistry 2005 

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    Event date: 2005.8

    Language:English   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

  28. Discrete Metal Array in Artificial DNA International conference

    NTU-SNU-UT Tri-Department Chemistry Symposium 2004 

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    Event date: 2004.12

    Language:English   Presentation type:Oral presentation (invited, special)  

  29. Metal-Wire in Artificial DNA

    The 6th International Conference on Nano-Molecular Electronics (ISNME 2004) 

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    Event date: 2004.12

    Language:English   Presentation type:Oral presentation (invited, special)  

    Country:Japan  

▼display all

KAKENHI (Grants-in-Aid for Scientific Research) 33

  1. Liquid-crystalline nano space as novel reaction fields

    Grant number:19H00902  2019.4 - 2022.3

    Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (A)

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\45890000 ( Direct Cost: \35300000 、 Indirect Cost:\10590000 )

  2. Analysis, reaction, and functionalization of isolated molecules using molecular pits organized on substrates

    Grant number:23K17929  2023.6 - 2025.3

    Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Research (Exploratory)

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    Authorship:Principal investigator 

    Grant amount:\6500000 ( Direct Cost: \5000000 、 Indirect Cost:\1500000 )

  3. ナノ-マクロ機能変換場としての液晶性ナノ空間

    Grant number:22H02094  2022.4

    日本学術振興会  科学研究費補助金  基盤研究B

    田中健太郎

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    Authorship:Principal investigator 

    Grant amount:\17420000 ( Direct Cost: \13400000 、 Indirect Cost:\4020000 )

  4. Liquid-Crystallin Nano-Space for Nano-Macro Functional Conversion

    Grant number:22H02094  2022.4 - 2025.3

    Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

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    Authorship:Principal investigator 

    Grant amount:\17420000 ( Direct Cost: \13400000 、 Indirect Cost:\4020000 )

  5. Template synthesis of molecularly well-defined surface modified with nano-rods

    Grant number:19K22199  2019.6 - 2021.3

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

    Tanaka Kentaro

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    Authorship:Principal investigator  Grant type:Competitive

    Grant amount:\6500000 ( Direct Cost: \5000000 、 Indirect Cost:\1500000 )

    Discrete and shape-persistent molecular nanotubes have great potential to be molecular recognition sites, molecular transporters, and nano reactors. In this study, we developed molecular nanotubes which have unique nanospaces to be template for chemical reactions and organized the tubes parallelly to construct novel chemical nanospaces. Macrocyclic molecules were used as the components of the nanotubes and organized through molecular interactions such as metal complexation and p-p interaction. We found that the nanotube was oriented parallelly in a crystal. The obtained nanospace is chiral and anisotropic, and has potential to be a unique molecular container or a template for synthesis of nanorods.

  6. Molecular architecture of molecular spaces through self-assembly

    Grant number:15H02167  2015.4 - 2018.3

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

    Tanaka Kentaro, Yamada Yasuyuki, Kawano Shin-ichiro, Yamada Yasuyuki, Kawano Shin-ichiro

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    Authorship:Principal investigator 

    Grant amount:\44200000 ( Direct Cost: \34000000 、 Indirect Cost:\10200000 )

    The aim of this study was generation of emerging flexible molecular functions through formation of dimentionally-controled discrete or consecutive molecular spaces in molecular assemblies constructed via self-assembly. We have obtained the research findings listed below. 1) Invention of stimuli-responsive spin arrays and molecular reaction fields which were formed by reversible self-assembly reactions. 2) Invention of novel liquid crystals of macrocyclic mesogens. 3) Two-dimensional molecular assemblies to form novel electronic materials and molecular recognition sites. 4) Invention of discrete three-dimensional molecular spaces surrounded by pai-conjugated walls as molecular recognition sites.

  7. Formation of one dimentional metal-organic frameworks toward inter-cellular comunication

    Grant number:15K13656  2015.4 - 2017.3

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

    Tanaka Kentaro, YAMADA Yasuyuki, KAWANO Shin-ichiro, YAMADA Yasuyuki, KAWANO Shin-ichiro

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    Authorship:Principal investigator 

    Grant amount:\3900000 ( Direct Cost: \3000000 、 Indirect Cost:\900000 )

    This research aims construction of "1D MOF" toward connection of multi living cells for formation of communication between them. We synthesized variety of metallomacrocycles and 1D MOF by bridging the macrocycles by bridging metal legands such as DABCO. The structures and ability of gust accommodation were confirmed. These features demonstrate that the 1D MOFs are good candidates for the molecular cannula.

  8. Coordination Programming of Soft Chemical Nanospaces through Hierarchical Organization of Metal Complexes

    Grant number:21108012  2009.7 - 2014.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

    TANAKA Kentaro, YAMADA Yasuyuki, KAWANO Shin-ichiro, YAMADA Yasuyuki, KAWANO Shin-ichiro

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    Authorship:Principal investigator 

    Grant amount:\86190000 ( Direct Cost: \66300000 、 Indirect Cost:\19890000 )

    We are investigating programmable and hierarchical molecular architectures toward generation of chemical and physical properties derived from intermolecular communications. Electronic communication between molecules is sensitive to their relative orientation. Mechanically interlocked supramolecular motives, such as catenanes and rotaxanes, are promising molecular systems to array functionalized building blocks to regulate their precise intermolecular communications, because two or more molecular components are inseparable but their interactions are flexibly convertible in these supramolecular systems. Recently, we have reported a mechanically linked cofacially stacked arrays of a metalloporphyrin and metallophthalocyanine units by formation of a four-fold rotaxane and its switchable spin-spin communication induced by external stimuli.

  9. Programmable Hierarchical Organization of Metal Complexes and Architecture of Functionalized Chemical Nanospaces

    Grant number:20350025  2008 - 2010

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

    TANAKA Kentaro, YAMADA Yasuyuki, YAMADA Yasuyuki

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    Authorship:Principal investigator 

    Grant amount:\19500000 ( Direct Cost: \15000000 、 Indirect Cost:\4500000 )

    This research project aimed to establish strategies to architect hierarchical assemblage of metal complexes and to utilize them as fuctionalized chemical nanospaces. We have achieved to obtain precisely designed assemblies of metal complexes on bioinspired and supramolecular templates and to find switching abilities of their functions such as spin-spin interactions by external stimuli. We have also synthesized novel liquid crystals which are consisted of macro cyclic metal complexes.

  10. 生体高分子をテンプレートとした金属錯体の機能集積

    Grant number:18033012  2006 - 2007

    日本学術振興会  科学研究費助成事業  特定領域研究

    田中 健太郎, 塩谷 光彦, 塩谷 光彦

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    Authorship:Principal investigator 

    Grant amount:\3900000 ( Direct Cost: \3900000 )

    分子と分子の間のコミュニケーションを制御し、複合的な機能を生み出すためには、分子間の空間的な相対配置をデザインどおり精密に分子組織を構築することが必要である。本研究では、金属配位子を導入したヌクレオシドやアミノ酸を用い、DNAやペプチドの高次構造中で、金属錯体の精密集積化について検討を行った。今まで、DNA二重鎖間の分子認識や会合力を担う核酸塩基間の水素結合を金属配位結合に置き換えた、金属錯体型人工DNAを構築してきた。人工DNAをテンプレートとした異種金属イオンの集積プログラミングを行った。また、DNAと同様に、ペプチドも一次元的な配列構造と三次元的な空間配置がデザインしやすいため、金属錯体の集積プログラミングに適したモチーフである。結晶中で生じることが知られている一次元型のハロゲン架橋白金錯体ワイヤーを溶液中、ディスクリートな形で生成する方法論を見いだした。これらの方法論は、様々な数、様々なシークエンス、様々な配位子にも有効であり、精密な金属錯体配列化の方法論として有用である。このような階層的な分子構築を行うことにより、将来的に電子的な相互作用や複合的な反応性を分子や分子集合体の中に精密にプログラムすることができるようになると期待される。

  11. Creation of Metal-mediated Nanolink Supramolecules

    Grant number:17069010  2005 - 2009

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research on Priority Areas

    SHIONOYA Mitsuhiko, TANAKA Kentaro, HIRAOKA Shuichi, TASHIRO Shohei, UBE Hitoshi, TAKEZAWA Yusuke, TANAKA Kentaro, HIRAOKA Shuichi, TASHIRO Shohei, UBE Hitoshi, TAKEZAWA Yusuke

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    Authorship:Collaborating Investigator(s) (not designated on Grant-in-Aid) 

    This study aimed at creation of metal-mediated nanolink supramolecules that shows specific chemical and physical properties and dynamic functions on the surface of a solid. As the As the result, a method of conduction measurement in artificial metallo-DNA linking carbon nanotube electrodes, an arrangement of Magnus'-type metal stacks in a molecular cage, a synthetic method of metal wire using an oxime-type macrocycle have been established. These findings show that such supramolecular metal complexes are useful for nanolink molecules as key materials.

  12. 走査型プローブ顕微鏡を用いた多種官能基の電気化学ナノパターニングと機能的分子集積

    Grant number:17655058  2005 - 2006

    日本学術振興会  科学研究費助成事業  萌芽研究

    田中 健太郎, 塩谷 光彦, 塩谷 光彦

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    Authorship:Principal investigator 

    Grant amount:\3300000 ( Direct Cost: \3300000 )

    シリコン基板上の有機単分子膜の構造・物性を制御することは、リソグラフィーや半導体産業などへの応用の観点から、今日まで広く研究されている。末端アルケンを用い、水素終端したシリコン(111)表面(H-Si(111))上にハイドロシリレーションによって作成した有機単分子膜は、(1)H-Si(111)の表面構造が原子レベルで規則的であること、(2)基板と有機分子がSi-C共有結合によって固定されることから、単分子膜の反応性と配向性がSi(111)の単結晶構造と有機分子の骨格構造の相関性に大きく影響されると考えられる。本研究では、ジアルキル型単分子膜2C18が、結晶性の非常に高い単分子膜を形成することを見出した。また、その結晶性の高さから、Si基板上で1層だけの有機単分子膜が安定な絶縁層となることを見出した。今後、有機FETなどの構築へ向けて検討を行う。

  13. 生体高分子をテンプレートとした金属錯体の機能集積

    Grant number:17036011  2005

    日本学術振興会  科学研究費助成事業  特定領域研究

    田中 健太郎, 塩谷 光彦, 塩谷 光彦

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    Authorship:Principal investigator 

    Grant amount:\1500000 ( Direct Cost: \1500000 )

    異種金属錯体の空間配置選択的な集積化を目指し、メチオニンとアラニンの交互配列からなる環状ヘキサペプチドcyclo(L-Ala-L-Met)_3(1)をデザインした。この環状ペプチドは、C_3対照な構造上に、側鎖としてソフトな金属配位子であるチオエーテル基を、主鎖にハードな金属配位子であるカルボニル基を持ち、異なる種類の金属イオンの位置特異的な集積化が期待できる。詳細な^1H-NMRスペクトルおよびESI-TOFマススペクトルの測定、結晶構造解析により、環状ペプチド1はダイマーを形成しながら、3つのAg^+イオン、1つのCa^<2+>イオンと定量的に相互作用し、カプセル型四核錯体(2:1-Ag^+-Ca^<2+>=2:3:1)を形成することが明らかとなった。
    一方我々は、DNA核酸塩基間の水素結合を基にした二重鎖の分子認識や会合力を金属錯形成に置き換えた人工DNAを報告してきた。金属錯体型人工DNAを用いることにより、金属錯体の精密集積化を行った。DNA二重鎖中にプログラムした金属配位子の配列をテンプレートに、金属錯体を集積化することが期待できる。ヒドロキシピリドン型ヌクレオシド(H)とピリジン型ヌクレオシド(P)を配列化した人工DNA二重鎖d(GHPHC)_2およびd(GHHPHHC)_2を合成し、金属イオンの集積化を行った。HはCu^<2+>イオンと平面四配位型錯体を形成し、またPはHg^<2+>と直線二配位構造を形成することにより、それぞれ定量的かつ位置選択的にH-Cu^<2+>-H、P-Hg^<2+>-P塩基対を形成した。
    以上のように、人工バイオ分子が複数種の金属錯体の精密集積場となることが明らかとなった。

  14. Programming Spatial Arrangements and Specific Dynamic Function of Metal Complexes using Artificial Ligands with Multi-Binding Sites

    Grant number:16105001  2004 - 2008

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

    SHIONOYA Mitsuhiko, TANAKA Kentaro, HIRAOKA Shuichi, TASHRO Shohei, SHIRO Motoo, KATO Tatsuhisa, KIMURA Eiichi, UBE Hitoshi, TANAKA Kentaro, HIRAOKA Shuichi, TASHRO Shohei, SHIRO Motoo, KATO Tatsuhisa, KIMURA Eiichi, UBE Hitoshi

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    Authorship:Coinvestigator(s) 

    In this study, we have synthesized a variety of functional metal complexes with the aid of bio-inspired and completely artificial ligands with multi-binding sites which include precisely programmed information on the spatial arrangements of metals, and explored specific properties and dynamic functions based on the modes of metal arrays. As the result, heterologous metal arrays using artificial DNA, nanocapsules with dynamic functions, and molecular motional devices such as molecular ball bearings and a molecular crank mechanism have been successfully constructed.

  15. 生体高分子をモティーフとした金属錯体集積場の構築と動的機能発現

    Grant number:16685006  2004 - 2006

    日本学術振興会  科学研究費助成事業  若手研究(A)

    田中 健太郎

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    Authorship:Principal investigator 

    Grant amount:\30420000 ( Direct Cost: \23400000 、 Indirect Cost:\7020000 )

    高分子に通じる合成方法を用い、機能性ビルディングブロックを「数」、「組成」、「配列」、「空間配置」において分布なく集積する手法の開発は、ファインな分子機能の創製だけでなく、新しい物性の発見にもつながりうる。DNAやペプチドなどの生体高分子は、ビルディングブロックであるアミノ酸を逐次、縮合反応により連結していくため、デザインした「長さ」、「配列」を持つ生体高分子を合成することができる。本研究では、人工DNAをテンプレートとした異種金属イオンの集積プログラミングを行った。金属イオンのハード・ソフト、配置数、配置構造、電荷の違いを利用し、人工ヌクレオシドと金属イオンの結合特性を選択することができる。よって、DNAの合成手法を用いることにより、DNA二重鎖中に金属イオンの配列をプログラムすることができる。まず、ヒドロキシピリドン型ヌクレオシド(H)とピリジン型ヌクレオシド(P)を配列化した人工DNA二重鎖、d(GHPHC)_2を合成し、金属イオンの集積化を行った。吸収スペクトルやCDスペクトルによる滴定実験、マススペクトル測定によって、HがCu^<2+>イオンと平面四配位型H-Cu^<2+>-H塩基対を、またPがHg^<2+>と直線二配位構造P-Hg^<2+>-P塩基対を形成し、定量的かつ位置選択的に金属イオンアレイ(Cu^<2+>-Hg^<2+>-Cu^<2+>)を形成できることが明らかとなった。この方法論を拡張することにより、人工DNA内で5-10個の金属イオンの配列を自在に構築することができた。この方法は人工DNA鎖と金属イオンを水溶液中で混合するだけで、分子量、配列に分布を持たない、ディスクリートな集積型金属錯体を構築することが特徴であるので、金属錯体間の機能コミュニケーションを制御する場として、将来的な応用を目指す。

  16. Creation of structures and functions of artificial DNAs directed towards nano-assembly of metal complexes

    Grant number:14340206  2002 - 2003

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

    SHIONOYA Mitsuhiko, HIRAOKA Shuich, TANAKA Kentaro, HIRAOKA Shuich, TANAKA Kentaro

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    Authorship:Coinvestigator(s) 

    The strategy of replacing DNA natural bases by alternative ones has allowed the modification of DNA in a highly specific and site-selective manner, because DNA has a structural basis to array predesigned building blocks. We have recently envisioned the replacement of hydrogen-bonded base pairing present in natural DNA by metalmediated base pairing. Incorporation of such metal-induced base pairs into DNA would not only affect the assembly-disassembly processes and the structure of DNA double strands but also confer a variety of metal-based functions upon DNA. The chemistry thus interfaces with both life sciences and materials science
    Along this line, we designed and synthesized metal-mediated base pairs with nucleosides bearing a phenylenediamine, a catechol, a 2-aminophenol, a pyridine, or a hydroxypyridone as the nucleobase. Some of them were successfully incorporated into DNA and were found to stabilize the duplex or triplex structures. Recently, we reported the synthesis of a series of artificial oligonucleotides, d(5 -GH_nC-3 ) (n = 1-5), using hydroxypyridone nucleobases (H) as flat bidentate ligands. Right-handed double helices of the oligonucleotides, nCu^<2+> d(5 -GH_nC-3 )_2 (n = 1-5), were quantitatively formed through Cu^<2+>-mediated alternative base pairing (H-Cu^<2+>-H), where the Cu^<2+> incorporated into each complex were aligned along the helix axes inside the duplexes with the Cu^<2+>-Cu^<2+> of 3.7 -0.1 angstrom. The Cu^<2+> ions were coupled ferromagnetically with one another through unpaired d electrons to form magnetic chains.

  17. DNA塩基配列情報に基づく金属イオン誘起型分子集積

    Grant number:14654120  2002 - 2003

    日本学術振興会  科学研究費助成事業  萌芽研究

    塩谷 光彦, 平岡 秀一, 田中 健太郎, 平岡 秀一, 田中 健太郎

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    金属イオン誘起型分子集積のモデルとして、任意の一本鎖鋳型DNAに対して、四つの核酸塩基型ビルディングブロックが、水素結合による塩基対形成と金属錯生成による主鎖形成により相補的に集積する系を構築することを目的とした。具体的には、DNAの主鎖のリン酸ジエステル結合を金属配位結合にし、可逆的に主鎖を形成するシステムを考えた。まず、3'-位と5'-位の水酸基をチオール基に変換したチミジンおよびアデノシンを合成した。天然のチミジンを原料とし、官能基変換を行い、NMR、Mass、X線構造解析などにより、最終化合物の構造を確認した。アデノシン型人工ヌクレオシドの合成は、チミジン型の共通合成中間体を経る塩基交換反応により効率よく行った。鋳型DNAのある場合とない場合の種々の金属イオンとの錯形成をNMRおよび紫外吸収スペクトルなどを用いて検討した。その結果、鋳型DNAのない場合は、金属イオンと人工ヌクレオシドが2:2で安定な錯体を形成するが、配位子交換を経て、オリゴマー構造を形成することがわかってきた。また、鋳型DNAが存在する場合は、核酸塩基間の水素結合形成が確認されたが、まだ、期待している二重鎖構造ができているかどうかは明らかになっていない。また、3'-位と5'-位が同じ単座配位子の場合、3'-位と5'-位の向きを制御することは困難であることがわかった。そこで、3'-位を三座配位子に変換したものを合成し、3'-位と5'-位の配位子が一つの金属イオンに結合できるような人工ヌクレオシドをデザイン・合成した。

  18. 人工DNAを用いる超分子レドックスシステムの構築

    Grant number:13128202  2001 - 2003

    日本学術振興会  科学研究費助成事業  特定領域研究

    塩谷 光彦, 平岡 秀一, 田中 健太郎, 平岡 秀一, 田中 健太郎

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    本研究では、金属錯体型人工DNAを用いて、レドックス活性金属イオンの空間配列を設計・合成し、新しい構造・機能を創出し実用化を図ることを目的とした。DNAは遺伝情報を司る生体高分子であるが、我々はその分子構造を基に新しい機能性分子を創製する研究を行っている。まず、核酸塩基を金属配位子に置き換えた数種の人工DNAを化学的に合成した。これらの人工DNAは、水素結合の代わりに金属イオンと錯体をつくることにより塩基対を形成して、二重らせん構造となる。これらの人工DNAは、二重らせんの中心に、「数」と「順序」を制御して金属イオンを配列化する場として優れている。例えば、ヒドロキシピリドンを核酸塩基として用いた人工DNAの中心に、磁性をもつCu^<2+>イオンを思いどおりに1〜5個、一次元的に並べることを吸収スペクトルによる滴定実験により明らかにした。CDスペクトルによる滴定実験より、これらの銅錯体は右巻きの二重らせん構造であることが推察された。二重らせん構造の中でCu^<2+>イオンは平面四配位型をとり、Cu^<2+>-Cu^<2+>間約3.7オングストロームの距離でスタッキングしている。また、Cu^<2+>イオン間には強磁性的な相互作用がみられ、Cu^<2+>イオンの数に応じてスピン量子数が系統的に変化することをEPR測定により明らかにした。現在は、これらの結果を踏まえて、複数種の人工核酸塩基を用いて、異種金属イオンの配列化を検討している。

  19. 一本鎖DNAをテンプレートにした金属錯体の機能的集積化

    Grant number:13031018  2001 - 2002

    日本学術振興会  科学研究費助成事業  特定領域研究(A)

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    本研究は、金属イオン誘起型人工DNAを用いて、鋳型DNAの分子情報を転写する手法を確立し、新しい分子情報伝達システムを創出することを目的としている。具体的には、一つの核酸塩基と二つの金属配位部分を有する四つのビルディングブロックが金属錯形成により主鎖を形成するような人工DNAを合成した。4種類の天然型核酸塩基のいずれか一つと二つの金属結合部位を分子内にもつ4種類の構造ユニット(A, T, C, Gに対応)を数工程で合成し、これらのうちアデニン誘導体がZn^<II>イオンとの錯形成を介し、一次元鎖状構造を形成することをX線構造解析により明らかにした。このZn^<II>鎖状錯体と、チミンオリゴマーである(dT)_<70>との相互作用を融解実験で調べたところ、天然型DNAと同様に260nmの吸収に淡色効果が見られ、二本の鎖がハイブリッドしていることが示唆された。次のアプローチとして、天然型ヌクレオシドにより近い構造をもつ金属配位型人工ヌクレオシドを検討している。まず、チミジンの3'-と5'-水酸基をアミノ基、チオール基、メチルチオ基に変換したものを合成した。また、これらの合成中間体の塩基交換反応により、アデニン誘導体に変換できることも見出した。二つの置換活性な配位座をもった白金錯体やパラジウム錯体の存在下、これらが一本鎖鋳型DNA(例えば、polydA)上でどのように配列するかについて現在検討している。これらのシステムを、メッセンジャーRNAをターゲットとする新アンチセンス法や、鋳型DNAのもつ分子情報の転写などに展開する予定である。
    l

  20. Construction of Molecular Devise using Metal Complex-type Artificial DNA 60187333

    Grant number:13554024  2001 - 2002

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

    TANAKA Kentaro, ASAO Tetsuji, HIRAOKA Shuichi, ASAO Tetsuji, HIRAOKA Shuichi

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    DNA has a structural basis to array functionalized building blocks. In this study, one to five Cu^<2+>-mediated base pairs of hydroxypyridone nucleobases have been systematically incorporated into the middle of a DNA duplex, resulting in the formation of a magnetic chain by the line-up of mono- to pentanuclear Cu^<2+> complexes stacked within the DNA helix. The Cu^<2+> ions in each complex couple ferromagnetically with one another through unpaired d electrons. An outline of a right-handed, double-stranded structure with Cu^<2+> array inside the DNA is proposed, where the Cu^<2+>-Cu^<2+> distance is almost the same as that between natural base pairs. This strategy represents a new method for arranging metal ions in solution in a discrete and predictable fashion and contrasts with the non-biological approach of others, leading to the possibility of metal-based molecular devices such as molecular magnets and wires.

  21. アキラルな配位子を用いた集積型金属錯体による不斉空間の構築

    Grant number:12874081  2000 - 2002

    日本学術振興会  科学研究費助成事業  萌芽的研究

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    金属イオンと配位子の間に形成される結合は、それぞれ特有の方向、強さ、交換速度をもっており、分子の集合体をコントロールするための有用な構成要素になる。DNAやタンパク質のような生体高分子や、目的に合わせてデザインした有機分子を、鋳型分子や架橋配位子として用いることにより、金属特有の分子集合体をつくる研究を進めた。本年度は、自然分晶する環状亜鉛四核錯体、ホモキラルな二つの三次元ネットワークが相互貫入した銀錯体、化学組成の異なるホモキラルな二つの三次元ネットワークが相互貫入した亜鉛錯体の合成に成功した。最後の例は、二つの3次元(3D)ネットが相互に貫入した構造をもち、相互貫入型金属錯体で自然分晶した最初の例である。120_iの角度で結合した二つのpyhdyl基を有する二座配位子、2, 4-di(4-pyhdyl)-1, 3, 5-triazine(DPT)、とZn(II)により異なる化学組成を持つ二つのキラルな三次元ネットワークが相互に貫入した構造を生じることがX線結晶構造解析より明らかとなった。この構造はCd(II)の場合も同様であったが、Co(II)やNi(II)などの場合は、ジグザクの一次元ポリマー錯体であった。今後、DNAやタンパク質のような生体高分子を鋳型にしたときの、錯形成について検討する予定である。これらの結果は偶然見い出されたものだが,得られた知見をもとに一般性を高めることが今後の課題である。

  22. 金属錯生成で二重鎖を形成する人工DNAの創製

    Grant number:12740357  2000 - 2002

    日本学術振興会  科学研究費助成事業  奨励研究(A)

    田中 健太郎

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    Grant amount:\2200000 ( Direct Cost: \2200000 )

    本研究では、新しい機能性分子の創製を目的とし、遺伝情報を司る生体高分子であるDNAの核酸塩基間の水素結合を基にした二重鎖の分子認識や会合力、または主鎖の形成を、金属錯形成に置き換えた人工DNAの構築を行った。このような人工DNAは金属イオンの存在下、二重鎖が会合し、DNA内へ金属イオンを固定化することが可能である。金属錯体は結合角などの幾何学的性質や、結合の動力学や熱力学、また、光学的、酸化還元的、磁気的な特性が通常の有機化合物とは大きく異なるため、核酸に金属錯体を導入することにより新しい機能性分子としての人工DNAの構築が期待できる。
    天然の核酸塩基の代わりに金属配位子(o-フェニレンジアミン、カテコール、2-アミノフェノール、ピリジン、ヒドロキシピリドンなど)を導入することにより、水素結合ではなく、金属イオンとの錯生成をとおして塩基対を形成する人エヌクレオシドを合成した。ピリジンやヒドロキシピリドンを核酸塩基としたヌクレオチドをDNAシークエンス中に導入した場合、人工塩基対に対し1当量のAg(I)やCu(II)イオンを加えることにより、金属錯体型塩基対を形成し、DNA二重鎖解離温度が上昇した。このような二重らせん構造の熱的安定化は天然型DNAには見られないことから、これらの人工DNAは、外部因子によりDNA二重鎖構造を制御する方法論となりうる。金属錯体型塩基対を有する人工DNAは、DNAの遺伝情報を担うアルファベットの拡張といった可能性を有しているとともに、DNA骨格を利用した金属イオンの集積場として機能性分子への応用にも興味が持たれる。

  23. Controlled Metal Assembly in Metal Chelator-type Artificial DNAs

    Grant number:12440185  2000 - 2001

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

    SHIONOYA Mitsuhikko, TANAK Kentaro, TANAK Kentaro

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    The purpose of this work is to construct artificial DNAs directed tow ard gene control and functonalized molecules in which hydrogen-bonded base pairs are replaced by metal coordinative base pairs. In this research, we developed the synthesis of hydroxypyridone-type nucledside and examined its Cu(11)-mediated base pairing by ESI-TOF mass spectrometry and absorption tech niques. In addition, its phosphoroamidite derivative was prepared and furth ermore introduced into the middle or the terminal of oligoduplexes by the automatic DMA synthesizer. The structures of these oligomers were confirmed by MAIDI-TOF mass spectrometry. It was found by the melting experiment that Cu(ll)-mediated base pairs introduced inside the DMA stabilized the therma stability of the duplexes. The hydroxypyridone itself hardly binds to Cu(ll) ion under this condition, that is, in the range of micro mol order of cone entration and at pH 7. Thus Cu(ll)-mediated base pair is formed only when hydroxypyridone base pair is incorporated into DMA oligomers under this condition. That is, the single-stranded oligomer bearing hydroxypyridone can be regarded as a very large ligand for metal ions, and forms much more stable Cu(ll) complex in the hydrophobia environment with the aid of multi-point hydrogen bonding and π-π stacking interactions between thewo strands. We now trying to incorporate more than two metal-mediated base pairs into DNA oligomers toward nano-assembly of metals and gene regulation.

  24. キラルな生体分子やアキラルな配分子を用いる金属錯体の不斉集積化

    Grant number:12023209  2000 - 2001

    日本学術振興会  科学研究費助成事業  特定領域研究(A)

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    本研究は、キラルな生体分子やアキラルな配位子と金属イオンの集積化により、不斉分子認識や不斉誘導を可能にする不斉空間を構築し、自然界にない新しい構造・機能(生物学的機能、機能性素子等)を創出することを目的とし、以下の知見を見いだした。
    1.金属錯体を基盤とした金属配位型ヌクレオシドの簡易合成法、および天然型DNAへの導入法を確立することに成功した。
    2.特に目的に合わせた金属イオンの空間配列を設計できると考え、人工核酸を導入した一本鎖DNAおよび二重鎖DNAの金属イオンにる会合を検討した。
    3.アキラルな配位子と亜鉛イオンや銀イオンを用いて、不斉を有する環状錯体(環状構造や相互嵌入型三次元高分子錯体)を作成し、新しい不斉空間を構築した。
    以上をもとに、キラルな生体分子やアキラルな配位子と金属イオンの集積化により、不斉空間を構築する一般的な方法を検討した。

  25. 生体分子と金属錯体の構造融合による集積型機能性金属錯体の創製

    Grant number:11136255  1999

    日本学術振興会  科学研究費助成事業  特定領域研究(A)

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    1.側鎖に金属錯体を有する環状ペプチド
    グリシンと、金属配位能を有するチオール基をもつL-システインの繰返し配列を持つ、環状ペプチド金属錯体cyclo[L-Cys(terpyPt)Gly]_n (n=3-5)の合成法を確立した。金属錯体部分は、酸あるいは金属イオンの処理により。容易に除去できることがわかった。これらの成果を1報の学術論文に発表した。これらがアニオン性高分子であるDNAに強く結合することが、円二色性スペクトルやNMRの測定により明らかになった。相互作用様式について、現在検討中である。
    2.自然分晶する亜鉛四核錯体
    二つのビピリジン部分をもつDPTZと亜鉛イオンから、亜鉛四核錯体がほぼ定量的に得られた。X線結晶解析より、それぞれの単結晶は自然分晶しており、4つの亜鉛中心はall-∧かall一Δであることが明らかにされた。四角構造の内孔に取り込まれている過塩素酸イオンは、四核集積化における鋳型の役割を果たしている。これらの結果については、論文投稿中である。
    3.二つの3次元鏡像型銀錯体のinterpenetrating
    三つのビピリジン部分をもつ平面型芳香族配位子を用いて、二つの3次元構造がinterpenetratingした珍しい構造の銀錯体を一段階で定量的に合成することに成功した。二つの3次元構造は、幾何学的には同等だが、お互いに鏡像体の関係にある。これらの結果については、論文投稿中である。

  26. 生体分子の再構築による遺伝子発現制御法の開発

    Grant number:11116230  1999

    日本学術振興会  科学研究費助成事業  特定領域研究(A)

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    1.金属イオンにより塩基対を形成する人工DNA
    金属イオンと四配位型2:1錯体あるいは六配位型3:1錯体を形成することが可能なο-phenylenediamine,catechol,ο-aminophenolを導入した3種の人工β-C-ヌクレオシドを合成した。これら3種類のヌクレオシドは、パラジウムなどの金属イオンと2:1錯体を形成し、それぞれ異なる電荷数をもつ塩基対をつくることが確認された。また、catech01型ヌクレオシドを種々の配列をもつDNAオリゴマーに組込み、これらの金属イオンにより誘起される二重鎖形成について検討した。
    2.集積型金属錯体によるアンチセンス法の開発
    4種の天然型核酸塩基のいずれか一つと二つの金属配位部分をもつ化合物を合成し、これらがZn^<11>イオンとの錯形成を介し、鎖状構造をつくることをX線結晶解析より明らかにした。これらは、DNAのリン酸ジエステル結合を金属錯体で置換した人工の一本鎖DNAと見なせる。例えば、アデニン部分をもつ化合物とZn^<11>との鎖状錯体は、相補的なチミンのオリゴマーである(dT)_<70>とお互いにハイブリッドしていることが示唆された。
    3.側鎖に金属錯体を有する環状ペプチドとDNA結合能
    グリシンと、金属配位能を有するチオール基をもつL-システインの繰返し配列を持つ、環状ペプチド金属錯体cyclo[L-Cys(terpyPt)Gly]_n(n=3-5)の合成法を確立した。これらがアニオン性高分子であるDNAに強く結合することが、円二色性スペクトルやNMRの測定により明らかになった。相互作用様式について、現在検討中である。

  27. 生体機能のコントロールを目指した金属イオン誘起型人工核酸の合成と機能化

    Grant number:10877374  1998 - 1999

    日本学術振興会  科学研究費助成事業  萌芽的研究

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    金属配位子を核酸塩基に人工的に導入することにより、DNAの高次構造を任意にデザインすることが可能であると考えられる。本研究では、天然の核酸塩基の代わりに金属配位型塩基を導入し、水素結合の代わりに金属錯生成を通して二重らせん構造を形成することが期待される人工DNAを合成することを目的とする。中心金属イオンの酸化還元等に伴うDNA全体の大きな構造変化を通して、転写等の生体機能を人為的にコントロールできると期待された。平成11年度は錯体型人工ヌクレオシドの設計、合成と、合成DNAの基本的な構造、物性評価に重点を置いた。まず、金属イオンと四配位型2:1錯体あるいは六配位型3:1錯体を形成することが可能なo-phenylenediamine,catechol,o-aminophenolを導入した3種の人工β-C-ヌクレオシドを合成した。o-phenylenediamine部分を有するヌクレオシドは、リチオ化物のリボノラクトンへの付加を鍵反応とする、RNA型リボヌクレオシド経由のルートにより合成した。また、catecholやo-aminophenolを有するヌクレオシドについては、ルイス酸を用いるFriedel-Crafts型反応を経由し、直接デオキシリボヌクレオシド体へ導いた。これらの研究成果を2報の学術論文に発表した。これらと各種金属イオンとの溶液内錯生成の検討を行った結果、例えば、パラジウムイオンと2:1平面4配位型錯体を形成することがわかった。また、catechol型を組み込んだ人工DNAオリゴマーをフォスフォロアミダイト法により作成し、現在、金属イオンとの錯形成による二重らせん構造についての評価を行なっている。

  28. DNAと金属錯体の構造融合による集積型機能性金属錯体の創製

    Grant number:10149260  1998

    日本学術振興会  科学研究費助成事業  特定領域研究(A)

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    DNAは核酸塩基間の相補的な水素結合により二本の鎖が特異的に会合し、塩基対間のスタッキングにより二重らせん構造を形成する。この水素結合による会合力を他の力に置き換えることにより、どのような機能の発現が期待できるだろうか。本年度は、金属錯生成を通して二本鎖構造を形成する人工DNAのビルディングブロックとなる3種のキレート型人工ヌクレオシドの合成を行った。具体的には、金属イオンと平面四配位型錯体を形成することが可能なフェニレンジアミン、アミノフェノール、カテコールを導入した3種の人工β-Cヌクレオシドを合成した。この人工ヌクレオシドは水素結合の代わりに金属錯形成により塩基対を形成することができる。例えば、フェニレンジアミンヌクレオシドと硝酸パラジウムとの錯形成をNMRおよびESIマススペクトルで調べた結果、ヌクレオシドとパラジウムが中性水中で安定な2:1錯体を形成することがわかった。現在、これらを用いたオリゴヌクレオチドを合成すべく、アミダイト法を使う自動合成、およびトリエステル法を使うバッチ合成を行っている。今後、この人工DNAの機能性材料への応用や遺伝子の人工コントロールへの応用を検討する。

  29. 核酸の特定部位を標的とする新規金属錯体の合成と機能解析

    Grant number:10169262  1998

    日本学術振興会  科学研究費助成事業  特定領域研究(A)

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    本年度は、(1)金属錯生成を通して二本鎖構造を形成する人工DNAのビルディングブロックとなる3種のキレート型人エヌクレオシドの合成、(2)機能性金属錯体を周囲に配列した大環状ペプチド金属錯体の合成を行った。前者については、金属錯生成を通して二本鎖構造を形成する人工DNAの創製を目的として、金属イオンと錯体を形成するo-phenylenediamine,o-aminophenol,catecholを導入した3種の人工β-C-ヌクレオシドを合成した。この人工ヌクレオシドは水素結合の代わりに金属錯形成により塩基対を形成することができる。例えば、フェニレンジアミン型ヌクレオシドと硝酸パラジウムとの錯形成をNMRおよびESIマススペクトルで調べた結果、ヌクレオシドとパラジウムが中性水中で安定な2:1錯体を形成することがわかった。現在、これらを用いたオリゴヌクレオチドを合成すべく、アミダイト法を使う自動合成、およびトリエステル法を使うバッチ合成を行っている。後者については、ペプチドを基盤とする分子認識素子を創製することを目的として、グリシンと、金属キレート能を有するチオール残基をもつシステインの繰り返し配列を持った、大環状ペプチド金属錯体(cyclo[L-Cys(terpyPt)Gly]_3およびcyclo[L-Cys(terpyPt)Gly]_4)の合成法を確立し、それらのアニオン捕捉能を種々の分光学的手法により明らかにした。これらは、アニオン性高分子であるDNAと相互作用をもつことが円二色性スペクトルやNMRの測定で明らかになった。現在、大環状ペプチド金属錯体の結晶構造やDNAとの相互作用について検討している。

  30. 核酸の特定部位を標的とする新規金属錯体の合成と機能解析

    Grant number:09273251  1997

    日本学術振興会  科学研究費助成事業  重点領域研究

    塩谷 光彦, 田中 健太郎, 田中 健太郎

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    遺伝子発現調節領域や染色体末端テロメアDNAを標的とする金属錯体:DNAのT塩基に選択的に結合する亜鉛錯体が、転写調節領域のATクラスター部位の二本鎖構造を不安定化することを見出した。また、大環状テルビウム錯体がテロメアDNAに結合し、蛍光を発することを見出した。制ガン剤開発と関連してテロメラーゼ活性について検討中である。
    金属錯形成により自発的に集積する人工DNA:金属錯形成や芳香環スタッキングにより一本鎖鋳型DNA上に自発的に集まることが期待される核酸モノマー4種類を合成した。現在、核酸モノマーが一本鎖DNA上に相補的に配列するかどうかを調べている。
    金属配位型核酸塩基を構成ユニットにもつ人工DNA:天然核酸塩基の代わりに金属配位子を有し、金属錯生成により二本鎖をつくる人工DNAを合成した。今年度は、フェニレンジアミン型核酸塩基をオリゴマーDNA中に導入し、金属イオンを活性点とするDNA構造変換を行う予定である。DNAの構造を利用した機能性材料を創成するというコンセプトに立ち、金属錯生成により二重鎖構造を作る新しい人工DNAの合成を行っている。今年度は、フェニレンジアミン基をもつデオキシリボヌクレオチドの合成に成功した。DNA自動合成機を駆使して、これをDNAの任意の場所に任意の数だけ導入する予定である。本研究は今後、生体機能の制御、分子レベルの電線など、新しい電気的、光学的、磁気的な機能性材料への応用を目指す。

  31. Development of Metal Complexes with Functions of Recognition and Tranformation of Nucleic Acids for Control of Gene Expression

    Grant number:08457623  1996 - 1997

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

    SHIONOYA Mitsuhiko, TANAKA Kentaro, TANAKA Kentaro

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    We previously demonstrated that Zn^<II>-cyclen complexes bind selecively and reversibly to thymine (or uracil) base in aqueous solution at physiological pH.These zinc complexes also lowered the melting temperatures of double-stranded poly (A) ・Poly (U) and poly (dA) ・poly (dT), indicating that the double-stranded structures of the polynucleotides are destabilized by the strong interaction between these complexes and thymine (or uracil) bases. We have further studied the interactions between metal complexes and DNA duplexes containing AT-rich sequences which are often seen in transcriptional regulatory domains. For example, Zn^<II>-cyclen complex destabilized the double-stranded structure of oligomeric DNAs with a sequence of adenovirus TATA-box, and consequently lowered the melting temperature (T_m) depending on the concentration of the zinc complex and the solution pH.In contrast, Ni^<II>-and Cu^<II>-cyclen complexes raised the T_m. In addition, for the purpose of creating artificial DNAs as functionalized materials, we synthesized a novel nucleoside bearing a phenylenediamine subunit for metal coordination. While hydrogen donding is one of the primary driving forces to form double helixes in natural DNA,the artificial DNAs with this nucleobase are expected to form double stranded structures by metal coordination, in which metals may align along the helix axis. Hence, these metal aligned structures in the DNA have possibility of application to molecular wire, optical devices, and drugs, etc.

  32. 遺伝子調節領域のATクラスター部位を認識・変換する金属錯体

    Grant number:08877339  1996

    日本学術振興会  科学研究費助成事業  萌芽的研究

    塩谷 光彦, 田中 健太郎, 王子田 彰夫, 田中 健太郎, 王子田 彰夫

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    蛋白質は、α-ヘリックス、β-シートなどの特殊な構造部位によりDNAの特定位置に結合するが、このような相互作用は通常タンパク質全体の高次構造を必要とする。申請者は、DNA結合性金属錯体をオリゴペプチドに担持することによりDNA上でオリゴペプチドの折れたたみが誘起され、三者による超分子が形成されると考えた。本研究では、DNAの特定部位に相補的なオリドペプチド-金属錯体を合成し、DNAとの相互作用を種々の分光学的手法より明らかにした。特に、専属錯体の核酸塩基認識能と核酸高次構造変換能の関係を明らかにし、核酸高次構造を認識・変換する金属錯体の一般性の高い分子設計法の確立に重点をおいた。具体的には、シスチンを中央のリンカーとしメリオニンやシステインの残基を金属の配位子とする、二回対称性のオリゴペプチド-金属(銅、亜鉛、白金など)錯体を合成し、それをDNA転写調節領域の回文配列の認識に適用した。まず、核酸の特定部位に結合する新規オリゴペプリド金属錯体の分子設計し、配位子の合成(バッチ法、固相法、自動合成法)および金属錯体の合成を行った。次に、金属錯体(特に白金錯体)の溶液内構造、溶液平衡の解析を多核多次元NMR、質量分析、紫外可視吸収スペクトルなどにより明らかにした。現在、金属中心の酸化還元反応を利用してオリゴペプチド-金属錯体の高次構造を変化させ、DNAの湾曲を制御することを検討中である。

  33. 金属錯体によるDNAの特殊構造の認識および変換

    Grant number:08772049  1996

    日本学術振興会  科学研究費助成事業  奨励研究(A)

    田中 健太郎

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    Grant amount:\1000000 ( Direct Cost: \1000000 )

    DNAの湾曲構造は、あらゆる種類のDNA中に存在し、DNAの複製、転写、組み換え、あるいは染色体構造の構築という諸過程において重要な機能を果たしていることが知られている。湾曲DNA構造は、比較的短い(dA)トラクトが繰り返し出現するところに見られるが、このような塩基配列はほとんどの場合、各遺伝子のプロモーターおよびその上流の発現調節領域に存在する。本研究は、チミン塩基を認識する金属錯体を新たに設計・合成し、転写調節領域のATクラスター部位の高次構造を変換することにより遺伝子発現制御を行なうことを目的とした。遺伝子プロモーター領域のATクラスター部位を融解する金属錯体の合成:チミン塩基に選択的に結合する亜鉛錯体が、ウイルスDNAの転写領域に存在するTATA boxを含む19mer DNAの二本鎖構造を不安定化し、その融解温度を低下させることを見出した。これは亜鉛錯体特有のもので、銅錯体やニッケル錯体の場合には、逆に融解温度を上昇させた。現在、イミノプロトンNMRによりAT塩基対の解離過程を解析した。その結果、亜鉛錯体は最初にATクラスター部位に結合し、その部分の高次構造の対称性を著しく低下させることを見出した。また、AT塩基対の両塩基に同時に結合することが期待されるBifunctionalな金属錯体を3種類合成した。これらとATクラスター部位を含みヘアピンタイプのオリゴヌクレオチドとの相互作用を検討中である。

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Teaching Experience (On-campus) 11

  1. Core Inorganic Chemistry

    2021

  2. Colloquium Molecular Architecture 1

    2020

  3. Colloquium Molecular Architecture 3

    2020

  4. Core Inorganic Chemistry

    2020

  5. Chemistry Seminars I

    2020

  6. Analytical Chemistry II

    2020

  7. Analytical Chemistry I

    2020

  8. Inorganic Physical Instrumental Analysis

    2020

  9. Laboratory Experiments in Analytical Chemistry

    2020

  10. Colloquium Molecular Architecture 4

    2020

  11. Colloquium Molecular Architecture 2

    2020

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Teaching Experience (Off-campus) 25

  1. 分子化学特別講義A

    2023.4 - 2024.3 Keio University)

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    Level:Postgraduate 

  2. 分子化学特別講義A

    2022.4 - 2023.3 Keio University)

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    Level:Postgraduate 

  3. 環境物質科学特別講義I

    2022.4 - 2023.3 Hokkaido University)

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    Level:Postgraduate  Country:Japan

  4. 分子化学特別講義A

    2021.4 - 2022.3 Keio University)

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  5. 分子化学特別講義A

    2020.4 - 2021.3 Keio University)

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  6. 分子化学特別講義A

    2019.4 - 2020.3 Keio University)

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  7. 分子化学特別講義A

    2018.4 - 2019.3 Keio University)

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  8. 分子化学特別講義A

    2017.4 - 2018.3 Keio University)

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  9. 先導物質科学研究所セミナー

    2016.4 - 2017.3 Kyushu University)

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  10. 分子化学特別講義A

    2016.4 - 2017.3 Keio University)

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  11. 化学特別講義

    2016.4 - 2017.3 University of Tsukuba)

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  12. 化学特別講義2

    2016.4 - 2017.3 Tokyo University of Science)

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  13. 分子化学特別講義A

    2015.4 - 2016.3 Keio University)

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  14. 分子化学特別講義A

    2014.4 - 2015.3 Keio University)

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  15. 分子化学特別講義A

    2013.4 - 2014.3 Keio University)

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  16. 分子化学特別講義A

    2012.4 - 2013.3 Keio University)

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  17. 分子化学特別講義A

    2011.4 - 2012.3 Keio University)

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  18. 分子化学特別講義A

    2010.4 - 2011.3 Keio University)

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  19. 分子化学特別講義A

    2009.4 - 2010.3 Keio University)

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  20. 生命先端工学特論

    2009.4 - 2010.3 Osaka University)

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  21. 化学特別講義

    2007.4 - 2008.3 University of Tsukuba)

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  22. 化学専攻セミナー

    2006.4 - 2007.3 Tokyo Institute of Technology)

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  23. 生物機能科学特別講義

    2006.4 - 2007.3 Yamaguchi University)

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  24. 生体分子機能工学特別講義第四

    2003.4 - 2004.3 Tokyo Institute of Technology)

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  25. 薬学セミナー

    2003.4 - 2004.3 The University of Tokyo)

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