電子移動還元およびラジカル種によるDNA損傷機構の解明

2008 年度 研究成果報告書

• 研究課題/領域番号: 19750034
• 研究種目: 若手研究(B)
• 配分区分: 補助金
• 研究分野: 有機化学
• 研究機関: 大阪大学
• 研究代表者: 大久保 敬 大阪大学, 大学院工学研究科, 特任研究員 (00379140)
• 研究期間 (年度): 2007 – 2008
• キーワード: 有機物理化学 / 電子移動化学

研究概要

DNAの損傷は突然変異を引き起こし、細胞の死やがん化の原因となる。そのためこのDNA損傷の化学反応を制御する機構の解明は、次世代の医療の新手法開発にもつながる極めて重要な課題である。本研究では、様々なラジカル種(アルキルラジカル・活性酸素種)とDNAおよび核酸塩基との反応について、中間体の検出や各種速度論的解析の結果をもとに損傷機構の解明を行った。

研究成果

• [雑誌論文] Aliphatic C-H Bond Activation Initiated by a (μ-η^2:η2-Peroxo)dicopper(II) Complex in Comparison with Cumylperoxyl Radical (2009)
  • 著者名/発表者名: Matsumoto, T., Ohkubo, K., Honda, K., Yazawa, A., Furutachi, H., Fujinami, S.,; Fukuzumi, S., Suzuki, M.
  • 雑誌名: J. Am. Chem. Soc. 131(in press)
• [雑誌論文] Tuning Charge Transfer in Novel Reaction Center Mimics Based on Th-Functionalized Fullerenes (2009)
  • 著者名/発表者名: Spanig F., Kovacs, C., Hauke, F., Hartnagel, U., Ohkubo, K., Fukuzumi, S., Guldi, D. M., Hirsch, A.
  • 雑誌名: J. Am. Chem. Soc. 131(in press)
• [雑誌論文] Photoinduced Electron-Transfer Reduction of a Hydrochloride Salt of Dodecaphenylporphyrin with Conformational Distortion (2009)
  • 著者名/発表者名: Nakanishi, T., Kojima, T., Ohkubo, K., Fukuzumi, S.
  • 雑誌名: J. Am. Chem. Soc. 131 ページ: 577-584
• [雑誌論文] Metal Quinolinolate-Fullerene(s) Donor-Acceptor Complexes: Evidence for Organic LED Molecules Acting as Electron Donors in Photoinduced Electron-Transfer Reactions (2008)
  • 著者名/発表者名: D'Souza, F., Maligaspe, E., Zandler, M. E., Subbaiyan, N. K., Ohkubo, K., Fukuzumi, S.
  • 雑誌名: J. Am. Chem. Soc. 130 ページ: 16959-16967
• [雑誌論文] "Umpolung" Photoinduced Charge Separation in an Anion-bound Supramolecular Complex (2008)
  • 著者名/発表者名: Sessler, J. L., Karnas, E., Kim, S. K., Ou, Z., Zhang, M., Kadish, K. M., Ohkubo, K., Fukuzumi, S.
  • 雑誌名: J. Am. Chem. Soc. 130 ページ: 15256-15257
• [雑誌論文] Proton Shift upon One-Electron Reduction in Ruthenium-Coordinated Pterins (2008)
  • 著者名/発表者名: Miyazaki, S., Ohkubo, K., Kojima, T., Fukuzumi, S.
  • 雑誌名: Angew. Chem. Int. Ed. 47 ページ: 9669-9672
• [雑誌論文] (Pentamethylcyclopentadienyl)ruthenium π-Complexes of Metalloporphyrins: Platforms with Novel Photo- and Electrochemical Properties (2008)
  • 著者名/発表者名: Cuesta, L., Karnas, E., Kynch, V. M., Sessler, J. L., Kajonkijya, W., Zhu, W., Zhang, M., Ou, Z., Kadish, K. M., Ohkubo, K., Fukuzumi, S.
  • 雑誌名: Chem. Eur. J. 14 ページ: 10206-10210
• [雑誌論文] Highly Selective Synthesis of the Ring-B Reduced Chlorins by Ferric Chloride Mediated Oxidation of Bacteriochlorins: Effects of the Fused Imide vs Isocyclic Ring in Photophysical and Electrochemical Properties (2008)
  • 著者名/発表者名: Liu, C., Dobhal, M. P., Ethirajan, M., Missert, J. R., Pandey, R. K., Balasubramanian, S., Sukumaran, D. K., Zhang, M., Kadish, K. M., Ohkubo, K., Fukuzumi, S.
  • 雑誌名: J. Am. Chem. Soc. 130 ページ: 14311-14323
• [雑誌論文] A Discrete Supramolecular Conglomerate Composed of Two Saddle-Distorted Zinc(II)-Phthalocyanine Complexes and a Doubly Protonated Porphyrin with Saddle-Distortion Undergoing Efficient Photoinduced Electron Transfer (2008)
  • 著者名/発表者名: Kojima, T., Honda, T., Ohkubo, K., Shiro, M., Kusukawa, T., Fukuda, T., Kobayashi, N., Fukuzumi, S.
  • 雑誌名: Angew. Chem., Int. Ed. 47 ページ: 6712-6716
• [雑誌論文] Androgynous Porphyrins. Silver(II) Quinoxalinoporphyrins Act as Both Good Electron Donors and Acceptors (2008)
  • 著者名/発表者名: Fukuzumi, S., Ohkubo, K., Zhu, W., Sintic, M., Khoury, T., Sintic, P. J., E, W., Ou, Z., Crossley, M. J., Kadish, K. M.
  • 雑誌名: J. Am. Chem. Soc. 130 ページ: 9451-9458
• [雑誌論文] Face-to-Face Held Pacman Type Porphyrin-Fullerene Dyads : Design, Synthesis, Charge Transfer Interactions and Photophysical Studies (2008)
  • 著者名/発表者名: D'Souza, F., Maligaspe, E., Karr, P. A., Schumacher, A. L., Ojaimi, M. E., Gros, C. P., Barbe, J.-M., Ohkubo, K., Fukuzumi, S.
  • 雑誌名: hem. Eur. J. 14 ページ: 674-681
• [雑誌論文] Constracting Photodynamics between Dithiapyrene-C60 and Pyrene-C60 Dyads (2008)
  • 著者名/発表者名: Guldi, D. M., Spaning, F., Kreher, D., Perepichka, I. F., Bryce, M. R., Ohkubo, K., Fukuzumi, S.
  • 雑誌名: Chem. Eur. J. 14 ページ: 250-258
• [雑誌論文] Spectroscopic Characterization of Photolytically Generated Radical Ion Pairs in Single-Wall Carbon Nanotubes Bearing Surface-Immobilized Tetrathiafulvalens (2008)
  • 著者名/発表者名: Herranz, M. A., Ehli, C., Campidelli, S., Gutierrez, M., Hug, G. L., Ohkubo, K., Fukuzumi, S., Prato, M., Matin, N., Guldi, D. M.
  • 雑誌名: J. Am. Chem. Soc. 130 ページ: 66-73
• [雑誌論文] Design and Synthesis of Polymetallic Complexes Based on meso-Calix[4]pyrrole : Platform for Multielectron Chemistry (2007)
  • 著者名/発表者名: Custa, L., Gross, D., Lynch, V. M., Ou, Z., Kajokiiya, W., Ohkubo, K., Fukuzumi, S., Kadish, K. M., J. L. Sessler
  • 雑誌名: J. Am. Chem. Soc. 129 ページ: 11696-11697
• [雑誌論文] Selective Inclusion of Electron-Donating Molecules into Porphyrin Nanochannels Derived from Self-Assembly of Saddle-Distorted Dicationic Porphyrins and Photoinduced Electron Transfer from the Guest Molecules to the Porphyrin Dications (2007)
  • 著者名/発表者名: Kojima, T., Nakanishi, T., Harada, R., Ohkubo, K., Yamauchi, S., Fukuzumi, S.
  • 雑誌名: Chem. Eur. J. 36 ページ: 8714-8725
• [雑誌論文] Synthesis and Characterization of Mononuclear Ruthenium(III)-Pyridylamine Complexes and Mechanistic Insights into Their Catalytic Alkene Functionalization with m-Chloroperbenzoic Acid (2007)
  • 著者名/発表者名: Kojima, T., Hayashi, K., Iizuka, S., Tani, F., Naruta, Y., Kawano, M., Ohashi, Y., Hirai, Y., Ohkubo, K., Fukuzumi, S.
  • 雑誌名: Chem. Eur. J. 13 ページ: 8212-8222
• [雑誌論文] Intramolecular Electron Transfer within the Substituted Tetrathiafulvalene-Quinone Dyads : FAcilitated by Metal Ion and Photomodulation in the Presence of Spiropyran (2007)
  • 著者名/発表者名: Wu, H., Zhang, D., Su, L., Ohkubo, K., Zhang, C., Yin, S., Mao, L., Shuai, Z., Fukuzumi, S., Zhu, D.
  • 雑誌名: J. Am. Chem. Soc. 129 ページ: 6839-6846
• [雑誌論文] Modulation of Characteristics of a Ruthenium-Coordinated Flavin Analog Showing an Unprecedented Coordination Mode (2007)
  • 著者名/発表者名: Miyazaki, S., Ohkubo, K., Kojima, T., Fukuzumi, S.
  • 雑誌名: Angew. Chem. Int. Ed. 46 ページ: 905-908
• [学会発表] Rational Design of Long-Lived Charge Separation (2008)
  • 著者名/発表者名: Kei Ohkubo
  • 学会等名: Osaka University Forum 2008
  • 発表場所: Milton Marks Conference Center "Auditorium" San Francisco, USA
  • 年月日: 20081208-10
• [学会発表] A Discrete Supramolecular Conglomerate Composed of Saddle-Distorted Porphyrin Dication and Zn(II)-Phthalocyanine Complexes (2008)
  • 著者名/発表者名: Tatsuhiko Honda, Takahiko Kojima, Kei Ohkubo, Motoo Shiro, Takahiro Kusukawa, Takamitsu Fukuda, Nagao Kobayashi, Shunichi Fukuzumi
  • 学会等名: The 4^<th> Asian Biological Inorganic Chemistry Conference(AsBIC IV)
  • 発表場所: Jeju, Korea
  • 年月日: 20081110-13
• [学会発表] Homogeneous and Heterogeneoues Catalytic Reduction of Dioxygen Using Cobalt Corroles (2008)
  • 著者名/発表者名: Kei Ohkubo, Jing Shen, Claude P. Gros, Jean-Michel Barbe, Karl M. Kadish, Roger Guilard, Shunichi Fukuzumi
  • 学会等名: The 4th Asian Biological Inorganic Chemistry Conference (AsBIC IV)
  • 発表場所: Jeju, Korea
  • 年月日: 20081110-13
• [学会発表] Elongation of Charge-Separation Lifetime of Zinc Quinoxalino- porphyrin-Gold Quinoxalinoporphyrin by Binding of Scandium Ion (2008)
  • 著者名/発表者名: Kei Ohkubo, Rachel Garcia, Paul J. Sintic, Tony Khoury, Maxwell J. Crossley, Karl M. Kadish, Houston),Shunichi Fukuzumi
  • 学会等名: The 5^<th> Asian-Oceanian Photochemistry Conference
  • 発表場所: Beijing, China
  • 年月日: 20081101-05
• [学会発表] Effects of Magnesium Ion on Photoinduced Electron Transfer in Zinc Phthalocyanine-Perylenebisimide Dyad and Triad (2008)
  • 著者名/発表者名: Kei Ohkubo, Fernando Fenandez-Lazaro, Angela Sastre-Santos, Shunichi Fukuzumi
  • 学会等名: 2008 Korea-Japan Symposium on Frontier Photoscience (KJFP 2008)
  • 発表場所: Jeju, Korea
  • 年月日: 20080925-28
• [学会発表] Formation of the Charge-Separated State in N,N-Dimethylaniline-Flavin Dyad with Millisecond Lifetime in Solution at Room Temperature (2008)
  • 著者名/発表者名: Motonobu Murakami, Kei Ohkubo, Shunichi Fukuzumi
  • 学会等名: 2008 Korea-Japan Symposium on Frontier Photoscience (KJFP 2008)
  • 発表場所: Jeju, Korea
  • 年月日: 20080925-28
• [学会発表] Closely Linked Electron Donor-Acceptor Dyads with Much Longer Charge-Separation Lifetimes than Natural Photosynthetic Reaction Center (2008)
  • 著者名/発表者名: Kei Ohkubo
  • 学会等名: 5th International Conference on Porphyrins and Phthalocyanines (ICPP-5)
  • 発表場所: Moscow, Russia
  • 年月日: 20080707-11
• [学会発表] Photodynamics of Supramolecule Composed of Saddle-Distorted Protonated Porphyrin and Zn-Phthalocyanine (2008)
  • 著者名/発表者名: Tatsuhiko Honda, Takahiko Kojima, Tatsuaki Nakanishi, Takamitsu Fukuda, Nagao Kobayashi, Kei Ohkubo, Shunichi Fukuzumi
  • 学会等名: 5th International Conference on Porphyrins and Phthalocyanines (ICPP-5)
  • 発表場所: Moscow, Russia
  • 年月日: 20080707-11
• [学会発表] A Supramolecular Assembly Composed of Saddle-Distorted Protonated Porphyrin and Zn-Phthalocyanine (2008)
  • 著者名/発表者名: Takahiko Kojima, Tatsuhiko Honda, Tatsuaki Nakanishi, Kei Ohkubo, Takamitsu Fukuda, Nagao Kobayashi, and Shunichi Fukuzumi
  • 学会等名: 5th International Conference on Porphyrins and Phthalocyanines (ICPP-5)
  • 発表場所: Moscow, Russia
  • 年月日: 20080707-11
• [学会発表] Photoinduced Charge Separation of Electron Donor-Substituted Flavin and Supramolecular Formation with Fullerene Receptor by Hydrogen Bonding (2008)
  • 著者名/発表者名: Motonobu Murakami, Kei Ohkubo, Vito Sgobba, Dirk M. Guldi, Florian Wessendorf, Andreas Hirsch, Shunichi Fukuzumi
  • 学会等名: 213th ECS Meeting
  • 発表場所: Phoenix, Arizona, USA
  • 年月日: 20080518-22
• [学会発表] A Supramolecular Complex between an Electron Donor-Substituted Flavin and Fullerene with Receptors by Hydrogen Bonding (2008)
  • 著者名/発表者名: Motonobu Murakami, Kei Ohkubo, Vito Sgobba, Dirk M. Guldi, Florian Wessendorf, Andreas Hirsch, and Shunichi Fukuzumi
  • 学会等名: The 1st International Global COE Symposium on Bio-Environmental Chemistry (GCOEBEC-1)
  • 年月日: 20080127-29
• [学会発表] Free Radical-Scavenging Reactions by Neurotransmitters (2008)
  • 著者名/発表者名: Tomonori Kawashima, Kei Ohkubo, Yoshihiko Moro-oka, Shunichi Fukuzumi
  • 学会等名: The 1st International Global COE Symposium on Bio-Environmental Chemistry (GCOEBEC-1)
  • 年月日: 20080127-29
• [学会発表] Dynamics in Photoinduced Electron-Transfer Reduction of Diprotonated Porphyrins with Conformational Distortion (2008)
  • 著者名/発表者名: Tatsuaki Nakanishi, Kei Ohkubo, Takahiko Kojima, Shunichi Fukuzumi
  • 学会等名: The 1st International Global COE Symposium on Bio-Environmental Chemistry (GCOEBEC-1)
  • 発表場所: 吹田
  • 年月日: 20080127-29
• [学会発表] Photophysical And Electrochemical Properties of Metallobacteriochlorins for Photodynamic Therapy (2007)
  • 著者名/発表者名: Kei Ohkubo, Xiang Zheng, Yihui Chen, Ravindra K. Pandey, Riqiang Zhan, Karl M. Kadish, Shunichi Fukuzumi
  • 学会等名: 211th ECS Meeting
  • 発表場所: Chicago, Illinois, USA
  • 年月日: 20070506-11
• [学会発表] Electron-Transfer Properties of Substituted Bi-, Ter-, and Quaterpyrroles (2007)
  • 著者名/発表者名: Wenbo E, Kei Ohkubo, David Sanchez-Garcia, Elizabeth Karnas, Min Zhang, Jonathan L. Sessler, Shunichi Fukuzumi, Karl M. Kadisha
  • 学会等名: 211th ECS Meeting
  • 発表場所: Chicago, Illinois, USA
  • 年月日: 20070506-11
• [学会発表] Photoinduced Electron Transfer IN Silicon Phthalocyanines Functionalized with C_<60> (2007)
  • 著者名/発表者名: Angela Sastre-Santos, Luis Martin-Gomis, Maria Pascual del Riquelme, Fernando Fernandez-Lazaro, Kei Ohkubo, Shunichi Fukuzumi
  • 学会等名: 211th ECS Meeting
  • 発表場所: Chicago, Illinois, USA
  • 年月日: 20070506-11
• [学会発表] 天然を凌駕する電荷分離寿命を有するドナー・アクセプター連結分子を用いた光触媒反応 (2007)
  • 著者名/発表者名: Kei Ohkubo
  • 学会等名: 新物質創製研究アスペクト研究交流会
  • 発表場所: 筑波大学
  • 年月日: 2007-10-06
• [学会発表] 長寿命の光電荷分離状態を有するドナー・アクセプター連結系分子の開発と応用 (2007)
  • 著者名/発表者名: Kei Ohkubo
  • 学会等名: 第1回デバイス物性研究会
  • 発表場所: 大阪大学
  • 年月日: 2007-04-13
• [産業財産権] キノリニウムイオン誘導体、キノリニウムイオン誘導体の製造方法、キノリニウムイオン誘導体を用いた製品、キノリニウムイオン誘導体を用いた還元方法および酸化方法 (2009)
  • 発明者名: 福住俊一, 小谷弘明, 大久保敬
  • 権利者名: 大阪大学
  • 産業財産権番号: 特願2009-533049
  • 出願年月日: 2009-03-10
• [産業財産権] 新規9-置換アクリジニウム誘導体、および9-置換アクリジニウム誘導体を用いた芳香族アルデヒドと過酸化水素の同時製造方法 (2008)
  • 発明者名: 大久保敬, 福住俊一, 岩田亮介, 水島健太郎, 鈴木信夫, 相馬和憲
  • 権利者名: 東京化成工業株式会社
  • 産業財産権番号: 特願2008-255128
  • 出願年月日: 2008-09-03
• [産業財産権] 水素発生触媒 (2007)
  • 発明者名: 福住俊一, 小谷弘明, 大久保敬, 花崎亮
  • 権利者名: JST
  • 産業財産権番号: 特願2007-247656
  • 出願年月日: 2007-09-25