Synthesis, Reactivity, and Spectroscopic Studies of Multi-copper Enzyme Models

• Project/Area Number: 24550080
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: University of Hyogo (2014); Kyushu University (2012-2013)
• Principal Investigator: OHTA Takehiro 兵庫県立大学, 生命理学研究科, 助教 (70509950)
• Project Period (FY): 2012-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥5,590,000 (Direct Cost: ¥4,300,000、Indirect Cost: ¥1,290,000); Fiscal Year 2014: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2013: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000); Fiscal Year 2012: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
• Keywords: 生体模倣金属錯体 / マルチ銅酵素 / 酸素活性化 / 分子触媒 / 生体分子 / 燃料電池 / 銅酸素錯体

Outline of Final Research Achievements

New multi-copper enzyme model complexes, and related dioxygen activating enzyme model complexes were synthesized. Dioxygen binding and activation mechanism were studied with characterizing dioxygen binding reaction intermediates using spectroscopic methods. Reactivity of these enzyme model complexes were studied by electrochemical dioxygen reduction reaction. These studies contribute to energy conversion chemistry relating fuel cell system, unrevealing reaction mechanism of dioxygen activating enzymes.

Research Products

• [Journal Article] Nitric Oxide Activation by caa3 Oxidoreductase from Thermus thermophiles (2015)
  • Author(s): T. Ohta, T. Soulimane, T. Kitagawa, C. Varotsis
  • Journal Title: Physical Chemistry Chemical Physics Volume: 17 Issue: 16 Pages: 10894-10898
  • DOI: 10.1039/c5cp01013f
  • Peer Reviewed
• [Journal Article] Nuclear Resonance Vibrational Spectroscopic Studies of Iron-containing Biomolecules (2014)
  • Author(s): T. Ohta and M. Seto
  • Journal Title: Nihon Kessho Gakkaishi Volume: 56 Issue: 5 Pages: 329-335
  • DOI: 10.5940/jcrsj.56.329
  • NAID: 130004714204
  • ISSN: 0369-4585, 1884-5576
  • Peer Reviewed / Open Access
• [Journal Article] Isolation of a MnIV Acylperoxo Complex and Its Monooxidation Ability (2013)
  • Author(s): Kikunaga, Takahiro; Matsumoto, Takahiro; Ohta, Takehiro; Nakai, Hidetaka; Naruta, Yoshinori; Ahn, Kwang-Hyun; Watanabe, Yoshihito; Ogo, Seiji
  • Journal Title: Chem. Commun. Volume: 49(75) Issue: 75 Pages: 8356-8358
  • DOI: 10.1039/c3cc43447h
  • Peer Reviewed
• [Journal Article] The protein effect in the structure of two ferryl-oxo intermediates at the same oxidation level in the heme copper binuclear center of cytochrome c oxidase (2013)
  • Author(s): E. Pinakoulaki, V. Daskalakis, T. Ohta, O.-M. H. Richter, K. Budiman, T. Kitagawa, B. Ludwig, C. Varotsis
  • Journal Title: J. Biol. Chem. Volume: 288 Issue: 28 Pages: 20261-20266
  • DOI: 10.1074/jbc.m113.468488
  • Peer Reviewed
• [Journal Article] Nuclear Resonance Vibrational Spectroscopic and Computational Study of High-valent Diiron Complexes Relevant to Enzyme Intermediates (2013)
  • Author(s): K. Park, C. B. Bell III, L. V. Liu, D. Wang, G. Xue, T. Kwak, S. D. Wong, K. M. Light, J. Zhao, E. E. Alp, Y. Yoda, M. Saito, Y. Kobayashi, T. Ohta, M. Seto, L. Que Jr, E. I. Solomon
  • Journal Title: Proc. Natl. Acad. Sci. USA Volume: 110 Issue: 16 Pages: 6275-6280
  • DOI: 10.1073/pnas.1304238110
  • Peer Reviewed
• [Journal Article] Axial Ligand Effects on Vibrational Dynamics of Iron in Heme Carbonyl Studied by Nuclear Resonance Vibrational Spectroscopy (2013)
  • Author(s): T. Ohta, J. -G. Liu, and Y. Naruta
  • Journal Title: Coord. Chem. Rev. Volume: 257 Issue: 2 Pages: 407-413
  • DOI: 10.1016/j.ccr.2012.05.009
  • Peer Reviewed
• [Journal Article] Crystal structure of aldoxime dehydratase and its catalytic mechanism involved in carbon-nitrogen triple-bond synthesis (2013)
  • Author(s): Nomura, J., Hashimoto, H., Ohta, T., Hashimoto, Y., Wada, K., Naruta, Y., Oinuma, K-I., & Kobayashi, M.
  • Journal Title: Proc. Natl. Acad. Sci. USA Volume: 110 Issue: 8 Pages: 2810-2815
  • DOI: 10.1073/pnas.1200338110
  • Peer Reviewed
• [Journal Article] Axial ligand effects on vibrational dynamics of iron in heme carbonyl studied by nuclear resonance vibrational spectroscopy (2012)
  • Author(s): Ohta, T., Liu, J.-G., Saito, M., Kobayashi, Y., Yoda, Y., Seto, M., Naruta, Y.
  • Journal Title: Journal of Physical Chemistry B Volume: 116 Issue: 47 Pages: 13831-13838
  • DOI: 10.1021/jp304398g
  • Peer Reviewed
• [Presentation] To Be Anounced (2016)
  • Author(s): T. Ohta
  • Organizer: The 9th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Nanjing, China
  • Year and Date: 2016-07-03 – 2016-07-08
  • Invited
• [Presentation] Reactivity and Spectroscopic Studies of Oxygen Reduction Reaction of Bio-Inspired Molecular Catalysts (2015)
  • Author(s): T. Ohta
  • Organizer: The 227th Electrochemical Society Meeting
  • Place of Presentation: Chicago, Illinois, USA
  • Year and Date: 2015-05-24 – 2015-05-28
  • Invited
• [Presentation] Structure-reactivity Correlation in Oxygen-activating Heme Models (2014)
  • Author(s): T. Ohta
  • Organizer: The 8th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Istanbul Lutfi Kirdar Convention & Exhibition Centre, Turkey
  • Year and Date: 2014-06-22 – 2014-06-27
  • Invited
• [Presentation] マルチ銅酸化酵素を規範とした新規多核銅錯体の合成と反応性 (2014)
  • Author(s): 太田 雄大・成田 吉徳
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] Structure-reactivity correlations in O2 activating heme models (2014)
  • Author(s): T. Ohta
  • Organizer: The 8th International Conference on Porphyrins and Phthalocyanines
  • Place of Presentation: Istanbul, Turkey
  • Invited
• [Presentation] マルチ銅酸化酵素を規範とした新規多核銅錯体の合成と反応性 (2013)
  • Author(s): 太田 雄大・成田 吉徳
  • Organizer: 錯体化学会第63回討論会
  • Place of Presentation: 琉球大学
• [Presentation] Mechanistic Studies of Dioxygen Activation by Functional Heme Models (2012)
  • Author(s): T. Ohta, P. Nagaraju, J-.G. Liu, Y. Naruta
  • Organizer: 6th Asian Biological Inorganic Chemistry Conference
  • Place of Presentation: 香港（中国）
• [Presentation] 酸素活性化ヘム酵素モデル錯体の反応機構解析 (2012)
  • Author(s): 太田雄大, P. Nagaraju, 劉 勁剛, 成田吉徳
  • Organizer: 第62回錯体化学討会
  • Place of Presentation: 富山