Synthesis of Molecular Catalysts for Interconversion between Water and Oxygen

2009 Fiscal Year Final Research Report

• Project/Area Number: 17105003
• Research Category: Grant-in-Aid for Scientific Research (S)
• Allocation Type: Single-year Grants
• Research Field: Synthetic chemistry
• Research Institution: Kyushu University
• Principal Investigator: NARUTA Yoshinori Kyushu University, 先導物質化学研究所, 主幹教授 (00108979)
• Co-Investigator(Kenkyū-buntansha): TANI Fumito 九州大学, 先導物質化学研究所, 准教授 (80281195) ; OHOTA Takehiro 九州大学, 先導物質化学研究所, 助教 (70509950) ; SHIMAZAKI Yuichi 九州大学, 先導物質化学研究所, 助教 (80335992) ; CHISHIRO Takefumi 九州大学, 先導物質化学研究所, 特任助教 (90398107) ; LIU Jin-gang 九州大学, 先導物質化学研究所, 学術研究員 (70380540) ; OUYANG Jing-mei 九州大学, 先導物質化学研究所, 学術研究員 (10423500)
• Co-Investigator(Renkei-kenkyūsha): OGURA Takashi 兵庫県立大学, 大学院・理学研究科, 教授 (70183770)
• Project Period (FY): 2005 – 2009
• Keywords: 環境調和型反応 / 分子触媒 / 生物無機化学 / 光合成 / 酸素発生中心 / 呼吸 / 末端酸化酵素 / 燃料電池

Research Abstract

The decomposition of water to oxygen/hydrogen by the renewable energy and its inverse reaction, oxygen reduction to water, are fundamental ones in hydrogen economy. Creation of catalysts to perform both four-electron reactions in high energy-efficiency is important for realizing it. However, since the existing catalysts are still immature and less efficient, we have studied to obtain deep understanding on these reactions modeling of metalloenzymes, which work in photosynthesis and respiration. According to this research, we succeeded to elucidate both reactions mechanism with elaborate (functional) models of the enzymes and to propose them as the excellent molecule catalysts.

Research Products

• [Journal Article] Formation of an End-On Ferric-Peroxo Intermediate upon One-ElectronReduction of a Ferric-Superoxo Heme. (2010)
  • Author(s): J.-G. Liu, Y. Shimizu, T. Ohta, Y. Naruta
  • Journal Title: J. Am. Chem. Soc 132 Pages: 3672-3673
  • Peer Reviewed
• [Journal Article] Copper(II) and Nickel(II) hexafluorophosphate complexes Derived from a Monoanionic Porphyrin Analogue: solvato-and Thermchromism of the Ni complexes by Spin-Interconversion (2010)
  • Author(s): M. Ishida, Y. Naruta, F. Tani
  • Journal Title: Dalton Trans 39 Pages: 2651-2659
  • Peer Reviewed
• [Journal Article] A Novel Porphyrin-related Macrocycle with an Embedded 1, 10-phenanthroline moiety as a fluorescent Mg(II) Ion Sensor (2010)
  • Author(s): M. Ishida, Y. Naruta, F. Tani
  • Journal Title: Angew. Chem. Int. Ed 49 Pages: 91-94
  • Peer Reviewed
• [Journal Article] Using Synthetic Models to Probe the O2 Metabolic Mechanism in Heme-Containing Enzymes (2009)
  • Author(s): J.-G. Liu, T. Ohta, F. Tani, Y. Naruta
  • Journal Title: Science of Future Molecular Systems 3 Pages: 30-36
• [Journal Article] Characterization of a Hydroperoxo-Heme Intermediate of a Synthetic Model: Conversion of a Side-on Peroxy to an End-on Hydroperoxy Complex (2009)
  • Author(s): J.-G. Liu, T. Ohta, S. Yamaguchi, T. Ogura, S. Sakamoto, Y. Maeda, Y. Naruta
  • Journal Title: Angew. Chem. Int. Ed 48 Pages: 9262-9267
  • Peer Reviewed
• [Journal Article] Synthesis and Characterization of a New Prostaglandin H Synthase Model (2009)
  • Author(s): J.J. Reddy, T. Ohta, Y. Naruta
  • Journal Title: Tetrahedron Lett 50 Pages: 3418-3421
  • Peer Reviewed
• [Journal Article] Kinetic Investigation of the Process of Encapsulation of Small Hydrocarbon into a Cavitand Porphyrin. (2007)
  • Author(s): J. Nakazawa, Y. Sakae, M. Aida, Y. Naruta
  • Journal Title: J. Org. Chem 72 Pages: 9448-9455
  • Peer Reviewed
• [Journal Article] Synthetic Models of the Active Site of Cytochrome c Oxidase: Influence of a Tridentate vs Tetradentate Copper Chelate Bearing a His-Tyr linkage Mimic on the Dioxygen Adduct Formation by Heme/Cu Complexes (2007)
  • Author(s): J.-G. Liu, Y. Naruta, F. Tani
  • Journal Title: Chem. Eur. J. 13 Pages: 6365-6378
  • Peer Reviewed
• [Journal Article] 水素エネルギー社会の鍵 (2007)
  • Author(s): 成田吉徳, 化学工業
  • Journal Title: グリーン水素生産 58 Pages: 39-45
• [Journal Article] Characterization of Phenoxyl Radical in Model Complexes for the CuB site of Cytochrome c Oxidase: Steady-State and Transient Absorption, UV resonance Raman, EPR, and DFT Studies for [MIIBIAIPBr]Br (2006)
  • Author(s): Y. Nagano, J.-G. Liu, Y. Naruta, T. Ikoma, S. Tero-Kubota, T. Kitagawa
  • Journal Title: J. Am. Chem. Soc 128(45) Pages: 14560-14570
  • Peer Reviewed
• [Journal Article] 光合成モデル系 (2006)
  • Author(s): 成田吉徳, 現代科学
  • Journal Title: 水の酸化による酸素発生 No.424 Pages: 24-30
• [Journal Article] Syntheses, Crystal Structures, and Single Small Molecule Encapsulation Properties of Cavitand-Porphyrins, J. Nakazawa (2006)
  • Author(s): M. Mizuki, J. Hagiwara, Y. Shimazaki, F. Tani, Y. Naruta
  • Journal Title: Bull. Chem. Soc 79 Pages: 1431-1443
  • Peer Reviewed
• [Journal Article] Size-selective and Reversible Encapsulation of Single Small Hydrocarbon Molecules by a Cavitand-Porphyrin Species (2005)
  • Author(s): J. Nakazawa, J. Hagiwara, M. Mizuki, Y. Shimazaki, F. Tani, Y. Naruta
  • Journal Title: Angew. Chem. Int. Ed 44 Pages: 3744-3746
  • Peer Reviewed
• [Journal Article] An Elaborate Functional Model of Cytochrome c Oxidase Active Site Displaying a Unique Conversion of a Heme-μ-peroxo-CuII Species to a Heme-superoxo/CuI (2005)
  • Author(s): J.-G. Liu, Y. Naruta, F. Tani
  • Journal Title: Angew. Chem. Int. Ed 44 Pages: 1836-1840
• [Journal Article] UV Resonance Raman Study of Model Complexes of the CuB Site of Cytochrome c Oxidase (2005)
  • Author(s): Y. Nagano, J.-G. Liu, Y. Naruta, T. Kitagawa
  • Journal Title: J. Mol. Struct 735-736 Pages: 279-291
• [Journal Article] Selective Formation of a Stableμ-Peroxo Ferric Heme-CuII Complex from the Correspondingμ-Oxo FeIII-CuII Species and Hydrogen Peroxide (2005)
  • Author(s): T. Chishiro, Y. Shimazaki, F. Tani, Y. Naruta
  • Journal Title: Chem Commun (8) Pages: 1079-1081
• [Presentation] Synthetic Heme Models Mimic the Formation of Peroxo- and Hydroperoxo-heme Intermediates Relevant to Dioxygen Activation in Heme-containing Enzymes (2010)
  • Author(s): J. -G. Liu
  • Organizer: AsianInternational Conference in Coordination, Organometallic, and Inorganic Chemistry in 90th Annual Spring Meeting of CSJ
  • Place of Presentation: Funabashi
  • Year and Date: 2010-03-28
• [Presentation] Peroxy to tan end-on Hydroperoxy (2010)
  • Author(s): J. -G. Liu, T. Ohta, Y. Naruta
  • Organizer: Recent progress in Porphyrin-related Chemistry (40th international Workshop on Future Molecular Systems 2010)
  • Place of Presentation: Fukuoka, Japan
  • Year and Date: 2010-02-01
• [Presentation] Dioxygen Activation on Chemical Models of Heme Enzymes (2009)
  • Author(s): Y. Naruta
  • Organizer: 12th international Symposium on Physical Organic Chemistry (KISPOC-12)
  • Place of Presentation: Kyushu University, Fukuoka, Japan
  • Year and Date: 2009-12-16
• [Presentation] Dioxygen Activation on Chemical Models of Heme Enzymes, Symposium of Advancement on Biological Inorganic Chemsitry (SaBIC) (2009)
  • Author(s): Y. Naruta
  • Organizer: Tata Institute of Fundamental Research
  • Place of Presentation: Mumbai, India
  • Year and Date: 2009-11-04
• [Presentation] Preparation of End-on Peroxy and Hydroperoxy Intermediates Relevant to Dioxygen Activation in Heme Enzymes and Cytochrome c Oxidase (2009)
  • Author(s): Y. Naruta
  • Organizer: International Workshop on Metalloprotein Functions, University of Hyogo
  • Place of Presentation: Harima, Japan
  • Year and Date: 2009-07-31
• [Presentation] Simulation of O2 Activation/Reduction with Enzyme Active Site Models of Terminal Oxidases (2009)
  • Author(s): Y. Naruta, J. -G. Liu, T. Ohta, H. Ogura
  • Organizer: 14th International Conference on Biological Inorganic Chemistry (ICBIC-14)
  • Place of Presentation: Nagoya, Japan
  • Year and Date: 2009-07-26
• [Presentation] Selective Preparation of End-on Metal Peroxy Complexes in a Solution and Their Relevance to Dioxygen Activation (2008)
  • Author(s): Y. Naruta, J. -G. Liu, T. Ota, S. Yamaguchi, T. Ogura
  • Organizer: 4th Asian Bioinorganic Chemistry Conference (AsBIC IV)
  • Place of Presentation: Jeju, Korea
  • Year and Date: 20081110-20081113
• [Presentation] 化学モデルを用いたヘムにおける酸素活性化とチトクロムc酸化酵素酸素代謝機構 (2008)
  • Author(s): 成田吉徳
  • Organizer: 2008年度分子研研究会「配位子場制御に基づく機能性錯体の創成と応用～生体から触媒およびデバイスまで」
  • Place of Presentation: 岡崎
  • Year and Date: 20080718-20080719
• [Presentation] エネルギー変換酵素と触媒―理想と現実をつなぐ課題と展望 (2008)
  • Author(s): 成田吉徳
  • Organizer: 日本化学会第89春季年会(アドバンストテクノロジープログラム:材料科学-未来材料)
  • Place of Presentation: 船橋
  • Year and Date: 20080327-20080330
• [Presentation] Selective Preparation of End-on Ferric-Peroxo, Ferrous-Superoxo, and Ferric-Hydroperoxo Species in Solution (2008)
  • Author(s): Y. Naruta
  • Organizer: International Union of Material Research Society-International Conference
  • Place of Presentation: in Asia, Nagoya
  • Year and Date: 2008-12-12
• [Presentation] Oxygen Activation and Oxygen Reduction with Bio-inspired Chemical Models (2008)
  • Author(s): Y. Naruta
  • Organizer: 3rd Joint Symposium of Core Research Institutes, ‘Multidisciplinary Approach for Materials Synthesis'
  • Place of Presentation: Fukuoka
  • Year and Date: 2008-03-15
• [Presentation] Mutual Conversion Reactions between Water and Oxygen with Metal Complexes (2007)
  • Author(s): Y. Naruta
  • Organizer: 57th Coordination Chemistry Symposium
  • Place of Presentation: Nagoya
  • Year and Date: 2007-09-25
• [Presentation] Oxygen Activation with Bio-inspired Model Complexes Relating to cytochrome c Oxidase (2006)
  • Author(s): Y, Naruta
  • Organizer: Asian Bioinorganic Chemistry Symposium (AsBIC-3)
  • Place of Presentation: Nanjin, China
  • Year and Date: 20061031-20061103
• [Presentation] Modeling Study of Dioxygen Activation in Cytochrome c Oxidase Active Site (2006)
  • Author(s): Y. Naruta
  • Organizer: Taiwan Bioinorganic Symposium 2006 (TBICS-2006)
  • Place of Presentation: Taipei, ROC
  • Year and Date: 20061006-20061007
• [Presentation] Manganeseporphyrin Dimers: functional Relevance to Oxygen Evolving Complex in PhotosystemII (2006)
  • Author(s): Y. Naruta, Y. Shimazaki, F. Tani, E.I. Solomon, S. DeBeer Geroge
  • Organizer: 4th International Conference on Porphyrins and Phthalocyanines (ICPP-4)
  • Place of Presentation: Rome, Italy
  • Year and Date: 20060702-20060707
• [Presentation] Hydrogen Production with Renewable Energy (2006)
  • Author(s): Y. Naruta
  • Organizer: Green Sastainable Chemistry Lectures, JCII
  • Place of Presentation: Tokyo, Japan
  • Year and Date: 2006-12-07
• [Presentation] Dioxygen Activation Chemistry of Metalloenzymes and Models (2005)
  • Author(s): Y. Naruta
  • Organizer: PACIFICHEM-2005 (Symposium: Dioxygen Activation Chemistry of Metalloenzymes and Models)
  • Place of Presentation: Honolulu, Hawaii, USA
  • Year and Date: 20051215-20051220
• [Presentation] Modeling Study of Oxygen Activation in Cytochrome c Oxidase: Roles of Residues at the Active Site (2005)
  • Author(s): Y. Naruta, J. -G. Liu, X. -M. Ouyang, T. Chishiro, T. Higa, F. Tani
  • Organizer: 12th International conference in Bioinorganic Chemistry (ICBIC-12)
  • Place of Presentation: Ann Arbor, USA
  • Year and Date: 20050731-20050805
• [Book] Chemistry: Life and Living enriched by Elements (2006)
  • Author(s): Y. Naruta
  • Total Pages: 130-145
  • Publisher: Kubapro, Tokyo
• [Remarks] 報道関係:報文No. 5は次の新聞において報道された:平成21年10月31日付け読売新聞、西日本新聞;同11月13日付け科学新聞次の論文誌にハイライトとして紹介された:Nature, 2010年464巻、pp. 168-169(1月14日); Angew. Chem. Int. Ed. 2010年49巻pp. 2099-2101(3月15日).
  • URL: http://www.narutalab.ifoc.kyushu-u.ac.jp