高難度な酸素添加反応を触媒する生体反応活性種の解明

• Project Area: Stimuli-responsive Chemical Species for the Creation of Functional Molecules
• Project/Area Number: 25109523
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Nagoya Institute of Technology
• Principal Investigator: 増田 秀樹 名古屋工業大学, 工学(系)研究科(研究院), 教授 (50209441)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥7,280,000 (Direct Cost: ¥5,600,000、Indirect Cost: ¥1,680,000); Fiscal Year 2014: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000); Fiscal Year 2013: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
• Keywords: 高難度酸化反応 / 混合原子価二核銅錯体 / チロシナーゼモデル / メタンモノオキシゲナーゼモデル / メタンモノオキシゲナーゼ / チロシナーゼ / ビスμオキソ型銅二核錯体 / μーη２：η２型二核銅錯体 / 異種二核銅錯体

Outline of Annual Research Achievements

メタンモノオキシゲナーゼやチロシナーゼ等の酸素添加酵素における優れた生体系反応場を規範とした活性部位を、遷移金属錯体を用いて設計•合成し、酸素捕捉活性化機能を発現させ、その活性種の構造と機能の解明を、人工酵素を用いて行うことが本研究の目的とした。銅系メタンモノオキシゲナーゼで時間が得られている二核系銅(II,III)錯体をオリジナルな設計思想をもとに合成し、その活性種の解明を遂行した。そして２種類の混合原子価二核銅(II,III)錯体の合成に成功した。また、チロシナーゼの反応活性種がビスμオキソ種なのかμ－η2：η2パーオキソ種なのか未解明であったが、本研究ではその２つの二核銅錯体を作り分けることに成功し、それらの基質に対する反応性を検討したところ、μ－η2：η2パーオキソ種のみがチロシナーゼ活性を示し、これが反応中間体であることを明らかとした。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Role of the Amide Carbonyl Groups in Nitrile Hydratase Active Site for Nitrile Coordination Using Co(III) Complex with N2S3-type Ligand (2015)
  • Author(s): T. Yano, T. Ikeda, T. Shibayama, T. Inomata, Y. Funahashi, T. Ozawa, and H. Masuda
  • Journal Title: Chem. Lett. Volume: 44 Issue: 6 Pages: 761-763
  • DOI: 10.1246/cl.150084
  • NAID: 130005074571
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Preparation and characterization of cobalt(II) phthalocyanine complex-encapsulated zeolite-X (2015)
  • Author(s): N. Ohata, Y. Ito, D. Nakane, H. Kitamura, and H. Masuda
  • Journal Title: J. Porph. Phthal. Volume: 19 Issue: 01-03 Pages: 372-376
  • DOI: 10.1142/s1088424615500315
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Organocatalytic Enantioselective Decarboxylative Reaction of Malonic Acid Half Thioesters with Cyclic N-Sulfonyl Ketimines by Using N-Heteroarenesulfonyl Cinchona Alkaloid Amides (2015)
  • Author(s): S. Nakamura, M. Sano, A. Toda, D. Nakane, and H. Masuda
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 10 Pages: 1-5
  • DOI: 10.1002/chem.201406270
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Organocatalytic Enantioselective Addition of Thiols to Ketimines Derived from Isatins (2015)
  • Author(s): S. Nakamura, S. Takahashi, D. Nakane, and H. Masuda
  • Journal Title: Org. Lett. Volume: 17 Issue: 1 Pages: 106-109
  • DOI: 10.1021/ol503309s
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Nitrosyl and carbene iron complexes bearin κ3-SNS thioamide pincer type ligand (2015)
  • Author(s): T. Suzuki, Yuji Kajita, Tomohiro Ozawa, Tomohiko Inomata, and H. Masuda
  • Journal Title: Dalton Trans. Volume: 44 Issue: 3 Pages: 1017-1022
  • DOI: 10.1039/c4dt03128h
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Novel Square-planar Ni(II) Complex with an Amino-carboxamido-dithiolato Type Ligand as an Active Site Model of NiSOD (2014)
  • Author(s): D. Nakane, Y. Wasada-Tsutsui, Y. Funahashi, T. Hatanaka, T. Ozawa, and H. Masuda
  • Journal Title: Inorg. Chem. Volume: 53 Pages: 6512-6523
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Direct Asymmetric Mannich-Type Reaction of α-Isocyanoacetates with Ketimines using Cinchona Alkaloid/Copper(II) Catalysts (2014)
  • Author(s): M. Hayashi, M. Iwanaga, N. Shiomi, D. Nakane, H. Masuda, and S. Nakamura
  • Journal Title: Angew. Chem. Int. Ed. Volume: 53 Issue: 32 Pages: 8411-8415
  • DOI: 10.1002/anie.201404629
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Unique Functions of Metal Complexes Inspired by Control of Coordination Environment around Metal Ions (2014)
  • Author(s): H. Masuda
  • Journal Title: Bulletin of Japan Society of Coordination Chemistry Volume: 63 Issue: 0 Pages: 2-18
  • DOI: 10.4019/bjscc.63.2
  • NAID: 130004688198
  • ISSN: 1882-6954, 1883-1737
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Deprotonation/Protonation-Driven Change of The o-Donor Ability of a Sulfur Atom in Iron(II) Complexes with a Thioamide SNS Pincer Type Ligand (2014)
  • Author(s): T. Suzuki, Y. Kajita, and H. Masuda
  • Journal Title: Dalton Trans. Volume: (in press) Issue: 25 Pages: 9732-9739
  • DOI: 10.1039/c4dt00524d
  • Peer Reviewed / Open Access
• [Journal Article] Au Nanoparticles Modified with Artificial Siderophore-Fe3+ complexes: Selective Adsorption and Aggregation of Microbes using “Coordination Programming, (2014)
  • Author(s): T. Inomata, T. Murase, H. Ido, T. Ozawa, and H. Masuda
  • Journal Title: Chem. Lett. Volume: 43 Issue: 7 Pages: 1146-1148
  • DOI: 10.1246/cl.140270
  • NAID: 130004868218
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Adsorption and Selective Detection of Microbes using a Au Substrate Modified with a Hydroxamate- and Catecholate-Type Artificial Siderophore-Fe3+ Complexes (2013)
  • Author(s): T. Inomata, H. Tanabashi, Y. Funahashi, T. Ozawa, H. Masuda
  • Journal Title: Dalton Transaction Volume: 42 Issue: 45 Pages: 16043-16048
  • DOI: 10.1039/c3dt51448j
  • Peer Reviewed
• [Journal Article] Enantioselective monofluoromethylation of aldehydes with 2-fluoro-1,3-benzodithiole-1,1,3,3-tetraoxide catalyzed by a bifunctional cinchona alkaloid-derived thiourea-titanium complex (2013)
  • Author(s): H. Ma, K. Matsuzaki, Y.-D. Yang, E. Tokunaga, D. Nakane, T. Ozawa, H. Masuda, N. Shibata
  • Journal Title: Chem. Comm. Volume: 49 Issue: 95 Pages: 11206-11208
  • DOI: 10.1039/c3cc46544f
  • Peer Reviewed
• [Journal Article] Stereoselective Synthesis of Vinyl Triflones and Heteroaryl Triflones via Anionic O→Cvinyl/N→Cvinyl Trifluoromethanesulfonyl Migration Reactions (2013)
  • Author(s): Xiu-Hua Xu, Misaki Taniguchi, Xin Wang, Etsuko Tokunaga, Tomohiro Ozawa, Hideki Masuda, and Norio Shibata
  • Journal Title: Angew. Chem. Int. Ed Volume: 52 Pages: 12628-12631
  • Peer Reviewed
• [Journal Article] A Phosphonium-Type Ionic Liquid-Modified Au Electrode: A New Platform for Entrapping Functional Molecules on Substrate Surfaces (2013)
  • Author(s): T. Kitagawa, T. Inomata, Y. Funahashi, T, Ozawa, H. Masuda
  • Journal Title: Chemical Communications Volume: 49 Issue: 86 Pages: 10184-10186
  • DOI: 10.1039/c3cc45251d
  • Peer Reviewed
• [Journal Article] Superoxide disproportionation driven by zinc complexes with various steric and electrostatic properties (2013)
  • Author(s): Akira Wada, Koichiro Jitsukawa, Hideki Masuda
  • Journal Title: Angew Chem Int Ed. Volume: 52 Issue: 47 Pages: 12293-12293
  • DOI: 10.1002/anie.201305459
  • Peer Reviewed / Open Access
• [Presentation] Electrochemical Hydrogenation of Dinitrogen to Ammonia Using Titanocene Dichloride in an Ionic Liquid and its evaluation of ionic liquid by SEIRAS (2014)
  • Author(s): H. Masuda
  • Organizer: 4th Asian Conference on Coordination Chemistry
  • Place of Presentation: Jeju/Korea
  • Year and Date: 2014-11-04 – 2014-11-08
  • Invited
• [Presentation] SYNTHESES AND REACTIVITIES OF DINUCLEAR COPPER COMPLEXES AS STRUCTURAL AND FUNCTIONAL MODELS OF TYROSINASE (2014)
  • Author(s): H. Masuda
  • Organizer: 41st-International Conference on Coordination Chemistry (ICCC41)
  • Place of Presentation: Singapore
  • Year and Date: 2014-07-21 – 2014-07-25
  • Invited
• [Presentation] Syntheses and Reactivities of Dinuclear Copper Complexes as Structural/Functional Models of Tyrosinase (2013)
  • Author(s): H. Masuda
  • Organizer: The 2nd Japan-France Coordination Chemistry Symposium 2013
  • Place of Presentation: Nara, Japan
  • Invited
• [Presentation] Electrochemical Hydrogenation of Dinitrogen to Ammonia Using Titanocene Dichloride in an Ionic Liquid and its evaluation of ionic liquid by SEIRAS (2013)
  • Author(s): H. Masuda
  • Organizer: 4th Asian Conference on Coordination Chemistry
  • Place of Presentation: Jeju, Korea
  • Invited
• [Presentation] 金属錯体の配位環境制御による機能発現 (2013)
  • Author(s): 増田秀樹
  • Organizer: 錯体化学会第６３討論会
  • Place of Presentation: 那覇、沖縄県
  • Invited
• [Book] 無機化学 -マンガ＋要点整理＋演習問題でわかる- (2014)
  • Author(s): 齋藤勝弘，増田秀樹
  • Total Pages: 207
  • Publisher: オーム社
• [Book] 錯体化学会選書１０ 金属錯体の量子・計算化学 (2014)
  • Author(s): 山口兆，榊茂好，増田秀樹
  • Total Pages: 529
  • Publisher: 三共出版
• [Book] 化学版 これって英語で言えますか (2013)
  • Author(s): 斉藤勝弘、増田秀樹
  • Total Pages: 185
  • Publisher: 講談社サイエンティフィック
• [Remarks] 増田研究室
  • URL: http://www.ach.nitech.ac.jp/~inorg/masuda/Japanese/
• [Remarks] 名古屋工業大学 研究者情報
  • URL: http://researcher.nitech.ac.jp
• [Patent(Industrial Property Rights)] ナノ分散液の製造方法およびナノ分散液 (2015)
  • Inventor(s): 増田秀樹，猪股智彦，中根大輔，矢野卓真，中田朋子，市川雄貴
  • Industrial Property Rights Holder: 増田秀樹，猪股智彦，中根大輔，矢野卓真，中田朋子，市川雄貴
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2015-047566
  • Filing Date: 2015-03-01
• [Patent(Industrial Property Rights)] 混合原子価２核銅錯体およびそれを用いてメタンをメタノールに変換する製造方法 (2014)
  • Inventor(s): 増田秀樹、小澤智宏，猪股智彦，落合達矢
  • Industrial Property Rights Holder: 増田秀樹、小澤智宏，猪股智彦，落合達矢
  • Industrial Property Rights Type: 特許
  • Industrial Property Number: 2014-157249
  • Filing Date: 2014-08-01