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Structures and functions of reaction spaces constructed using metalloprotiens

Research Project

Project/Area Number 16074208
Research Category

Grant-in-Aid for Scientific Research on Priority Areas

Allocation TypeSingle-year Grants
Review Section Science and Engineering
Research InstitutionNagoya University

Principal Investigator

WATANABE Yoshihito  Nagoya University, Research Center for Materials Science, Professor (10201245)

Co-Investigator(Kenkyū-buntansha) NAKAJIMA Hiroshi  Nagoya University, Graduate School of Science, Associate Professor (00283151)
UENO Takafumi  Nagoya University, Graduate School of Science, Assistant Professor (70332179)
Project Period (FY) 2004 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥59,000,000 (Direct Cost: ¥59,000,000)
Fiscal Year 2007: ¥10,500,000 (Direct Cost: ¥10,500,000)
Fiscal Year 2006: ¥31,000,000 (Direct Cost: ¥31,000,000)
Fiscal Year 2005: ¥10,500,000 (Direct Cost: ¥10,500,000)
Fiscal Year 2004: ¥7,000,000 (Direct Cost: ¥7,000,000)
KeywordsFerritin / Suzuki coupling / myoglobin / palladium / oraganometal complex / biocalalyst / metalloprotein / artificial protein / 結晶構造 / 還元反応 / 金属クラスター / Pdクラスター / 有機金属酵素 / 合金 / コア・シェル構造 / ナノクラスター / ヘムオキシゲナーゼ / 電子伝達 / 酸化還元 / ヘム / 水素結合
Research Abstract

Last year, we have specified the amino acid residues responsible for capturing Pd2+ ions on the interior surface of ap-ferritin by X-ray crystal structural studies. In addition, we have examined the residues which ligate to Au3+ ions and found that some of the Au ion binding sites in apo-ferritin are different from those of Pd ions with different coordi-nation structures. On the basis of these observation, we have prepared two type of metal nano-clusters, i.e., alloy and core/shell as shown in Schem 1. In the co-reduction, Au and Pd ions coexist in the apo-ferritin cage. The number of each ion in the cage is regulated by the affinity of each ions to its specific amino acid residues. Consequently, the alloy nano-particle was composed of 133 Au atoms and 165 Pd atoms ((AuPd)・apo-ferritin). On the other hand, we have successfully prepared Au-core/Pd-shell([Au] (Pd)) and Pd-core/Au-shell ([Pd] (Au)) types of nano-particles composed of 201 Au atoms/305 Pd atoms and 169 Au atoms/65Pd atoms, respectively. Among those apo-ferritin composites, [Au] (Pd) apo-ferritin shows the highest catalytic activity for the hydrogenation of olefins.
In a separate experiment, we have examined a possible incorporation of organometallic compounds such as [Pd(allyl)C1]2 and [Rh(norbornadiene)C1]2 in apo-ferritin. The crystal structure of Pd(allyl)・apo-ferritin clearly shows that the allyl group ligates to Pd ion in apo-ferritin.

Report

(5 results)
  • 2007 Annual Research Report   Final Research Report Summary
  • 2006 Annual Research Report
  • 2005 Annual Research Report
  • 2004 Annual Research Report
  • Research Products

    (46 results)

All 2008 2007 2006 2005 2004 Other

All Journal Article (29 results) (of which Peer Reviewed: 11 results) Presentation (13 results) Book (2 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Molecular Design of Heteroprotein Assemblies Providing a Bionanocup as a Chemical Reactor2008

    • Author(s)
      T. Koshiyama, N. Yokoi, T. Ueno, S. Kanamaru, S. Nagano, Y. Shiro, F. Arisaka, and Y. Watanabe
    • Journal Title

      Small 4

      Pages: 50-54

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ligand Design for the Improvement of Stability of Metal Complex・Protein Hybrid2008

    • Author(s)
      N. Yokoi, T. Ueno, T. Matsui, M.Ikeda-Saito, and Y. Watanabe
    • Journal Title

      Chem. Commun.

      Pages: 229-231

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrogen Peroxide Dependent Monooxygenations by Tricking the Substrate Recognition of Cytochrome P450_<BSβ>"2007

    • Author(s)
      O. Shoji, T. Fujishiro, H. Nakajima, M. Kim, S. Nagano, Y. Shiro, Y. Watanabe
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 3656-3659

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Design and Structure Analysis of Artificial Metalloproteins : Selective Coordination of His64 to Copper Complexes with Square-Planar Structure in the apo-Myoglobin Scaffold2007

    • Author(s)
      S. Abe, T. Ueno, P. A. N. Reddy, S. Okazaki, T. Hikage, A. Suzuki, T. Yamane, H. Nakajima, Y. Watanabe
    • Journal Title

      Inorg. Chem. 46

      Pages: 5137-5139

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Incorporation of a Phebox Rhodium Complex into apo-Myoglobin Affords a Stable Organometallic Protein Showing Unprecedented Arrangement of the Complex in the Cavity2007

    • Author(s)
      Y. Satake, S. Abe, S. Okazaki, N. Ban, T. Hikage, T. Ueno, H. Nakajima, A. Suzuki, T. Yamane, H. Nishiyama, Y. Watanabe
    • Journal Title

      Organometallics 26

      Pages: 4904-4908

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Design of Artificial Metalloenzymes using Non-Covalent Insertion of a Metal Complexes into a protein Scaffold2007

    • Author(s)
      T. Ueno, T. Koshiyama, S. Abe, N. Yokoi, M. Ohashi, H. Nakajima, Y. Watanabe
    • Journal Title

      J. Organometallic Chem. 692

      Pages: 142-147

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Hydrogen Peroxide Dependent Monooxygenations by Tricking the Substrate Recognition of Cytochrome P450BS ・"2007

    • Author(s)
      0. Shoji, T. Fujishiro, H. Nakajima, M. Kim, S. Nagano, Y. Shiro., Y. Watanabe
    • Journal Title

      Angew. Chem. Int. Ed. 46 (Selected as Very Important Paper)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Design and Structure Analysis of Artificial Metalloproteins : Selective Coordination of His64 to Copper Complexes with Square-Planar Structure in the apo-Myoglobin Scaffold.2007

    • Author(s)
      S. Abe, T. Ueno, P. A. N Reddy, S. Okazaki, T. Hikage, A. Suzuki, T Yamane, H. Nakajina., Y. Watanabe.
    • Journal Title

      Inorg. Chem. 46 (selected as a cover picture)

      Pages: 5137-5139

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Incorporation of a Phebox Rhodium Complex into apo-Myoglobin Affords a Stable Organometallic Protein Showing Unprecedented Arrangement of the Complex in the Cavity2007

    • Author(s)
      Y. Satake, S. Abe, S. Okazaki, N. Ban, T. Hikage, T. Ueno, B. Nakajima, A. Suzuki, T. Yamane. B. Nishiyana, Y. Watanabe
    • Journal Title

      Organometallics 26

      Pages: 4904-4908

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Design of Artificial Metalloenzymes using Non-Covalent Insertion of a Metal Complexes into a protein Scaffold.2007

    • Author(s)
      T. Ueno, T. Koshiyama, S. Abe, N. Yokoi, M. Ohashi, H. Nakajina, Y. Watanabe
    • Journal Title

      J. Organometallic Chem. 692

      Pages: 142-147

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Hydrogen Peroxide Dependent Monooxygenations by Tricking te substrate Recognition of Cytochrome P450_<BSβ>2007

    • Author(s)
      O. Shoji, T. Fujishiro, H. Nakajima, M.Kim, S. Nagano, Y: Shiro, and Y. Wata-nabe,
    • Journal Title

      Angew. Chem. Int. Ed. 46

      Pages: 3656-3659

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Design and Structure Analysis of Artificial Metalloproteins: Selective Coordinati-on of His64 to Copper Complexes with Square-Planar Structure in the apo-Myo-globin Scaffold2007

    • Author(s)
      S. Abe, T. Ueno, P.A.N. Reddy, S. Okazaki, T. Hikage, A. Suzuki, T. Yamane, H. Nakajima, and Y. Wat-anabe
    • Journal Title

      Inorg. Chem. 46

      Pages: 5137-5139

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Incorporation of a Phebox Rhodium Complex into apo-Myoglobin Affords a Stab-le Organometallic Protein Showing Unprecedented Arrangement of the Complex in the Cavity2007

    • Author(s)
      Y. Satake, S. Abe, S. Okazaki, N. Ban, T. Hikage, T. Ueno, H. Nakajima, A. Suzuki, T. Yamane, H. Nis-hiyama, and Y. Watanabe
    • Journal Title

      Organometallics 26

      Pages: 4904-4908

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Reactivities of Oxo and peroxo Intermediates Studied by Hemoprotein Mutants2007

    • Author(s)
      Y. Watanabe, H. Nakajima, and T. Ueno
    • Journal Title

      Acc. Chem. Res. 40

      Pages: 554-562

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Coordination Design of Artificial Metalloproteins Utilizing Protein Vacant Space2007

    • Author(s)
      T. Ueno, S. Abe, N. Yokoi, and Y. Watanabe
    • Journal Title

      Coord. Chem. Rev. 251

      Pages: 2717-2731

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hydrogen Peroxide Dependent Monooxygenations by Tricking the Substrate Recognition of Cytochrome P450_<BSβ">2007

    • Author(s)
      O.Shoji, T.Fujishiro, H.Nakajima, M.Kim, S.Nagano, Y.Shiro, Y.Watanabe
    • Journal Title

      Angew. Chem. Int. Ed. 46(In press)(On Line公開中)

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Conformational Changes during Apoplastocyanin Folding Observed by Photocleavable Modification and Transient Grating2006

    • Author(s)
      S.Hirota, Y.Fujimoto, J.Choi, N.Baden, N.Katagiri, M.Akiyama R., Hulsker, M.Ubbink, T.Okajima, T.Takabe, N.Funasaki, Y.Watanabe, M.Terazima
    • Journal Title

      J. Am. Chem. Soc. 128

      Pages: 7551-7558

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Design of Metal Cofactors Activated by Protein-Protein Electron Transfer System2006

    • Author(s)
      T.Ueno, N.Yokoi, M.Unno, T.Matsui, Y.Tokita, M.Yamada, M.Ikeda-Saito, H.Nakajima, Y.Watanabe
    • Journal Title

      Proc. Natl. Acad. Sci. USA 103

      Pages: 9416-9421

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Bionanotube Tetrapod Assembly by In Situ Synthesis of a Gold Nanocluster with (Gp5-His_6)_3 from Bacteriophage T4.2006

    • Author(s)
      T.Ueno, T.Koshiyama, T.Tsuruga, T.Goto, S.Kanamaru, F.Arisaka, Y.Watanabe
    • Journal Title

      Angew. Chem. Int. Ed. 45

      Pages: 4508-4512

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Reduction of Plastocyanin by Tyrosine-Containing Ologopeptides2006

    • Author(s)
      S.Hirota, H.Okumura, T.Kondoh, N.Funasaki, T.Takabe, Y.Watanabe
    • Journal Title

      J. Inorganic Biochemistry 100

      Pages: 1871-1878

    • Related Report
      2006 Annual Research Report
  • [Journal Article] Monooxygenation of an Aromatic Ring by F43W/H64D/V68I Myoglobin Mutant and Hydrogen Peroxide2005

    • Author(s)
      T.D.Pfister, T.Ohki, T.Ueno, I.Hara, S.Adachi, Y.Makino, N.Ueyama, Y.Lu, Y.Watanabe
    • Journal Title

      J.Biol.Chem. 280

      Pages: 12858-12866

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Coordinated Design of Cofactor and Active Site Structures in Development of New Protein Catalysts2005

    • Author(s)
      T.Ueno, T.Koshiyama, M.Ohashi, K.Kondo, M.Kono, A.Suzuki, T.Yamane, Y.Watanabe
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 6556-6562

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Reversible and Regioselective Reaction of La@C62 with Cyclopentadiene2005

    • Author(s)
      Y.Maeda, J.Miyashita, T.Hasegawa, T.Wakahara, T.Tsuchiya, T.Nakahodo, T.Akasaka, N.Mizorogi, K.Kobayashi, S.Nagase, T.Kato, N.Ban, H.Nakajima, Y.Watanabe
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 12190-12191

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Structural and Spectroscopic Characterization of (μ-Hydroxo or μ-Oxo)(μ-Peroxo)diiron(III) Complexes : Models for Peroxo Intermediates of Non-Heme Diiron Proteins2005

    • Author(s)
      X.Zhang, H.Furutachi, S.Fujinami, S.Nagatomo, Y.Maeda, Y.Watanabe, T.Kitagawa, M.Suzuki
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 826-827

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Reversible O-O Bond Cleavage and Formation of a Peroxo Moiety of a Peroxocarbonate Ligand Mediated by an Iron(III) Complex2005

    • Author(s)
      H.Furutachi, K.Hashimoto, S.Nagatomo, T.Endo, S.Fujinami, Y.Watanabe, T.Kitagawa, M.Suzuki
    • Journal Title

      J.Am.Chem.Soc. 127

      Pages: 4550-4551

    • Related Report
      2005 Annual Research Report
  • [Journal Article] Monooxygenation of an Aromatic Ring by F43W/H64D/V68I Myoglobin Mutant and Hydrogen Peroxide.2005

    • Author(s)
      T.D.Pfister, T.Ohki, T.Ueno, I.Hara, S.Adachi, Y.Makino, N.Ueyama, Y.Lu, Y.Watanabe
    • Journal Title

      J.Biol.Chem. 280(印刷中)

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Size Selective Olefin Hydrogenation by a Pd Nanocluster Provided in the Apo-Ferritin Cage2004

    • Author(s)
      T.Ueno, M.Suzuki, T.Goto, T.Matsumoto, K.Nagayama, Y.Watanabe
    • Journal Title

      Angew.Chem.Int.Ed. 43

      Pages: 2527-2530

    • Related Report
      2004 Annual Research Report
  • [Journal Article] Crystal Structures of Artificial Metalloproteins2004

    • Author(s)
      T.Ueno, M.Ohashi, M.Kono, K.Kondo A.Suzuki, T.Yamane, Y.Watanabe
    • Journal Title

      Inorg.Chem. 43

      Pages: 2852-2858

    • Related Report
      2004 Annual Research Report
  • [Journal Article] 蛋白質空間を利用した物質返還-ヘム酵素を中心とした金属酵素の分子設計2004

    • Author(s)
      渡辺 芳人
    • Journal Title

      蛋白質・核酸・酵素 49

      Pages: 2253-2259

    • Related Report
      2004 Annual Research Report
  • [Presentation] 有機金属酵素の分子設計:蛋白質内部空間への金属錯体、金属イオンの導入2008

    • Author(s)
      渡辺芳人
    • Organizer
      第2期菅野シンポジウム(第4回講演会)
    • Place of Presentation
      東京
    • Year and Date
      2008-03-08
    • Related Report
      2007 Annual Research Report
  • [Presentation] Coordination Chemistry in Protein Cages2008

    • Author(s)
      Y. Watanabe
    • Organizer
      Inorganic Chemistry Colloquium at Yale University
    • Place of Presentation
      New Haven, USA
    • Year and Date
      2008-02-26
    • Related Report
      2007 Annual Research Report
  • [Presentation] Coordination Chemistry in Protein Cages2008

    • Author(s)
      Y. Watanabe, T. Ueno, T. Koshiya-ma, M. Suzuki, S. Abe, and M Abe
    • Organizer
      The 10th Eurasia Conference on Chemical Sciences (EuAs C_2S-10)
    • Place of Presentation
      Manila, Phillipines
    • Related Report
      2007 Annual Research Report
  • [Presentation] 生体反応場錯体化学2008

    • Author(s)
      渡辺芳人
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Related Report
      2007 Annual Research Report
  • [Presentation] ナノサイズ空間を有する蛋白質を利用した金属微粒子作成2008

    • Author(s)
      渡辺芳人
    • Organizer
      日本化学会第88春季年会
    • Place of Presentation
      東京
    • Related Report
      2007 Annual Research Report
  • [Presentation] Transformation of Cytochrome P450BSβ into a Versatile Peroxygenase2007

    • Author(s)
      Y. Watanabe
    • Organizer
      The 4th joint IRTG SYMPOSIUM between Nagoya University and University of Munster
    • Place of Presentation
      Munster, Germany
    • Year and Date
      2007-09-06
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Construction of Organometalloproteins2007

    • Author(s)
      Y. Watanabe
    • Organizer
      The Second International Conference on Joint Project of Chemical Synthesis Core Research Institutions
    • Place of Presentation
      Kyoto, Japan.
    • Year and Date
      2007-08-07
    • Related Report
      2007 Annual Research Report
  • [Presentation] Transformation of Cytochrome P450BSβ into a Versatile Peroxygenase2007

    • Author(s)
      Y. Watanabe
    • Organizer
      The 4th joint IRTG SYMPOSIUM between Nagoya University and University of Munster
    • Place of Presentation
      Munster, Germany.
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Construction of Organometalloproteins: A New Approach for Bioinorganic Chemistry2007

    • Author(s)
      Y. Watanabe
    • Organizer
      Japan-USA Joint Symposium of Chemistry of Coordinati on Space
    • Place of Presentation
      Evanston, USA
    • Related Report
      2007 Annual Research Report
  • [Presentation] Construction of Organometalloproteins: A New Approach for Bioinorganic Chemistry2007

    • Author(s)
      Y. Watanabe
    • Organizer
      The First Asian Conference on Coordination Chemistry
    • Place of Presentation
      Okazaki, Japan
    • Related Report
      2007 Annual Research Report
  • [Presentation] Transformation of Cytochrome P450d_<BSβ> into a Versatile Peroxygenase2007

    • Author(s)
      Y. Watanabe
    • Organizer
      The 4th joint IRTG SYMPOSIUM between Nagoya University and University of Munster
    • Place of Presentation
      Munster, Germany
    • Related Report
      2007 Annual Research Report
  • [Presentation] Introduction of Metal Cofactors in Protein cages: Construction of Organometallo protein2007

    • Author(s)
      Y. Watanabe
    • Organizer
      The 67th Okazaki Conference
    • Place of Presentation
      Okazaki, Japan
    • Related Report
      2007 Annual Research Report
  • [Presentation] Molecular Design of Organometalloenzymes2007

    • Author(s)
      Y. Watanabe
    • Organizer
      The 11th International Chemical Conference, Taipei (ICCT)
    • Place of Presentation
      Hsinchu, Taiwan
    • Related Report
      2007 Annual Research Report
  • [Book] 金属酵素の設計に挑む2006

    • Author(s)
      渡辺芳人, 上野 隆史
    • Total Pages
      10
    • Publisher
      化学同人
    • Related Report
      2006 Annual Research Report
  • [Book] Functionalization of Myoglobin In Progress in Inorganic Chemistry2005

    • Author(s)
      Y.Watanabe, T.Hayashi
    • Total Pages
      43
    • Publisher
      Wiley-Interscience
    • Related Report
      2005 Annual Research Report
  • [Remarks]

    • URL

      http://bioinorg.chem.nagoya-u.ac.jp/

    • Related Report
      2007 Annual Research Report
  • [Patent(Industrial Property Rights)] 改変アポフェリチンの製造法とその利用2006

    • Inventor(s)
      上野 隆史, 渡辺芳人, 鈴木理子, 安部聡, 安部瑞恵, 平田邦夫, 山本雅貴, 高田昌樹
    • Industrial Property Rights Holder
      財団法人 名古屋産業科学研究所
    • Industrial Property Number
      2006-243246
    • Filing Date
      2006-09-07
    • Related Report
      2006 Annual Research Report

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Published: 2004-04-01   Modified: 2018-03-28  

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