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Development of Novel Artificial Dinuclear Metalloenzymes and Application to Catalytic Oxidation Reactions

Research Project

Project/Area Number 25620044
Research Category

Grant-in-Aid for Challenging Exploratory Research

Allocation TypeMulti-year Fund
Research Field Inorganic chemistry
Research InstitutionOsaka University

Principal Investigator

ITOH Shinobu  大阪大学, 工学(系)研究科(研究院), 教授 (30184659)

Co-Investigator(Renkei-kenkyūsha) SUGIMOTO Hideki  大阪大学, 大学院工学研究科, 准教授 (00315970)
FUJIEDA Nobutaka  大阪大学, 大学院工学研究科, 助教 (00452318)
Project Period (FY) 2013-04-01 – 2015-03-31
Project Status Completed (Fiscal Year 2014)
Budget Amount *help
¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2014: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000)
Fiscal Year 2013: ¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Keywords人工金属酵素 / 酸化酵素 / 遷移金属錯体 / 金属結合タンパク質 / チロシナーゼ / 超好熱菌 / コウジ菌 / 二核金属酵素 / 酸化反応 / 触媒反応 / 超好熱菌由来タンパク質
Outline of Final Research Achievements

In this study, novel artificial metalloenzymes have been developed using dicopper copper monooxygenase tyrosinase and metal-binding protein TM1459 from hyperthermophiles. The crystal structures of the deoxy-, met-, and oxy-forms of tyrosinase from Aspergillus oryzae and its mutants have been determined, and their spectroscopic and magnetic characteristics as well as the catalytic activity have been explored in detail. On the basis of those information, artificial dicopper enzymes have been developed for the catalytic phenol oxidation reactions. Furthermore, novel metalloenzymes containing several transition-metal ions such as Zn, Cu, Ni, Co, Fe, Mn, Cr, V, Ru, Os have been developed by using a simple metal-binding protein from Thermotoga maritima, and their crustal structures as well as the spectroscopic, magnetic properties and catalytic activity have been examined in detail.

Report

(3 results)
  • 2014 Annual Research Report   Final Research Report ( PDF )
  • 2013 Research-status Report
  • Research Products

    (21 results)

All 2015 2014 2013

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Acknowledgement Compliant: 2 results) Presentation (11 results) (of which Invited: 11 results) Book (2 results)

  • [Journal Article] Redox behavior of novel nickel and palladium complexes supported by trianionic non-innocent ligand containing β-diketiminate and phenol groups2015

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      J. Porphyrins Phthalocyanines

      Volume: 19 Issue: 01-03 Pages: 377-387

    • DOI

      10.1142/s1088424615500248

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Electrochemical reduction of dioxygen by copper complexes with pyridylalkylamine ligands dissolved in aqueous buffer solution: relationship between activity and redox potential2014

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Dalton Trans.

      Volume: 43 Issue: 28 Pages: 10705-10709

    • DOI

      10.1039/c4dt00606b

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Geometric control of nuclearity in copper(I)/dioxygen chemistry2014

    • Author(s)
      T. Abe, Y. Morimoto, T. Tano, K. Mieda, H. Sugimotok N. Fujieda, T. Ogura, and S. Itoh
    • Journal Title

      Inorganic Chemistry

      Volume: 53 Issue: 16 Pages: 8786-8794

    • DOI

      10.1021/ic501461n

    • Related Report
      2014 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Copper complexes supported by an N2S-tridentate ligand as active site models of copper monooxygenases2014

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Dalton Trans.

      Volume: 42 Issue: 12 Pages: 4871-4877

    • DOI

      10.1039/c3dt52952e

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Activation Mechanism of MelB Tyrosinase from Aspergillus oryzae by acidic treatment2013

    • Author(s)
      Fujieda, N., Murata, M., Yabuta, S., Ikeda, T., Shimokawa, C., Nakamura, Y., Hata, Y., and Itoh, S.
    • Journal Title

      J. Biol. Inorg. Chem.

      Volume: 18 Issue: 1 Pages: 19-26

    • DOI

      10.1007/s00775-012-0945-5

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Crystal Structures Of Copper-Depleted And Copper-Bound Fungal Pro-Tyrosinase: Insights Into Endogenous Cysteine-Dependent Copper Incorporation2013

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      J. Biol.Chem.

      Volume: 288 Issue: 30 Pages: 22128-22140

    • DOI

      10.1074/jbc.m113.477612

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Redox Properties of Mononuclear Copper(II)-Superoxide Complex2013

    • Author(s)
      Shinobu Itoh
    • Journal Title

      Inorg. Chem.

      Volume: 52 Issue: 18 Pages: 10431-10437

    • DOI

      10.1021/ic401261z

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Journal Article] Flavonolate Complexes of MII (M = Mn, Fe, Co, Ni, Cu, and Zn). Structural and Functional Models for the ES (Enzyme-Substrate) Complex of Quercetin 2,3-Dioxygenase2013

    • Author(s)
      Shinobu Itoh, et al.
    • Journal Title

      Inorg. Chem.

      Volume: 52 Issue: 19 Pages: 10936-10948

    • DOI

      10.1021/ic400972k

    • Related Report
      2013 Research-status Report
    • Peer Reviewed
  • [Presentation] Developing Mononuclear Copper Reaction Site for Oxygen Activation2015

    • Author(s)
      Shinobu Itoh
    • Organizer
      Gordon Research Conference (Metals in Biology)
    • Place of Presentation
      Ventura, California, USA
    • Year and Date
      2015-01-25 – 2015-01-30
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Oxygen Activation at Mononuclear Copper Reaction Center2014

    • Author(s)
      Shinobu Itoh
    • Organizer
      7th Asian Biological Inorganic Chemistry Conference (AsBIC7)
    • Place of Presentation
      Gold Coast, Australia
    • Year and Date
      2014-11-30 – 2014-12-05
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Molecular Oxygen Activation by Copper Proteins and Models2014

    • Author(s)
      Shinobu Itoh
    • Organizer
      9th International Copper Meeting
    • Place of Presentation
      Vivo Equense, Italy
    • Year and Date
      2014-10-05 – 2014-10-10
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Controlling Reactivity of Copper-Peroxide Complexes2014

    • Author(s)
      Shinobu Itoh
    • Organizer
      41th International Conference on Coordination Chemistry (ICCC-41)
    • Place of Presentation
      Suntec Singapore Convention & Exhibition Center, Singapore
    • Year and Date
      2014-07-21 – 2014-07-25
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Nickel-complex Catalyzed Hydroxylation of Aliphatic and Aromatic Compounds2014

    • Author(s)
      Shinobu Itoh
    • Organizer
      2014 Canada-Japan Workshop (pre-ISHC)
    • Place of Presentation
      University of Ottawa, Canada
    • Year and Date
      2014-07-05 – 2014-07-06
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] C-H Bond Activation by Copper Active-oxygen Complexes2014

    • Author(s)
      Shinobu Itoh
    • Organizer
      International Conference on Hydrogen Atom Transfer (iCHAT 2014)
    • Place of Presentation
      Rome, Italy
    • Year and Date
      2014-06-22 – 2014-06-26
    • Related Report
      2014 Annual Research Report
    • Invited
  • [Presentation] Mononuclear Copper Active Oxygen Complexes Relevant to the Reactive Intermediate Involved in Copper Monooxygenases2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      16th International Conference of Biological Inorganic Chemiastry (ICBIC16)
    • Place of Presentation
      Grenoble, France
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] Copper Complexes of Non-innocent β-Diketiminate Ligands2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      15th Asian Chemical Congress (15ACC)
    • Place of Presentation
      Singapore
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] Ligand Design for Oxygen Activation by Copper Complexes2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      The 2nd Canada-Japan Joint Symposium on Coordination Chemistry
    • Place of Presentation
      Okinawa
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] Oxygen Activation Chemistry at Mononuclear Copper Reaction Center2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      The 4th Asian Conference on Coordination Chemistry (ACCC4)
    • Place of Presentation
      Jeju, South Korea
    • Related Report
      2013 Research-status Report
    • Invited
  • [Presentation] Recent Advances in Copper-Dioxygen Chemistry2013

    • Author(s)
      Shinobu Itoh
    • Organizer
      Symposium on Modern Trends in Inorganic Chemistry–XV
    • Place of Presentation
      Roorkee, India
    • Related Report
      2013 Research-status Report
    • Invited
  • [Book] Chemical Science of π-Electron Systems2015

    • Author(s)
      Shinobu Itoh and Yuma Morimoto
    • Total Pages
      500
    • Publisher
      Springer
    • Related Report
      2014 Annual Research Report
  • [Book] Handbook of Metalloproteins to the Encyclopedia of Inorganic and Bioinorganic Chemistry2015

    • Author(s)
      Nobutaka Fujieda and Shinobu Itoh
    • Total Pages
      300
    • Publisher
      John Wiley & Sons
    • Related Report
      2014 Annual Research Report

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Published: 2014-07-25   Modified: 2019-07-29  

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