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New Development of Coordination Chemistry in Biorelated Metal Complexes of Cyclic Tetrapyrroles

Research Project

Project/Area Number 16H04119
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionKyushu University

Principal Investigator

Hisaeda Yoshio  九州大学, 工学研究院, 教授 (70150498)

Research Collaborator Shimakosi Hisashi  
Ono Toshikazu  
Koide Taro  
Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2018: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2017: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000)
Fiscal Year 2016: ¥9,100,000 (Direct Cost: ¥7,000,000、Indirect Cost: ¥2,100,000)
Keywords生体関連金属錯体 / 光増感剤 / ポルフィリン異性体 / 環状ピロール化合物 / ハイブリッド触媒 / 酸化還元反応 / バイオインスパイアード / 電解反応 / ポルフィセン / ビタミンB12 / 光反応 / 発光特性 / 触媒反応 / 脱ハロゲン化反応 / 二量化反応 / ピロール系金属錯体 / ビタミンB12誘導体 / トリフルオロメチル化反応 / 酸化チタン / コバルト錯体 / テトラピロール系金属錯体 / 電気化学反応
Outline of Final Research Achievements

As part of a study directed toward design of artificial enzymes based upon a hydrophobic vitamin B12, we report preparation of various nanomaterials with the vitamin B12 derivative and photosensitizers. We have been dealing with a hydrophobic vitamin B12, heptamethyl cobyrinate perchlorate, which has ester groups in place of the peripheral amide moieties of the naturally occurring vitamin B12. In order to construct a good catalytic system, we prepared various nanomaterials with vitamin B12 activities. One example is a vitamin B12-titanium dioxide hybrid catalyst. This bioinspired material has potential as catalytic systems for degradation of organic halide pollutants and for molecular transformations via radical intermediates under irradiation with UV or visible light, and offer scope for applications that are of great interest in terms of green chemistry. We also applied electrochemical catalytic system with hydrophobic vitamin B12 for trifluoromethylations and perfluoroalkylations.

Academic Significance and Societal Importance of the Research Achievements

これからの科学技術に期待されるのは環境との調和である。生体系の機能発現を範とし、それに工学的な発想を加味して生体系の機能を凌駕する技術を目指すバイオインスパイアード材料の開発が注目されている。生体系においてヘム、ビタミンB12などの環状テトラピロール系金属錯体は生命の色素と言われ、極めて重要で多彩な機能を発現している。これらを含む金属酵素は、高活性・高選択的であるが、構造安定性に欠け応用範囲が狭いなどの欠点も多い。そこで本研究では、単なる酵素機能のシミュレーションに留まらず、光増感剤と生体関連金属錯体の組み合わせにより革新的機能材料を開発し、生物無機化学の新領域を開拓した。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • Research Products

    (44 results)

All 2019 2018 2017 2016 Other

All Int'l Joint Research (1 results) Journal Article (26 results) (of which Int'l Joint Research: 4 results,  Peer Reviewed: 26 results,  Open Access: 8 results,  Acknowledgement Compliant: 6 results) Presentation (17 results) (of which Int'l Joint Research: 12 results,  Invited: 16 results)

  • [Int'l Joint Research] ポーランド科学アカデミー/有機化学研究所(ポーランド)

    • Related Report
      2018 Annual Research Report
  • [Journal Article] Redox behaviour of the β-dihydroporphycene cobalt complex: study on the effect of hydrogenation of the ligand2019

    • Author(s)
      Hashimoto Koichi, Koide Taro, Okawara Toru, Shimakoshi Hisashi, Hori Yuta, Shiota Yoshihito, Yoshizawa Kazunari, Hisaeda Yoshio
    • Journal Title

      Dalton Transactions

      Volume: 48 Issue: 3 Pages: 872-881

    • DOI

      10.1039/c8dt03743d

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Flexible-color tuning and white-light emission in three-, four-, and five-component host/guest co-crystals by charge-transfer emissions as well as effective energy transfers2019

    • Author(s)
      Toshikazu Ono, Yoshio Hisaeda
    • Journal Title

      J. Mater. Chem. C

      Volume: 7 Issue: 10 Pages: 2829-2842

    • DOI

      10.1039/c8tc06165c

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Photocatalytic function of the B12 complex with the cyclometalated iridium(III) complex as a photosensitizer under visible light irradiation2018

    • Author(s)
      H. Tian, H, Shimakoshi, S. Kim, G. Park, Y. You, Y. Hisaeda
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 3 Pages: 675-683

    • DOI

      10.1039/c8dt90007h

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Electrochemistry and catalytic properties of vitamin B12 derivatives in nonaqueous media2018

    • Author(s)
      H. Shimakoshi, Y. Hisaeda
    • Journal Title

      Current Opinion in Electrochemistry

      Volume: 8 Pages: 24-30

    • DOI

      10.1016/j.coelec.2017.12.001

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] First entry into nonmetal-centred porphycenes: synthesis of a phosphorus (V) complex of octaethylporphycene2018

    • Author(s)
      Abe Masaaki, Hiroto Mukotaka, Taro Fujioka, Toru Okawara, Kei Umegaki, Toshikazu Ono, Yoshio Hisaeda
    • Journal Title

      Dalton Transactions

      Volume: 47 Issue: 8 Pages: 2487-2491

    • DOI

      10.1039/c7dt04471b

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Piezofluorochromism in Charge‐Transfer Inclusion Crystals: The Influence of High Pressure versus Mechanical Grinding2018

    • Author(s)
      Toshikazu Ono, Yoshifumi Tsukiyama, Ai Taema, Hiroyasu Sato, Hidetoshi Kiyooka, Yuma Yamaguchi, Ayumi Nagahashi, Manami Nishiyama, Yuichi Akahama, Yoshiki Ozawa, Masaaki Abe, Yoshio Hisaeda
    • Journal Title

      ChemPhotoChem

      Volume: 印刷中 Issue: 5 Pages: 416-420

    • DOI

      10.1002/cptc.201700227

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Synthesis of Trifluoromethylated B12 Derivative and Photolysis of Cobalt(III)?Trifluoromethyl Bond2018

    • Author(s)
      Ono Toshikazu、Wakiya Kosuke、Hossain Md. Jakir、Shimakoshi Hisashi、Hisaeda Yoshio
    • Journal Title

      Chemistry Letters

      Volume: 47 Issue: 8 Pages: 979-981

    • DOI

      10.1246/cl.180355

    • NAID

      130007431003

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Cobalt?Carbon Bond Formation Reaction via Ligand Reduction of Porphycene?Cobalt(II) Complex and Its Noninnocent Reactivity2018

    • Author(s)
      Koide Taro、Aritome Isao、Saeki Tatsuya、Morita Yoshitsugu、Shiota Yoshihito、Yoshizawa Kazunari、Shimakoshi Hisashi、Hisaeda Yoshio
    • Journal Title

      ACS Omega

      Volume: 3 Issue: 4 Pages: 4027-4034

    • DOI

      10.1021/acsomega.8b00239

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Learning from B12 enzymes: biomimetic and bioinspired catalysts for eco-friendly organic synthesis2018

    • Author(s)
      Tahara Keishiro、Pan Ling、Ono Toshikazu、Hisaeda Yoshio
    • Journal Title

      Beilstein Journal of Organic Chemistry

      Volume: 14 Pages: 2553-2567

    • DOI

      10.3762/bjoc.14.232

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Visible Light‐Driven, One‐pot Amide Synthesis Catalyzed by the B 12 Model Complex under Aerobic Conditions2018

    • Author(s)
      Tian Hui、Shimakoshi Hisashi、Ono Toshikazu、Hisaeda Yoshio
    • Journal Title

      ChemPlusChem

      Volume: 84 Issue: 3 Pages: 237-240

    • DOI

      10.1002/cplu.201800522

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Switching of Monomer Fluorescence, Charge-Transfer Fluorescence, and Room-Temperature Phosphorescence Induced by Aromatic Guest Inclusion in a Supramolecular Host (Chem. Eur. J. 66/2018)2018

    • Author(s)
      Ono Toshikazu、Taema Ai、Goto Aiko、Hisaeda Yoshio
    • Journal Title

      Chemistry - A European Journal

      Volume: 24 Issue: 66 Pages: 17368-17368

    • DOI

      10.1002/chem.201805575

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Gram-scale synthesis of porphycenes through acid-catalyzed oxidative macrocyclizations of E/Z-mixed 5,6-diaryldipyrroethenes2018

    • Author(s)
      Toshikazu Ono, Ning Xu, Daiki Koga, Toshihiro Ideo, Manabu Sugimoto, Yoshio Hisaeda
    • Journal Title

      RSC Adv.

      Volume: 8 Issue: 69 Pages: 39269-39273

    • DOI

      10.1039/c8ra09040h

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Photocatalytic alkene reduction by a B12-TiO2 hybrid catalyst coupled with C-F bond cleavage for gem-difluoroolefin synthesis2017

    • Author(s)
      Tian Hui、Shimakoshi Hisashi、Imamura Kenji、Shiota Yoshihito、Yoshizawa Kazunari、Hisaeda Yoshio
    • Journal Title

      Chem. Commun.

      Volume: 53 Issue: 68 Pages: 9478-9481

    • DOI

      10.1039/c7cc04377e

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Hybrid Catalyst for Light-Driven Green Molecular Transformations2017

    • Author(s)
      H. Shimakoshi, Y. Hisaeda
    • Journal Title

      ChemPlusChem

      Volume: 82 Issue: 1 Pages: 18-29

    • DOI

      10.1002/cplu.201600303

    • Related Report
      2017 Annual Research Report 2016 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Facile synthesis of 9,10,19,20-tetraalkylporphycenes2017

    • Author(s)
      T. Ono, D. Koga, Y. Hisaeda
    • Journal Title

      Chem. Lett.

      Volume: 46 Issue: 2 Pages: 260-262

    • DOI

      10.1246/cl.161019

    • NAID

      130005317145

    • Related Report
      2017 Annual Research Report 2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Cathodic Reductive Couplings and Hydrogenations of Alkenes and Alkynes Catalyzed by the B12 Model Complex2017

    • Author(s)
      H. Shimakoshi, Z. Luo, K. Tomita, Y. Hisaeda
    • Journal Title

      J. Organomet. Chem.

      Volume: 印刷中 Pages: 71-77

    • DOI

      10.1016/j.jorganchem.2017.02.002

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Significant enhancement of visible light photocatalytic activity of the hybrid B12-PIL/rGO in the presence of Ru(bpy)32+ for DDT dehalogenation2017

    • Author(s)
      Ying Sun, Wei Zhang, Jian Tong, Yu Zhang, Shuyao Wu, Daliang Liu, Hisashi Shimakoshi, Yoshio Hisaeda, Xi-Ming Song
    • Journal Title

      RSC Advances

      Volume: 7 Issue: 31 Pages: 19197-19204

    • DOI

      10.1039/c7ra02062g

    • Related Report
      2017 Annual Research Report 2016 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Inclusion crystal growth and optical properties of organic charge transfer complexes built from small aromatic guest molecules and naphthalenediimide derivatives2017

    • Author(s)
      T. Ono, Y. Tsukiyama, A. Taema, Y. Hisaeda
    • Journal Title

      Chem. Lett.

      Volume: 印刷中 Issue: 6 Pages: 801-804

    • DOI

      10.1246/cl.170122

    • NAID

      130005689370

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Impact of the corrin framework of vitamin B12 on the electrochemical carbon-skeleton rearrangement in comparison to an imine/oxime planar ligand; tuning selectivity in 1,2-migration of a functional group by controlling electrolysis potential2017

    • Author(s)
      K. Tahara, L. Pan, R. Yamaguchi, H. Shimakoshi, M. Abe, Y. Hisaeda
    • Journal Title

      J. Inorg. Biochem.

      Volume: 175 Pages: 239-243

    • DOI

      10.1016/j.jinorgbio.2017.07.021

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] A Vitamin B12 Derivative Catalyzed Electrochemical Trifluoromethylation and Perfluoroalkylation of Arenes and Heteroarenes in Organic Media2017

    • Author(s)
      M. J. Hossain, T. Ono, K. Wakiya, Y. Hisaeda
    • Journal Title

      Chem. Commun.

      Volume: 53 Issue: 79 Pages: 10878-10881

    • DOI

      10.1039/c7cc06221d

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] meso-Tetraaryl(porphyrinato)cobalt(III)-Catalyzed Oxygenation of Disilanes under Aerobic Conditions2017

    • Author(s)
      J. Ohshita, Y. Matsumura, T. Nakayama, H. Yoshida, A. Kunai, Y. Hisaeda, T. Hayashi
    • Journal Title

      Chem. Lett.

      Volume: 46 Issue: 12 Pages: 1807-1809

    • DOI

      10.1246/cl.170857

    • NAID

      130006243159

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] The first synthesis of mesodicycloalkylporphycenes: ring strain effects on structural and optical properties of isomeric porphyrins2017

    • Author(s)
      T. Ono, D. Koga, K. Yoza, Y. Hisaeda
    • Journal Title

      Chem. Commun.

      Volume: 53 Issue: 91 Pages: 12258-12261

    • DOI

      10.1039/c7cc07170a

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Supramolecular System Composed of B12 Model Complex and Organic Photosensitizer: Impact of the Corrin Framework of B12 on the Visible-Light-Driven Dechlorination without the Use of Noble Metals2016

    • Author(s)
      K. Tahara, K. Mikuriya, T. Masuko, J. Kikuchi, Y. Hisaeda
    • Journal Title

      Supramolecular Chemistry

      Volume: 28 Issue: 1-2 Pages: 141-150

    • DOI

      10.1080/10610278.2015.1103373

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Intraprotein transmethylation via a CH3–Co(III) species in myoglobin reconstituted with a cobalt corrinoid complex2016

    • Author(s)
      Y. Morita, K. Oohora, A. Sawada, K. Doitomi, J. Ohbayashi, T. Kamachi, K. Yoshizawa, Y. Hisaeda, T. Hayashi
    • Journal Title

      Dalton Transactions

      Volume: 45 Issue: 8 Pages: 3277-3284

    • DOI

      10.1039/c5dt04109k

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access
  • [Journal Article] Electrochemistry and Catalytic Properties of Amphiphilic Vitamin B12 Derivatives in Nonaqueous Media2016

    • Author(s)
      M. Giedyk, H. Shimakoshi, K. Goliszewska, D. Gryko, Y. Hisaeda
    • Journal Title

      Dalton Trans

      Volume: 45 Issue: 20 Pages: 8340-8346

    • DOI

      10.1039/c6dt00355a

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Electrolysis of Trichloromethylated Organic Compounds under Aerobic Conditions Catalyzed by B12 Model Complex for Ester and Amide Formations2016

    • Author(s)
      H. Shimakoshi, Z. Luo, T. Inaba, Y. Hisaeda
    • Journal Title

      Dalton Trans.

      Volume: 45 Issue: 25 Pages: 10173-10180

    • DOI

      10.1039/c6dt00556j

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Bioinspired Catalytic System with Vitamin B12 Function2018

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      Conference on New Advances in the Chemistry of Porphyrinoids
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Facile Synthesis of Porphycene Derivatives and Reactivity of Cobalt Porphycene2018

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      10th International Conference on Porphyrins & Phthalocyanines (ICPP-10)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Electrochemical Perfluoroalkylation of Arenes and Heteroarenes Catalyzed by Vitamin B12 Derivative2018

    • Author(s)
      Y. Hisaeda, M. J. Hossain, T. Ono, H. Shimakoshi, H. Amii, D. Gryko
    • Organizer
      International Conference on Coordination Chemistry (ICCC)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Electrochemical Perfluoroalkylations of Arenes and Heteroarenes by Bioinspired Catalytic System2018

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      13th International Symposium on Organic Reaction (ISOR-13)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Bioinspired Catalysts with Vitamin B12 Function Activated by Photochemical and Electrochemical Methods2017

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      2nd International Symposium on Precisely Designed Catalysts with Customized Scaffolding
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Bioinspired Catalyst with Vitamin B12 Functions Activated by Photochemical or Electrochemical Methods2017

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      26th International Conference on Coordination and Bioinorganic Chemistry
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 生体関連色素の化学 “ビタミンB12酵素から学ぶバイオインスパイアード触媒”2017

    • Author(s)
      久枝良雄
    • Organizer
      ブルカー・バイオスピン株式会社 九州サービスセンター開所記念セミナー
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Bioinspired Catalytic Reactions Using Vitamin B12 Derivative2017

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      6th Asian Conference on Coordination Chemistry(
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 光化学的手法を用いたバイオインスパイアード触媒の開発2017

    • Author(s)
      久枝良雄
    • Organizer
      第29回配位化合物の光化学討論会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 人工酵素 バイオインスパイアード触媒2017

    • Author(s)
      久枝良雄
    • Organizer
      化学物質評価研究機構(CERI) 寄付講座 CERI公開講座 「先端材料化学から設計、構造・物性から機能化まで」
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Bioinspired Catalyst with Vitamin B12 Functions Using Photochemical and Electrochemical Methods2017

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      5th CMS International Symposium (CMS-5) on Photofunctional Chemistry and Molecular Systems
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] 光および電気化学活性化を用いたバイオインスパイアード触媒の創製2017

    • Author(s)
      久枝良雄
    • Organizer
      群馬大学元素科学国際教育研究センター主催講演会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Bioinspired Catalytic Reaction Lessons from Vitamin B12 Enzyme2016

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      8th Asian Biological Inorganic Chemistry Conference (AsBIC8-2016)
    • Place of Presentation
      Auckland, New Zealand
    • Year and Date
      2016-12-06
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Bioinspired Catalysts with Vitamin B12 Derivatives Using Photochemical and Electrochemical Methods2016

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      International Symposium on Catalysis and Fine Chemicals in Taipei-2016 (C&FC-2016)
    • Place of Presentation
      Taipei, Taiwan
    • Year and Date
      2016-11-12
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Bioinspired Catalysts based on Vitamin B12 Chemistry2016

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      9th International Conference on Porphyrins & Phthalocyanines(ICPP-9)
    • Place of Presentation
      Nanjing, China
    • Year and Date
      2016-07-05
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Bioinspired Catalysts with Vitamin B12 Functions Using Photosensitizer or Electrochemical Method2016

    • Author(s)
      Yoshio Hisaeda
    • Organizer
      The 12th International Symposium on Organic Reactions and The 6th German-Japanese Symposium on Electrosynthesis (ISOR-12 and GJSE-6)
    • Place of Presentation
      京都
    • Year and Date
      2016-04-22
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] ARTIFICIAL ENZYMES COMPOSED OF PHOTOSENSITIZER AND VITAMIN B12 DERIVATIVE2016

    • Author(s)
      Yoshio Hisaeda, Hisashi Shimakoshi, Takahiro Masuko, and Toshikazu Ono
    • Organizer
      26th IUPAC Symposium on Photochemistry
    • Place of Presentation
      大阪
    • Year and Date
      2016-04-06
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited

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Published: 2016-04-21   Modified: 2020-03-30  

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