Construction of an array of photosensitizers within a ring-shaped hemoprotein assembly toward a light harvesting system

• Project/Area Number: 25810099
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Bio-related chemistry
• Research Institution: Osaka University
• Principal Investigator: Oohora Koji 大阪大学, 工学(系)研究科(研究院), 助教 (10631202)
• Research Collaborator: HAYASHI Takashi ; MAHISMA Tsuyoshi
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2014: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2013: ¥2,600,000 (Direct Cost: ¥2,000,000、Indirect Cost: ¥600,000)
• Keywords: 光捕集 / ヘムタンパク質 / 超分子 / 光増感剤 / 超分子化学 / タンパク質集合体

Outline of Final Research Achievements

A hexameric tyrosine-coordinated heme protein (HTHP) containing photosensitizer molecules was prepared in an effort to construct a biomolecule with engineered photochemical properties. Zn protoporphyrin IX (ZnPP) and Zn chlorin e6 (ZnCe6) are inserted into the apoprotein of HTHP to yield reconstituted proteins which maintain the original hexameric structure of HTHP. The fluorescence quenching efficiencies provided by methyl viologen as an electron acceptor for the completely reconstituted proteins with ZnPP and ZnCe6 are 2.3 and 2.6 fold-higher than that of the corresponding partially photosensitizer-inserted proteins, respectively. This indicates that energy migration occurs among the photosensitizers bound within the protein matrices. These findings are expected to lead to development of new protein-based artificial light harvesting systems to demonstrate the light-driven energy conversion.

Research Products

• [Journal Article] Intraprotein transmethylation via a CH3–Co(III) species in myoglobin reconstituted with a cobalt corrinoid complex (2016)
  • 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
  • Peer Reviewed / Open Access
• [Journal Article] Crystal Structures and Coordination Behavior of Aqua- and Cyano-Co(III) Tetradehydrocorrins in the Heme Pocket of Myoglobin (2016)
  • Author(s): Y. Morita, K. Oohora, E. Mizohata, A. Sawada, T. Kamachi, K. Yoshizawa, T. Inoue, T. Hayashi
  • Journal Title: Inorganic Chemistry Volume: 55 Issue: 3 Pages: 1287-1295
  • DOI: 10.1021/acs.inorgchem.5b02598
  • Peer Reviewed
• [Journal Article] Oxygen-binding Protein Fiber and Microgel: Supramolecular Myoglobin–Poly(acrylate) Conjugates (2016)
  • Author(s): T. Ono, Y. Hisaoka, A. Onoda, K. Oohora, T. Hayashi
  • Journal Title: Chem. Asian J. Volume: 41 Issue: 7 Pages: 1036-1042
  • DOI: 10.1002/asia.201501415
  • Peer Reviewed
• [Journal Article] Energy migration within hexameric hemoprotein reconstituted with Zn porphyrinoid molecules (2015)
  • Author(s): Takashi Hayashi
  • Journal Title: Chemical Communications Volume: 51 Issue: 55 Pages: 11138-11140
  • DOI: 10.1039/c5cc02680f
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Meso-dibenzoporphycene has a Large Bathochromic Shift and a Porphycene Framework with an Anomalous Cis Tautomeric Form (2015)
  • Author(s): Koji Oohora, Ayumu Ogawa, Tamaki Fukuda, Akira Onoda, Jun-ya Hasegawa, Takashi Hayashi
  • Journal Title: Angew. Chem., Int. Ed. Volume: 印刷中 Issue: 21 Pages: 6227-6230
  • DOI: 10.1002/anie.201501496
  • Peer Reviewed
• [Journal Article] Co(II)/Co(I) Reduction-induced Axial Histidine-flipping in Myoglobin Reconstituted with a Cobalt Tetradehydrocorrin as a Methionine Synthase Model (2014)
  • Author(s): Takashi Hayashi, Yoshitsugu Morita, Eiichi Mizohata, Koji Oohora, Jun Ohbayashi, Tsuyoshi Inoue, and Yoshio Hisaeda
  • Journal Title: Chem. Commun. Volume: 50 Issue: 83 Pages: 12560-12563
  • DOI: 10.1039/c4cc05448b
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Hemoprotein-based Supramolecular Assembling Systems (2014)
  • Author(s): Koji Oohora, Takashi Hayashi
  • Journal Title: Curr. Opin. Chem. Biol. Volume: 19 Pages: 154-161
  • DOI: 10.1016/j.cbpa.2014.02.014
  • Peer Reviewed
• [Journal Article] C(sp3)-H Bond Hydroxylation Catalyzed by Myoglobin Reconstituted with Manganese Porphycene (2013)
  • Author(s): Koji Oohora, Yushi Kihira, Eiichi Mizohata, Tsuyoshi Inoue, Takashi Hayashi
  • Journal Title: J. Am. Chem. Soc. Volume: 135 Issue: 46 Pages: 17282-17285
  • DOI: 10.1021/ja409404k
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] A Zn Porphyrin Array within a Hexameric Hemoprotein Matrix Modified by Donor Photosensitizers toward an Artificial Light Harvesting System (2015)
  • Author(s): Tsuyoshi Mashima, Koji Oohora, Takashi Hayashi
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学（奈良県奈良市）
  • Year and Date: 2015-09-21
• [Presentation] ピレン分子を修飾した六量体ヘムタンパク質HTHPの超分子集積化 (2015)
  • Author(s): 平山 翔太・大洞 光司・林 高史
  • Organizer: 錯体化学会第65回討論会
  • Place of Presentation: 奈良女子大学（奈良県奈良市）
  • Year and Date: 2015-09-21
• [Presentation] 亜鉛置換型ヘムタンパク質環状六量体の光化学的性質 (2015)
  • Author(s): 大洞 光司・真島 剛史・平山 翔太・林 高史
  • Organizer: 第13回ホストゲスト化学シンポジウム
  • Place of Presentation: 東北大学河内北キャンパス（宮城県仙台市）
  • Year and Date: 2015-06-06
• [Presentation] Artificial light harvesting system by reconstitution of hexameric hemoprotein with Zn porphyrinoids (2015)
  • Author(s): Koji Oohora, Tsuyoshi Mashima, Takashi Hayashi
  • Organizer: 5th Georgian Bay International Conference on Bioinorganic Chemistry
  • Place of Presentation: オンタリオ、カナダ
  • Year and Date: 2015-05-20
  • Int'l Joint Research
• [Presentation] メソジベンゾポルフィセン(1):合成、構造および分光学的特性 (2015)
  • Author(s): 大洞 光司、小川 歩、長谷川 淳也、林 高史
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-25 – 2015-03-29
• [Presentation] メソジベンゾポルフィセン(2) 縮環ベンゼン部位の置換基効果 (2015)
  • Author(s): 田中靖之、小川 歩、大洞光司、林 高史
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-25 – 2015-03-29
• [Presentation] ヘムタンパク質環状六量体を用いた亜鉛クロリンe6の集積化 (2015)
  • Author(s): 真島剛史、大洞光司、林高史
  • Organizer: 日本大学
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-25 – 2015-03-29
• [Presentation] クリック反応を用いたアルキン導入de novoヘムタンパク質の重合 (2015)
  • Author(s): 古川 泰祐・大洞 光司・林 高史
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-25 – 2015-03-29
• [Presentation] 鉄及び亜鉛ポルフィリンを含むシトクロムb562超分子集合体における光誘起電子移動 (2015)
  • Author(s): 梶原 竜太、大洞 光司、林 高史
  • Organizer: 日本化学会第95春季年会
  • Place of Presentation: 日本大学
  • Year and Date: 2015-03-25 – 2015-03-29
• [Presentation] 二つの架橋部位にベンゼン環が縮環したジベンゾポルフィセンの合成と物性評価 (2014)
  • Author(s): 小川 歩、大洞光司、長谷川淳也、林 高史
  • Organizer: 第47回酸化反応討論会
  • Place of Presentation: 熊本大学
  • Year and Date: 2014-11-14 – 2014-11-15
• [Presentation] ヘムタンパク質環状六量体を用いた光増感色素集積体の構築とその光捕集能 (2014)
  • Author(s): 真島 剛史、大洞 光司、林 高史
  • Organizer: 錯体化学会第64回討論会
  • Place of Presentation: 中央大学
  • Year and Date: 2014-09-18 – 2014-09-20
• [Presentation] ヘムタンパク質環状集合体の補因子置換による光捕集系の構築 (2014)
  • Author(s): 大洞 光司、真島 剛史、林 高史
  • Organizer: 第8回バイオ関連化学シンポジウム
  • Place of Presentation: 岡山大学
  • Year and Date: 2014-09-11 – 2014-09-13
• [Presentation] ペプチド末端にクリック反応点を導入したde novoヘムタンパク質の調製 (2014)
  • Author(s): 古川泰祐, 大洞光司, 林高史
  • Organizer: 第8回バイオ関連化学シンポジウム
  • Place of Presentation: 岡山大学
  • Year and Date: 2014-09-11 – 2014-09-13
• [Presentation] Catalytic Alkane Hydroxylation by Myoglobin Containing a Manganese Porphycene Complex (2014)
  • Author(s): Koji Oohora, Hiroyuki Meichin, Yushi Kihira, Takako Nishiura, Takashi Hayashi
  • Organizer: 12th European Bbiological Biological Inorganic Chemistry Conference
  • Place of Presentation: University of Zurich
  • Year and Date: 2014-08-24 – 2014-08-28
• [Presentation] 亜鉛置換型ヘムタンパク質多量体における励起子カップリングとその光化学的性質 (2014)
  • Author(s): 大洞 光司、真島 剛史、藤巻 錦、林 高史
  • Organizer: 第12回ホスト・ゲスト化学シンポジウム
  • Place of Presentation: 東京工業大学
  • Year and Date: 2014-05-31 – 2014-06-01
• [Presentation] ヘムタンパク質環状六量体を用いた光増感色素の集積化 (2014)
  • Author(s): 真島 剛史、大洞 光司、林 高史
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] ヘムーへム励起子カップリングを示すヘムタンパク質超分子集合体 (2014)
  • Author(s): 大洞 光司、藤巻 錦、林 高史
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] ヘムタンパク質環状六量体を用いた光増感色素集積体の構築 (2013)
  • Author(s): 真島剛史、大洞光司、林 高史
  • Organizer: 錯体化学会第63回討論会
  • Place of Presentation: 琉球大学
• [Presentation] Zn-Porphyrin Array with Hexameric Hemoprotein Template (2013)
  • Author(s): 真島剛史、大洞光司、林 高史
  • Organizer: Japan-Taiwan Bilateral Workshop on Nano-Science 2013
  • Place of Presentation: 鹿児島大学
• [Presentation] 人工光捕集系を指向した亜鉛置換シトクロムb 562超分子集合体の構築 (2013)
  • Author(s): 藤巻 錦、大洞 光司、林 高史
  • Organizer: 第7回バイオ関連化学シンポジウム
  • Place of Presentation: 名古屋大学
• [Remarks] 大阪大学 林研究室
  • URL: http://www.chem.eng.osaka-u.ac.jp/~hayashiken/index.html
• [Remarks] 研究室ホームページ
  • URL: http://www.chem.eng.osaka-u.ac.jp/~hayashiken/index.html
• [Remarks] 大阪大学 林研究室ホームページ
  • URL: http://www.chem.eng.osaka-u.ac.jp/~hayashiken/index.html