クロロフィルを用いた自己集積型光応答ナノデバイスの構築

• Project/Area Number: 15033271
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Ritsumeikan University
• Principal Investigator: 民秋 均 立命館大学, 理工学部, 教授 (00192641)
• Project Period (FY): 2003 – 2004
• Project Status: Completed (Fiscal Year 2004)
• Budget Amount: ¥5,000,000 (Direct Cost: ¥5,000,000); Fiscal Year 2004: ¥2,500,000 (Direct Cost: ¥2,500,000); Fiscal Year 2003: ¥2,500,000 (Direct Cost: ¥2,500,000)
• Keywords: 光合成アンテナ / 光応答 / クロロフィル / 超分子 / 自己集積 / ポルフィリン

Research Abstract

緑色光合成細菌の膜外アンテナ部=クロロゾーム中では、クロロゾーム型クロロフィル分子が自己会合することによって、アンテナ色素部を形成している。このクロロゾーム型クロロフィルのモデル分子として有効であることが判明している「3^1-ヒドロキシ-13^1-オキソクロリン亜鉛錯体」の7・8位に様々な置換基を導入して、その自己会合に対する効果を検討した。π共役系の官能基を導入しても、単量体の最長吸収波長帯(Qy帯)にほとんど影響を与えなかった。これは、7・8位がQy遷移と直交したQx軸上にあるためであると考えられる。一方、自己会合体では、大きな平面性を有する置換基において、約10nmのより大きな長波長シフトが見られた。そのような置換基が会合体内で効果的に相互作用して、超分子構造を安定化していることが判った。また、配位能のあるホルミル基を導入しても、自己会合体形成の邪魔にならないことが判った。ホルミル基の電子吸引性のために可視吸収スペクトルには大きな摂動を与えるので、新たな領域での吸収帯を有する自己会合体の構築が可能になり、光エネルギー収穫とエネルギー伝達の両機能に対しても、微妙な調整が行うことが可能となった。
次に、光機能性界面デバイス構築のために、クロロフィル分子を固体界面に修飾することを試みた。クロロフィル分子に-S-S-基を導入し、その溶液を金板上にさらすことで、自己集積膜の調製を行った。S-Au結合に基づいて、クロロフィル分子が金上に修飾されたことが、化学反応性ならびに可視吸収スペクトルから判明した。

Research Products

• [Journal Article] Self-aggregation of synthetic zinc oxo-bacteriochlorins bearing substituents characteristic of chlorosomal chlorophylls (2005)
  • Author(s): M.Kunieda, H.Tamiaki
  • Journal Title: J.Org.Chem. 70 Pages: 820-828
• [Journal Article] Self-aggregation of protobacteriochlorophyll-d derivatives (2005)
  • Author(s): H.Tamiaki, H.Kitamoto, T.Watanabe, R.Shibata
  • Journal Title: Photochem.Photobiol. 81 Pages: 170-176
• [Journal Article] Effects of C8-substituents on spectroscopic and self-aggregation properties of synthetic bacteriochlorophyll-d analogues (2004)
  • Author(s): S.Sasaki, M.Omoda, H.Tamiaki
  • Journal Title: J.Photochem.Photobiol.A : Chem. 162 Pages: 307-315
• [Journal Article] Facile Synthesis of Chlorophyll Analog Possessing a Disulfide Bond and Formation of Self-Assembled Monolayer on Gold Surface (2004)
  • Author(s): Y.Saga, H.Tamiaki
  • Journal Title: J.Photochem.Photobiol.B : Biol. 73 Pages: 29-34
• [Journal Article] Diastereoselective self-aggregation of synthetic 3-(1-hydroxyethyl)-bacteriopyrochlorophyll-a as a novel photosynthetic antenna model absorbing near the infrared region (2004)
  • Author(s): M.Kunieda, T.Mizoguchi, H.Tamiaki
  • Journal Title: Photochem.Photobiol. 79 Pages: 55-61
• [Journal Article] Self-assembly of synthetic bacteriochlorophyll-f analogues possessing C8-formyl group (2004)
  • Author(s): S.Sasaki, H.Tamiaki
  • Journal Title: Bull.Chem.Soc.Jpn. 77 Pages: 797-800
• [Journal Article] Determination of 3^1-Stereochemistry in Synthetic Bacteriochlorophyll-d Homologs and Self-aggregation of Their Zinc Complexes (2004)
  • Author(s): H.Tamiaki, H.Kitamoto, A.Nishikawa, T.Hibino, R.Shibata
  • Journal Title: Bioorg.Med.Chem. 12 Pages: 1657-1666
• [Journal Article] Coaggregation of Amphiphilic Zinc Chlorins with Synthetic Surfactants in Aqueous Medium to an Artificial Supramolecular Light-Harvesting Antenna (2004)
  • Author(s): T.Miyatake, H.Tamiaki, M.Fujiwara, T.Matsushita
  • Journal Title: Bioorg.Med.Chem. 12 Pages: 2173-2178
• [Journal Article] Synthesis of a novel cyclic chlorophyll hetero-dyad as a model compound for stacked chlorophylls found in photosynthetic system (2004)
  • Author(s): N.Kosaka, H.Tamiaki
  • Journal Title: Eur.J.Org.Chem. 2004 Pages: 2325-2330
• [Journal Article] Comparison between chlorosomes containing bacteriochlorophyll-c and chlorosomes containing bacteriochlorophyll-d isolated from two substrains of green sulfur photosynthetic bacterium Chlorobium vibrioforme NCIB 8327 (2004)
  • Author(s): Y.Saga, H.Tamiaki
  • Journal Title: J.Photochem.Photobiol.B : Biol. 75 Pages: 89-97
• [Journal Article] Syntheses and optical properties of stable 8-alkylidene-bacteriochlorins mimicking the molecular structures of natural bacteriochlorophyll-b and g (2004)
  • Author(s): M.Kunieda, T.Mizoguchi, H.Tamiaki
  • Journal Title: Tetrahedron 60 Pages: 11349-11357
• [Journal Article] MAS NMR structures of aggregated cadmium chlorins reveal molecular control of self-assembly of chlorosomal bacteriochlorophylls (2004)
  • Author(s): I.de Boer, J.Matysik, K.Erkelens, S.Sasaki, T.Miyatake, S.Yagai, H.Tamiaki, A.R.Holzwarth, H.J.M.de Groot
  • Journal Title: J.Phys.Chem., B 108 Pages: 16556-16566
• [Patent(Industrial Property Rights)] メチル基転移酵素、そのDNA、及び特定部位にメチル基が導入されたポルフィリン型化合物の製造方法 (2004)
  • Inventor(s): 民秋 均, 原田 二朗, 佐賀 佳央
  • Industrial Property Rights Holder: 学校法人立命館と発明者
  • Industrial Property Number: 2004-242888
  • Filing Date: 2004-08-23
• [Publications] H.Tamiaki, M.Omoda, Y.Saga, H.Morishita: "Synthesis of Homologously Pure Bacteriochlorophyll-e and f Analogues from BChls-c/d via Transformation of the 7-Methyl to Formyl Group and Self-Aggregation of Synthetic Zinc Methyl Bacteriopheophorbides-c/d/e/f in Non-Polar Organic Solvent"Tetrahedron. 59. 4337-4350 (2003)
• [Publications] H.Morishita, H.Tamaki: "Synthesis of Specifically ^<18>O-Labeled Chlorophyll Derivatives at Carbonyl Oxygen Atoms by Acidic Hydrolysis of the Ethylene Ketal and Acetal"Bioorg.Med.Chem.. 11. 4049-4057 (2003)
• [Publications] H.Tamiaki, S.Kimura, T.Kimura: "Self-aggregation of synthetic 2^1-hydroxy-12^1/13^1-oxo-prophyrins"Tetrahedron. 59. 7423-7435 (2003)
• [Publications] H.Tamiaki, H.Kitamoto, A.Nishikawa, T.Hibino, R.Shibata: "Diastereoselective Self-Aggregation of Synthetic Zinc Bacteriochlorophyll-d Homologs"BIOMOLECULAR CHEMISTRY-A Bridge for the Future-. 184-187 (2003)
• [Publications] S.Sasaki, M.Omoda, H.Tamiaki: "Effects of C8-substituents on spectroscopic and self-aggregation properties of synthetic bacteriochlorophyll-d analogues"J.Photochem.Photobiol.A : Chem.. 162. 307-315 (2004)
• [Publications] M.Kunieda, T.Mizoguchi, H.Tamiaki: "Diastereoselective self-aggregation of synthetic 3-(1-hydroxyethyl)-bacteriopyrochlorophyll-a as a novel photosynthetic antenna model absorbing near the infrared region"Photochem.Photobiol.. 79. 55-61 (2004)
• [Publications] Y.Saga, H.Tamiaki: "Facile Synthesis of Chlorophyll Analog Possessing a Disulfide Bond and Formation of Self-Assembled Monolayer on Gold Surface"J.Photochem.PHotobiol.B : Biol.. 73. 29-34 (2004)
• [Publications] S.Sasaki, H.Tamiaki: "Self-assembly of synthetic bacteriochlorophyll-f analogues possessing C8-formyl group"Bull.Chem.Soc.Jpn.. 77(In press). (2004)
• [Publications] H.Tamiaki, T.Watanabe, M.Kunieda: "Self-aggregation of Synthetic Zinc 3^1-Hydroxy-13^1-Oxo-17,18-cis-Chlorin in a Non-Polar Organic Solvent"Res.Chem.Int.. 30(In press). (2004)
• [Publications] T.Miyatake, H.Tamiaki, M.Fujiwara, T.Matsushita: "Coaggregation of Amphiphilic Zinc Chlorins with Synthetic Surfactants in Aqueous Medium to an Artificial Supramolecular Light-Harvesting Antenna"Bioorg.Med.Chem.. 12(In press). (2004)
• [Publications] H.Tamiaki, H.Kitamoto, A.Nishikawa, T.Hibino, R.Shibata: "Determination of 3^1-Stereochemistry in Synthetic Bacteriochlorophyll-d Homologs and Self-aggregation of their Zinc Complexes"Bioorg.Med.Chem.. 12(In press). (2004)
• [Publications] N.Kosaka, H.Tamiaki: "Synthesis of a novel cyclic chlorophyll hetero-dyad as a model compound for stacked chlorophylls found in photosynthetic apparatus"Eur.J.Org.Chem.. (In press). (2004)