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: 17029065
• 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): 2005 – 2006
• Project Status: Completed (Fiscal Year 2006)
• Budget Amount: ¥5,000,000 (Direct Cost: ¥5,000,000); Fiscal Year 2006: ¥2,500,000 (Direct Cost: ¥2,500,000); Fiscal Year 2005: ¥2,500,000 (Direct Cost: ¥2,500,000)
• Keywords: 自己組織化 / 超分子化学 / ナノ材料 / 表面・界面物性 / 生体機能利用

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、通常のクロロフィルとは分子構造の異なる特別な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。そこで、天然型のクロロゾームクロロフィルを模した様々なモデル色素分子を合成して、多様な条件下でその自己会合体を創製し、その物性を検討しつつ、光応答ナノデバイスの構築を固体界面上で行った。
クロロゾームクロロフィルモデル分子に様々な官能基を導入する際には、これまでは有機合成化学的手法を駆使してきたが、選択的な官能基導入は困難を伴うことが多かった。そこで生合成に用いられている酵素を利用して、クロロフィルの位置・立体選択的変換を行った。活性化されていない20位の炭素上への直接メチル化に成功したのをはじめ、ピロールB環上のC7=C8二重結合の不斉還元にも世界で初めて成功した。さらに、17位上のエステルのゲラニルゲラニル鎖の位置選択的で段階的な不斉還元にも取り組んでいる。
次に、光機能性界面デバイス構築のために、より安定な自己会合体の構築を行った。アクリレートやジアセチレンの熱・光重合やシラノールの縮重合の利用を試みて、後者によって生成するポリシロキサンが有効であることが判った。このようにして構築された自己会合体は、残存シラノールによって水中では表面負電荷を有するために、正電荷を帯びた界面上に固定化でき、さらに幾層でも積層出来ることが判った。同様の静電的相互作用を利用して、負電荷を有するカルボン酸型クロロフィルを半導体表面に修飾して、色素増感型太陽電池を構築できることも判明した。

Research Products

• [Journal Article] Self-aggregation of Synthetic Zinc 3^1-Hydroxy-13^1-Oxo-17,18-cis-Chlorin in Non-Polar Organic Solvent (2007)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: Res. Chem. Int. 33 Pages: 161-168
• [Journal Article] Optical properties of synthetic porphyrins bearing or lacking an exo-five-membered ring and a keto carbonyl group on it, both of which are present in naturally occurring chlorophylls (2007)
  • Author(s): M.Kunieda, et al.
  • Journal Title: J.Photochem.Photobiol.A : Chem. 185 Pages: 321-330
• [Journal Article] The 17-propionate function of (bacterio)chlorophylls : biological implication of their long esterifying chains in photosynthetic systems (2007)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: Photochem. Photobiol. 83 Pages: 152-162
• [Journal Article] Self-aggregation of zinc chlorophylls possessing perfluoroalkyl chains in fluorous solvents : Selective extraction of the self-aggregates with fluorous phase and accelerated formation of the ordered supramolecules in this phase (2007)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: Bioorg. Med. Chem. Lett. 17 Pages: 1920-1923
• [Journal Article] Crystal Structures of CbiL, a Methyltransferase Involved in Anaerobic Vitamin B_<12> Biosynthesis, and its Complex with S-Adenosylhomocysteine : Implications for the Reaction Mechanism (2007)
  • Author(s): K.Wada, et al.
  • Journal Title: FEBS J. 274 Pages: 563-573
• [Journal Article] Regioisomerically controlled self-aggregation of zinc 3-hydroxymethyl-13-formyl-chlorin/porphyrin and their 3,13-inverted pigments (2007)
  • Author(s): M.Kunieda, et al.
  • Journal Title: J.Org.Chem. 72 Pages: 2442-2451
• [Journal Article] Aqueous Self-Aggregates of Amphiphilic Zinc 3^1-Hydroxy- and 3^1-Methoxy-chlorins for Supramolecular Light-Harvesting Systems (2007)
  • Author(s): T.Miyatake, et al.
  • Journal Title: Tetrahedron Lett. 48 Pages: 2251-2254
• [Journal Article] Synthetic hydroxymethyl-porphyrins for protection of carboxy group (2007)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: J.Porphyrins Phthalocyanines 11(印刷中)
• [Journal Article] Polarized Fluorescence of Aggregated Bacteriochlorophyll c and Baseplate Bacteriochlorophyll α in a Single Chlorosomes Isolated from Chloroflexus aurantiacus (2007)
  • Author(s): Y.Shibata, et al.
  • Journal Title: Biochemistry 46(印刷中)
• [Journal Article] Kinetic Analysis of Demetalation of Bacteriochlorophyll c and e Homologs Purified from Green Sulfur Photosynthetic Bacteria (2007)
  • Author(s): Y.Saga, et al.
  • Journal Title: FEBS Lett. 581 Pages: 1847-1850
• [Journal Article] A facile synthetic method for conversion of chlorophyll-α to bacteriochlorophyll-c (2007)
  • Author(s): S.Sasaki, et al.
  • Journal Title: J.Org.Chem. 72(印刷中)
• [Journal Article] Gallium (III) complexes of methyl pyropheophorbide-α as synthetic models for investigation of diastereomerically controlled axial ligation towards chlorophylls (2006)
  • Author(s): S.Sasaki, et al.
  • Journal Title: Bioorg.Med.Chem.Lett. 16 Pages: 1168-1171
• [Journal Article] Assembly of extramembranous light-harvesting complexes of green sulfur photosynthetic bacterium Chlorobium tepidum on glass surface by electrostatic layer-by-layer adsorption (2006)
  • Author(s): Y.Saga, et al.
  • Journal Title: Thin Solid Films 500 Pages: 278-282
• [Journal Article] Self-aggregation of synthetic zinc chlorophyll derivative possessing a perfluoroalkyl group in a fluorinated solvent (2006)
  • Author(s): R.Shibata, et al.
  • Journal Title: Bioorg.Med.Chem. 14 Pages: 2235-2241
• [Journal Article] Stereochemical determination of chlorophyll-d molecule from Acaryochloris marina and its modification to a self-aggregative chlorophyll as a model of green photosynthetic bacterial antennae (2006)
  • Author(s): T.Mizoguchi, et al.
  • Journal Title: Photochem.Photobiol.Sci. 5 Pages: 291-299
• [Journal Article] Self-aggregation of synthetic zinc chlorins possessing 13-ester-carbonyl group as chlorosomal chlorophyll models (2006)
  • Author(s): M.Kunieda, et al.
  • Journal Title: Eur.J.Org.Chem. 2006 Pages: 2352-2361
• [Journal Article] Single Supramolecule Spectroscopy of Natural and Alkaline-Treated Chlorosomes from Green Sulfur Photosynthetic Bacteria (2006)
  • Author(s): Y.Saga, et al.
  • Journal Title: J.Nanosci.Nanotech. 6 Pages: 1750-1757
• [Journal Article] Synthesis and Optical Properties of Bacteriochlorophyll-α Derivatives Having Various C3-Substituents on the Bacteriochlorin π-System (2006)
  • Author(s): S.Sasaki, et al.
  • Journal Title: J.Org.Chem. 71 Pages: 2648-2654
• [Journal Article] Analysis of photooxidized pigments in water-soluble chlorophyll protein complex isolated from Chenopodium album (2006)
  • Author(s): H.Hirabayashi, et al.
  • Journal Title: J.Photochem.Photobiol. A : Chem. 183 Pages: 121-125
• [Journal Article] Effects of plant carotenoid spacers on the performance of a dye-sensitized solar cell using a chlorophyll derivative : Enhancement of photocurrent determined by one electron-oxidation potential of each carotenoid (2006)
  • Author(s): X.-F.Wang, et al.
  • Journal Title: Chem.Phys.Lett. 423 Pages: 470-475
• [Journal Article] A Second Nitorogenase-like Enzyme for Bacteriochlorophyll Biosynthesis : Reconstitution of Chlorophyllide α Reductase with Purified X-protein (BchX) and YZ-protein (BchY-BchZ) from Rhodobacter capsulatus (2006)
  • Author(s): J.Nomata, et al.
  • Journal Title: J.Biol.Chem. 281 Pages: 15021-15028
• [Journal Article] Synthesis of Cyclic Chlorophyll Oligomers (2006)
  • Author(s): S.Sasaki, et al.
  • Journal Title: Tetrahedron. Lett. 47 Pages: 4965-4968
• [Journal Article] Trifluoroacetyl-chlorin as a new chemosensor for alcohol/amine detection (2006)
  • Author(s): S.Sasaki, et al.
  • Journal Title: Tetrahedron. Lett. 47 Pages: 4849-4852
• [Journal Article] Synthesis of Self-Aggregative (Bacterio)chlorophylls (2006)
  • Author(s): H.Tamiaki
  • Journal Title: J.Porphyrins Phthalocyanines 10 Pages: 407-407
• [Journal Article] Self-aggregation of synthetic zinc chlorophyll derivatives possessing perfluoroalkyl groups (2006)
  • Author(s): R.Shibata, et al.
  • Journal Title: J.Porphyrins Phthalocyanines 10 Pages: 861-861
• [Journal Article] Self-assemblies of amphiphilic zinc chlorins for supramolecular light-harvesting antenna (2006)
  • Author(s): T.Miyatake, et al.
  • Journal Title: J.Porphyrins Phthalocyanines 10 Pages: 347-347
• [Journal Article] Low-temperature fluorescence from single chlorosomes, photosynthetic antenna complexes of green filamentous and sulfur bacteria (2006)
  • Author(s): Y.Shibata, et al.
  • Journal Title: Biophys.J. 91 Pages: 3787-3796
• [Journal Article] Self-assembly of natural light-harvesting bacteriochlorophylls of green sulfur photosynthetic bacteria in silicate capsules as stable models of chlorosomes (2006)
  • Author(s): Y.Saga, et al.
  • Journal Title: Bioconjugate Chem. 17 Pages: 988-994
• [Journal Article] Crystal Structures of BchU, a Methyltransferase Involved in Bacteriochlorophyll c Biosynthesis, and Its Complex with S-Adenosylhomocystein : Implication for Reaction Mechanism (2006)
  • Author(s): K.Wada, et al.
  • Journal Title: J.Mol.Biol. 360 Pages: 843-853
• [Journal Article] Transmission Electron Microscopic Study on Supramolecular Nanostructures of Bacteriochlorophyll Self-Aggregates in Chlorosomes of Green Photosynthetic Bacteria (2006)
  • Author(s): Y.Saga, et al.
  • Journal Title: J.Biosci.Bioeng. 102 Pages: 118-123
• [Journal Article] Oligomethylene spacer length dependent interaction of synthetic galactolipids incorporated in phospholipid layers with ricin (2006)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: Colloids Surf B : Biointerfaces 53 Pages: 87-93
• [Journal Article] Synthesis of self-aggregative zinc chlorophylls possessing polymerizable esters as a stable model for main light-harvesting antennas of green photosynthetic bacteria (2006)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: International J. Photoenergy 2006
• [Journal Article] Structural detemination of dihydro- and tetrahydrogeranylgeranyl groups at the 17-proionate of bacteriochlorophylls-α (2006)
  • Author(s): T.Mizoguchi, et al.
  • Journal Title: FEBS Lett. 580 Pages: 6644-6648
• [Journal Article] Gallium (III) complexes of methyl pyropheophorbide-a as synthetic models for investigation of diastereomerically controlled axial ligation towards chlorophylls (2006)
  • Author(s): S.Sasaki, et al.
  • Journal Title: Bioorg.Med.Chem.Lett. 16 Pages: 1168-1171
• [Journal Article] Stereochemical determination of chlorophyll-d molecule from Acaryochloris marina and its modification to a self-aggregative chlorophyll as a model of green photosynthetic bacterial antenna (2006)
  • Author(s): T.Mizoguchi, et al.
  • Journal Title: Photochem.Photobiol.Sci. 5 Pages: 291-299
• [Journal Article] Assembly of extramembranous light-harvesting complexes of green sulfur photosynthetic bacterium Chlorobium tepidum on glass surface by electrostatic layer-by-layer adsorptio (2006)
  • Author(s): Y.Saga, et al.
  • Journal Title: Thin Solid Films 500 Pages: 278-282
• [Journal Article] Self-aggregation of synthetic zinc chlorins possessing 13-ester-carbonyl group as chlorosomal chlorophyll models (2006)
  • Author(s): M.Kunieda, et al.
  • Journal Title: Eur.J.Org.Chem. (印刷中)
• [Journal Article] Single supramolecule spectroscopy of natural and alkaline-treated chlorosomes from green sulfur photosynthetic bacteria (2006)
  • Author(s): Y.Saga, et al.
  • Journal Title: J.Nanosci.Nanotech 6(印刷中)
• [Journal Article] Self-aggregation of synthetic zinc 3^1-hydroxy-13^1-oxo-17,18-cis-chlorin in a non-polar organic solvent (2006)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: Res.Chem.Int. 32(印刷中)
• [Journal Article] Synthesis and optical properties of bacteriochlorophyll-a derivatives having various C3-substituents on the bacteriochlorin π-system (2006)
  • Author(s): S.Sasaki, et al.
  • Journal Title: J.Org.Chem. 71(印刷中)
• [Journal Article] Self-aggregation of synthetic protobacteriochlorophyll-d derivatives (2005)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: Photochem.Photobiol. 81 Pages: 170-176
• [Journal Article] Self-aggregation of synthetic zinc oxo-bacteriochlorins bearing substituents characteristic of chlorosomal chlorophylls (2005)
  • Author(s): M.Kunieda, et al.
  • Journal Title: J.Org.Chem. 70 Pages: 820-828
• [Journal Article] Excitation energy transfer in individual light-harvesting chlorosome from green photosynthetic bacterium Chloroflexus aurantiacus at cryogenic temperatur (2005)
  • Author(s): Y.Saga, et al.
  • Journal Title: Chem.Phys.Lett. 409 Pages: 34-37
• [Journal Article] Self-aggregates of natural and modified chlorophylls as photosynthetic light-harvesting antenna systems : Substituent effect on the B-ring (2005)
  • Author(s): H.Tamiaki
  • Journal Title: Photochem.Photobiol.Sci. 4 Pages: 675-680
• [Journal Article] Determination of stereochemistry of bacteriochlorophyll g_F and 8^1-hydroxy-chlorophyll a_F from Heliobacterium modesticaldum (2005)
  • Author(s): T.Mizoguchi, et al.
  • Journal Title: Photochem.Photobiol. 81 Pages: 666-667
• [Journal Article] Synthesis of regioselectively ^<18>O-labelled chlorophyll derivatives at the 3^1-and/or 13^1-positions through one-pot exchange of carbonyl oxygen atoms (2005)
  • Author(s): H.Morishita, et al.
  • Journal Title: Tetrahedron 61 Pages: 6097-6107
• [Journal Article] Bacteriochlorophyll-c homolog composition in green sulfur photosynthetic bacterium Chlorobium vibrioforme dependent on the concentration of sodium sulfide in liquid cultures (2005)
  • Author(s): Y.Saga, et al.
  • Journal Title: Photosynth.Res. 86 Pages: 123-130
• [Journal Article] Time-dependent self-assembly of 3^1-epimerically pure and mixed zinc methyl bacterionheonhorbides-d in an aqueous tetrahydrofuran solution (2005)
  • Author(s): T.Miyatake, et al.
  • Journal Title: Photosynth.Res. 86 Pages: 131-136
• [Journal Article] Different sensitivities to oxygen between two strains of the photosynthetic green sulfur bacterium Chlorobium vibrioforme NCIB 8327 with bacteriochlorophyll c and d (2005)
  • Author(s): J.Harada, et al.
  • Journal Title: Photosynth.Res. 86 Pages: 137-143
• [Journal Article] In vitro activity of C-20 methyltransferase, BchU, involved in bacteriochlorophyll c biosynthesis pathway in green sulfur bacteria (2005)
  • Author(s): J.Harada, et al.
  • Journal Title: FEBS Lett. 579 Pages: 1983-1987
• [Journal Article] Synthesis of strapped zinc chlorophyll derivatives and their complexation with a single axial ligand (2005)
  • Author(s): S.Sasaki, et al.
  • Journal Title: Tetrahedron 61 Pages: 8041-804
• [Journal Article] Chlorins programmed for self-assembly (2005)
  • Author(s): T.S.Balaban, et al.
  • Journal Title: Topics Curr.Chem. 258 Pages: 1-38
• [Journal Article] Self-aggregates of bacteriochlorophylls-c, d and e in a light-harvesting antenna system of green photosynthetic bacteria : Effect of stereochemistry at the chiral 3-(1-hydroxyethyl) group on the supramolecular arrangement of chlorophyllous pigments (2005)
  • Author(s): T.Miyatake, et al.
  • Journal Title: J.Photochem.Photobiol.C : Photochem.Rev. 6 Pages: 89-107
• [Journal Article] Synthesis of stereospecifically face-protected chlorophyll derivatives (2005)
  • Author(s): S.Sasaki, et al.
  • Journal Title: Tetrahedron Lett. 46 Pages: 7687-7689
• [Journal Article] Effects of peripheral substituents on diastereoselectivity of the fifth ligand binding to chlorophylls, and nomenclature of the asymmetric axial coordination sites (2005)
  • Author(s): T.Oba, et al.
  • Journal Title: Bioorg.Med.Chem. 13 Pages: 5733-573
• [Journal Article] Dye-sensitized solar cells using a chlorophyll a derivative as the sensitizer and carotenoids having different conjugation lengths as redox spacers (2005)
  • Author(s): X.-F.Wang, et al.
  • Journal Title: Chem.Phys.Lett. 408 Pages: 409-414
• [Journal Article] Crystallization and preliminary X-ray diffraction study of BchU, methyltransferase from Chlorobium tepidum involved in bacteriochlorophyll c biosynthesis (2005)
  • Author(s): J.Harada, et al.
  • Journal Title: Acta Crystal.F 61 Pages: 712-714
• [Journal Article] Self-aggregation of synthetic zinc 3-hydroxymethyl-purpurin-18 and N-hexylimide methyl esters in an aqueous solution as models of green photosynthetic bacterial chlorosome (2005)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: Chem.Lett. 34 Pages: 1344-1345
  • NAID: 10019351724
• [Journal Article] Generation of carotenoid radical cation in the vicinity of a chlorophyll derivative bound to titanium oxide, upon excitation of the chlorophyll derivative to the Qy state, as identified by time-resolved absorption spectroscopy (2005)
  • Author(s): X.-F.Wang, et al.
  • Journal Title: Chem.Phys.Lett. 416 Pages: 229-233
• [Journal Article] Self-organization of BChl c in chlorosomes studied by MAS NMR of aggregated Cd-chlorins (2005)
  • Author(s): I.de Boer, et al.
  • Journal Title: Photosynthesis : Fundamental Aspects to Global Perspectives (Ed by A.van der Est & D.Bruce) (Allen Press, Lawrence, KS) Pages: 121-122
• [Journal Article] Microscopic investigation of single chlorosomes from green photosynthetic bacteria at cryogenic temperature (2005)
  • Author(s): Y.Saga, et al.
  • Journal Title: Photosynthesis : Fundamental Aspects to Global Perspectives (Ed by A.van der Est & D.Bruce) (Allen Press, Lawrence, KS) Pages: 125-127
• [Journal Article] Self-aggregation of synthetic zinc 17,18-cis-bacteriochlorophyll-d derivative (2005)
  • Author(s): H.Tamiaki, et al.
  • Journal Title: Photosynthesis : Fundamental Aspects to Global Perspectives (Ed by A.van der Est & D.Bruce) (Allen Press, Lawrence, KS) Pages: 127-128
• [Journal Article] Self-aggregation of zinc oxo-bacteriochlorins as models of chlorosomal chlorophylls (2005)
  • Author(s): M.Kunieda, et al.
  • Journal Title: Photosynthesis : Fundamental Aspects to Global Perspectives (Ed by A.van der Est & D.Bruce) (Allen Press, Lawrence, KS) Pages: 128-130
• [Journal Article] Synthesis of ^<18>O-labelled (pyro)pheophytins including pheophytin-d (2005)
  • Author(s): H.Morishita, et al.
  • Journal Title: Photosynthesis : Fundamental Aspects to Global Perspectives (Ed by A.van der Est & D.Bruce) (Allen Press, Lawrence, KS) Pages: 796-797
• [Journal Article] クロロフィルの固体表面への組織化とその光応答 (2005)
  • Author(s): 佐賀佳央ら
  • Journal Title: 化学工業 56・4 Pages: 272-276