1993 年度実績報告書

生体電子移動の局所環境による制御とシステム最適化の分子機構-人工化を目指して-

研究課題

研究課題/領域番号	05305004
研究機関	京都大学
研究代表者	豊島喜則京都大学, 総合人間学部, 教授 (60013166)
研究分担者	森島洋太郎大阪大学, 理学部, 助教授 (70028249) 伊藤繁基礎生物学研究所, 助教授 (40108634) 渡辺正東京大学, 生産技術研究所, 教授 (70092385) 坂田祥光大阪大学, 産業科学研究所, 教授 (60029874) 垣谷俊昭名古屋大学, 理学部, 教授 (90027350)
キーワード	エネルギー変換 / 電子伝達 / 最適化 / 電荷分離 / 複合体 / 局所環境 / 自己調節機構 / 人工光合成
研究概要	生体エネルギー変換の主役である電子移動反応は、極めて効率よく行われていると同時に高度に発達した自己調節機能を有している。本研究では、1)生体エネルギー変換電子伝達系が有するこの優れた特性が個々の複合体で発現される機構と、2)システム全体としての最適化の機構を解明するとともに、3)それを人工化する上での諸問題を検討し、さらにその合成、構築を試みることを目標としている。本年度は、研究代表者を中心として各班員間で協議を行い、各班員の担当し得る範囲を相互に認識した上で実質的な協力体制を組み、1)、2)のテーマに焦点を合わせた研究を行った。 1.分子内及び単一複合体内での電子移動最適化機構の解明電子移動速度を決定する最も直接的な因子である酸化還元対のエネルギーギャップと相対空間配置について、遺伝子操作や再構成法などのそれらを一部改変する手法、有機合成化学的手法、および高分子、超分子構造体、LB膜などの分子の配向性制御技術を用いて検討し、これらの因子の最適化の基本原理を追求した。 2.複合体間及び、複合体と外界間の電子授受最適化機構の解明分子あるいは分子集合体内で起こる電荷分離を有効に外界へ取り出す方法の開発を目指す研究を、生体系で行われている機構を解明し、それを指針とすることで行った。これらの成果は平成5年12月に開かれた班会議で報告され、班員以外の研究者も交えて3日間に亘って検討された。その結果、それぞれの分担項目について一定の成果が得られていることが確認され、今後はさらに、人工光合成の構築とシステム化を目指したテーマ3にも取り組んでいくことを確認した。なお、班員の研究発表状況は、主たる論文2報づつとし11.に記した。

研究成果
(42件)

すべてその他

すべて文献書誌 (42件)

[文献書誌] Toyoshima,Y.(Wada,T.): "In vitro analysis of light-induced transcription in wheat psbD/C gene cluster using plastid extracts from dark-grown and short-term illuminated seedlings." Plant Physiology(in press). 104. (1994)
[文献書誌] Toyoshima,Y.(Araga,C.): "Functional reconstitution of the primary quinone acceptor,Q_A in the photosystem II core complexes." Biochim.Biophys.Acta. 1142. 36-42 (1993)
[文献書誌] Itoh,S.(Nagashima,K.V.P.): "Photo-oxidation of reaction center-bound cytchrome c and generation of membrane potential determined by carotenoid band shift in the purple photosynthetic bacterium,Rhodospirillium milischianum." Biochim.Biophys.Acta. 1140. 297-303 (1993)
[文献書誌] Itoh,S.(Ikegami,I.): "Reconstitution of the photosystem I secondary quinone acceptor(A_l)in the p700-F_X core isolated from Synechococcus PSS 6301." Plant and Cell Physiology. 34. 849-853 (1993)
[文献書誌] Akutsu,H.(Akutsu,H.): "L-Methionine methyl is specifically incorporated into the c-2 and c-7 positions of the porphyrin of cytchrome c3 in a strictly anaerobic bacterium,Desulfovibro vulgaris." J.Am.Chem.Soc.115. 12185-12186 (1993)
[文献書誌] Akutsu,H.(Odahara,T.): "Dynamic properties of nucleic acids in supramolecular systems as studied by ^<31>P NMR." J.Biochem.(in press). (1994)
[文献書誌] Miki,K.(Hayano,T.): "PDI and Glutathione-mediated reduction of the glutathionylated variant of human lysozyme." FEBS Lett.328. 203-208 (1993)
[文献書誌] Miki,K.(Miki,K.): "Crystallization and preliminary X-ray diffraction studies of photolyase(Photoreactivating enzyme)from the cyanobacterium Anacystis nidulans." J.Mol.Biol.233. 167-169 (1993)
[文献書誌] Inoue,Y.(Noguchi,T.): "Thermoluminescence emission at liquid helium temperatures from photosynthetic apparatus and purified pigments." Biochim.Biophys.Acta. 1141. 18-22 (1993)
[文献書誌] Inoue,Y.(Noguchi,T.): "FT-IR studies on the triplet atate of P_<680> in the photosystem II reaction center:Triplet equilibrium within a chlorophyll dimer." Biochemistry. 32. 7186-7195 (1993)
[文献書誌] Matsuura,K.(Matsuura,K.): "Electrochromic spectral band shift of carotenoids in the photosynthetic membranes of Rhodospirillum molischianum and Rhodospirillum photometricum." Biochim Biophys.Acta. 1140. 92-97 (1993)
[文献書誌] Matsuura,K.(Nagashima,K.V.P.): "Primary structure and transcription of genes encoding B870 and photosynthetic reaction center apoproteins from Rubrivivax gelatinosus." J.Biol.Chem.269. 2477-2484 (1994)
[文献書誌] Watanabe,T.(Maeda,H.): "Chemical environment heterogeneity around the two chlorophyll a' molecules in photosystem I." J Photochem.Photobiol.B:Biol.20. 139-143 (1993)
[文献書誌] Watanabe,T.(Nishiyama,Y.): "Purification and substrate specificity of chlorophyllase from Chlorella regularis." Chem Lett.69-72 (1994)
[文献書誌] Kakitani,T.(Kakitani,T.): "Reexamination of basic theory." Photochem.Photobiol.58. 175-177 (1993)
[文献書誌] Kakitani,T.(Nagae,H.): "Calculation of the excitation transfer matrix elements between the S2 or S1 state of carotenoid and the S2 or S1 state of bacteriochlorophyll." J.Chem.Phys.98. 8012-8023 (1993)
[文献書誌] Sumi,H.(Sumi,H.): "A new method for obtaining bound states of a lattice electron." J.Phys.Soc.Jpn.62. 1500-1508 (1993)
[文献書誌] Sumi,H.(Sumi,H.): "Dimensionality dependence in self-trapping of excitons." J Phys.Soc.Jpn.63. 524-534 (1994)
[文献書誌] Yamazaki,T.(Yamazaki,T.): "Excited-state properties of hypericin:Electronic spectra and fluorescence decay kinetics." J.Phys.Chem.97. 7870-7875 (1993)
[文献書誌] Yamazaki,T.(Yamazaki,T.): "Time-resolved fluorescence spectroscopy and photolysis of the photoreceptor blepharismin." Biochim.Biophys.acta. 1143. 319-326 (1993)
[文献書誌] Okada,T.(Imahori,H.): "Porphyrin-quinone compounds with a spacer of diacetylene unit." Chem.Lett.1215-1218 (1993)
[文献書誌] Okada,T.(Hirata,Y.): "Photophysical properties of diphenylacetylene derivatives in solution phase 3;Thermal repopulation of the S2 state of(Aminophenyl)phenylacethylene." J.Phys.Chem.97. 9677-9681 (1993)
[文献書誌] Sakata,Y.(Borovkov,V.): "Evidence for parallel photoinduced electron transfer in diquinone substituted porphyrins." Chem Lett.145-148 (1993)
[文献書誌] Sakata,Y.(Ponomarev,G.V.): "Synthesis and prpperties of cis-1,2-bis-(octaethylporphyrinyl)ethylene." Tetrahedron Lett.34. 2153-2156 (1993)
[文献書誌] Osuka,A.(Osuka,A.): "1,2-Phenylene-bridged diporphyrin linked with porphyrin monomer and pyromellitimide as a model for photosynthetic reaction center:Synthesis and photoinduced charge separation." J Am.Chem Soc.115. 4577-4589 (1993)
[文献書誌] Osuka,A.(Osuka,A.): "Synthesis and photoexcited dynamics of aromatic group-bridged carotenoid-porphyrin dyads and carotenoid-porphyrin-pyromellitimide triads." J.Ame.Chem.Soc.115. 9439-9452 (1993)
[文献書誌] Morishima,Y.(Morishima,Y.): "Synthesis and some fluorescence properties of Poly(2-methacrylamido-3-arylpropionic acid)." Macromolecules. 26. 789-796 (1993)
[文献書誌] Morishima,Y.(Morishima,Y.): "Effect of counterion condensation on the fluorescence quenching of phenan-threne covalently attached to polyelectrolytes." J.Polym.Sci.,Polym.Chem.Ed.31. 4293-4297 (1993)
[文献書誌] Fujihira,M.(Fujihira,M.): "A novel differential electrochemical mass spectroscopy(DEMS)with a stationary gas-permeable electrode in a rotational flow produced by a rotating rod." J.Electroanal.Chem.347. 457-463 (1993)
[文献書誌] Fujihira,M.(Frommer,J.): "Adsorption at domain edges." Nature. 364. 198-198 (1993)
[文献書誌] Kaneko,M.(Ramaraj,R.): "In situ spectrocyclic coltammetry investigations on the formation of water oxidation catalyst[(bpy)_2(H_2O)Ru-O-Ru(H_2O)(bpy)_2]^<4+> at a nafion-coated electrode." J.Electroanal.Chem.348. 367-376 (1993)
[文献書誌] Kaneko,M.(Nagai,K.): "Molecular distribution of photoluminescent Ru(bpy)_3^<2+> dispersed in a polymer film and the distance for the concentration quenching." J.Photochem.Photobiol.(in press). (1994)
[文献書誌] Matsuo,T.(Nakamura,H.): "Time-resolved electron spin resonance spectra of linked radical pairs on laser excitation of zink tetraphenylporphyrin-viologene systems." J.Phys.Che.97. 534-536 (1993)
[文献書誌] Matsuo,T.(Yamada,S.): "Asymmetric property of an ultrathin polymer film impregnated with amphilic polypyridine complex for photocatalytic reduction of viologen." J.Chem.Soc.Chem.Commun.16. 1288-1290 (1993)
[文献書誌] 豊島喜則: "日本膜学会編膜学実験シリーズ第I巻生体膜編クロマトフォア" 共立出版株式会社, 6 (1994)
[文献書誌] 阿久津秀雄: "水島・宇井編最新生体膜システム物理的手段による生体膜の構造解析" 講談社サイエンティフィック, 8 (1993)
[文献書誌] 阿久津秀雄: "植木・永井編著嫌気微生物学第4章硝酸還元細菌の生理・生化学" 養賢堂, 25 (1993)
[文献書誌] 阿久津秀雄: "日本膜学会編膜学実験シリーズ第I巻生体膜編膜研究技術" 共立出版株式会社, 8 (1994)
[文献書誌] Watanabe,T.: "Spectroscopic and redox requirements for pigments constituting plantphotosystem I and II reaction centers.In Redox mechanisms and interfacial properties of molecules of biological interest." The Electrochemical Society,Inc.,Pennington,NJ, 9 (1993)
[文献書誌] Kakitani,T.: "Excited state dynamics of retinal proteins by ETDA method.In Frontiers of Photobiology,A.Shima et al.ed." Elsevier Science Publishers, 6 (1993)
[文献書誌] 岡田正: "日本化学会編第4版実験化学講座11、反応と速度液相光反応" 丸善, 14 (1993)
[文献書誌] 森島洋太郎: "高分子化学第4章" 共立出版, (1993)

1993 年度 実績報告書

生体電子移動の局所環境による制御とシステム最適化の分子機構-人工化を目指して-

研究代表者

豊島 喜則 京都大学, 総合人間学部, 教授 (60013166)

研究成果

[文献書誌] Toyoshima,Y.(Wada,T.): "In vitro analysis of light-induced transcription in wheat psbD/C gene cluster using plastid extracts from dark-grown and short-term illuminated seedlings." Plant Physiology(in press). 104. (1994)

[文献書誌] Toyoshima,Y.(Araga,C.): "Functional reconstitution of the primary quinone acceptor,Q_A in the photosystem II core complexes." Biochim.Biophys.Acta. 1142. 36-42 (1993)

[文献書誌] Itoh,S.(Nagashima,K.V.P.): "Photo-oxidation of reaction center-bound cytchrome c and generation of membrane potential determined by carotenoid band shift in the purple photosynthetic bacterium,Rhodospirillium milischianum." Biochim.Biophys.Acta. 1140. 297-303 (1993)

[文献書誌] Itoh,S.(Ikegami,I.): "Reconstitution of the photosystem I secondary quinone acceptor(A_l)in the p700-F_X core isolated from Synechococcus PSS 6301." Plant and Cell Physiology. 34. 849-853 (1993)

[文献書誌] Akutsu,H.(Akutsu,H.): "L-Methionine methyl is specifically incorporated into the c-2 and c-7 positions of the porphyrin of cytchrome c3 in a strictly anaerobic bacterium,Desulfovibro vulgaris." J.Am.Chem.Soc.115. 12185-12186 (1993)

[文献書誌] Akutsu,H.(Odahara,T.): "Dynamic properties of nucleic acids in supramolecular systems as studied by ^<31>P NMR." J.Biochem.(in press). (1994)

[文献書誌] Miki,K.(Hayano,T.): "PDI and Glutathione-mediated reduction of the glutathionylated variant of human lysozyme." FEBS Lett.328. 203-208 (1993)

[文献書誌] Miki,K.(Miki,K.): "Crystallization and preliminary X-ray diffraction studies of photolyase(Photoreactivating enzyme)from the cyanobacterium Anacystis nidulans." J.Mol.Biol.233. 167-169 (1993)

[文献書誌] Inoue,Y.(Noguchi,T.): "Thermoluminescence emission at liquid helium temperatures from photosynthetic apparatus and purified pigments." Biochim.Biophys.Acta. 1141. 18-22 (1993)

[文献書誌] Inoue,Y.(Noguchi,T.): "FT-IR studies on the triplet atate of P_<680> in the photosystem II reaction center:Triplet equilibrium within a chlorophyll dimer." Biochemistry. 32. 7186-7195 (1993)

[文献書誌] Matsuura,K.(Matsuura,K.): "Electrochromic spectral band shift of carotenoids in the photosynthetic membranes of Rhodospirillum molischianum and Rhodospirillum photometricum." Biochim Biophys.Acta. 1140. 92-97 (1993)

[文献書誌] Matsuura,K.(Nagashima,K.V.P.): "Primary structure and transcription of genes encoding B870 and photosynthetic reaction center apoproteins from Rubrivivax gelatinosus." J.Biol.Chem.269. 2477-2484 (1994)

[文献書誌] Watanabe,T.(Maeda,H.): "Chemical environment heterogeneity around the two chlorophyll a' molecules in photosystem I." J Photochem.Photobiol.B:Biol.20. 139-143 (1993)

[文献書誌] Watanabe,T.(Nishiyama,Y.): "Purification and substrate specificity of chlorophyllase from Chlorella regularis." Chem Lett.69-72 (1994)

[文献書誌] Kakitani,T.(Kakitani,T.): "Reexamination of basic theory." Photochem.Photobiol.58. 175-177 (1993)

[文献書誌] Kakitani,T.(Nagae,H.): "Calculation of the excitation transfer matrix elements between the S2 or S1 state of carotenoid and the S2 or S1 state of bacteriochlorophyll." J.Chem.Phys.98. 8012-8023 (1993)

[文献書誌] Sumi,H.(Sumi,H.): "A new method for obtaining bound states of a lattice electron." J.Phys.Soc.Jpn.62. 1500-1508 (1993)

[文献書誌] Sumi,H.(Sumi,H.): "Dimensionality dependence in self-trapping of excitons." J Phys.Soc.Jpn.63. 524-534 (1994)

[文献書誌] Yamazaki,T.(Yamazaki,T.): "Excited-state properties of hypericin:Electronic spectra and fluorescence decay kinetics." J.Phys.Chem.97. 7870-7875 (1993)

[文献書誌] Yamazaki,T.(Yamazaki,T.): "Time-resolved fluorescence spectroscopy and photolysis of the photoreceptor blepharismin." Biochim.Biophys.acta. 1143. 319-326 (1993)

[文献書誌] Okada,T.(Imahori,H.): "Porphyrin-quinone compounds with a spacer of diacetylene unit." Chem.Lett.1215-1218 (1993)

[文献書誌] Okada,T.(Hirata,Y.): "Photophysical properties of diphenylacetylene derivatives in solution phase 3;Thermal repopulation of the S2 state of(Aminophenyl)phenylacethylene." J.Phys.Chem.97. 9677-9681 (1993)

[文献書誌] Sakata,Y.(Borovkov,V.): "Evidence for parallel photoinduced electron transfer in diquinone substituted porphyrins." Chem Lett.145-148 (1993)

[文献書誌] Sakata,Y.(Ponomarev,G.V.): "Synthesis and prpperties of cis-1,2-bis-(octaethylporphyrinyl)ethylene." Tetrahedron Lett.34. 2153-2156 (1993)

[文献書誌] Osuka,A.(Osuka,A.): "1,2-Phenylene-bridged diporphyrin linked with porphyrin monomer and pyromellitimide as a model for photosynthetic reaction center:Synthesis and photoinduced charge separation." J Am.Chem Soc.115. 4577-4589 (1993)

[文献書誌] Osuka,A.(Osuka,A.): "Synthesis and photoexcited dynamics of aromatic group-bridged carotenoid-porphyrin dyads and carotenoid-porphyrin-pyromellitimide triads." J.Ame.Chem.Soc.115. 9439-9452 (1993)

[文献書誌] Morishima,Y.(Morishima,Y.): "Synthesis and some fluorescence properties of Poly(2-methacrylamido-3-arylpropionic acid)." Macromolecules. 26. 789-796 (1993)

[文献書誌] Morishima,Y.(Morishima,Y.): "Effect of counterion condensation on the fluorescence quenching of phenan-threne covalently attached to polyelectrolytes." J.Polym.Sci.,Polym.Chem.Ed.31. 4293-4297 (1993)

[文献書誌] Fujihira,M.(Fujihira,M.): "A novel differential electrochemical mass spectroscopy(DEMS)with a stationary gas-permeable electrode in a rotational flow produced by a rotating rod." J.Electroanal.Chem.347. 457-463 (1993)

[文献書誌] Fujihira,M.(Frommer,J.): "Adsorption at domain edges." Nature. 364. 198-198 (1993)

[文献書誌] Kaneko,M.(Ramaraj,R.): "In situ spectrocyclic coltammetry investigations on the formation of water oxidation catalyst[(bpy)_2(H_2O)Ru-O-Ru(H_2O)(bpy)_2]^<4+> at a nafion-coated electrode." J.Electroanal.Chem.348. 367-376 (1993)

[文献書誌] Kaneko,M.(Nagai,K.): "Molecular distribution of photoluminescent Ru(bpy)_3^<2+> dispersed in a polymer film and the distance for the concentration quenching." J.Photochem.Photobiol.(in press). (1994)

[文献書誌] Matsuo,T.(Nakamura,H.): "Time-resolved electron spin resonance spectra of linked radical pairs on laser excitation of zink tetraphenylporphyrin-viologene systems." J.Phys.Che.97. 534-536 (1993)

[文献書誌] Matsuo,T.(Yamada,S.): "Asymmetric property of an ultrathin polymer film impregnated with amphilic polypyridine complex for photocatalytic reduction of viologen." J.Chem.Soc.Chem.Commun.16. 1288-1290 (1993)

[文献書誌] 豊島喜則: "日本膜学会編 膜学実験シリーズ 第I巻 生体膜編 クロマトフォア" 共立出版株式会社, 6 (1994)

[文献書誌] 阿久津秀雄: "水島・宇井編 最新生体膜システム 物理的手段による生体膜の構造解析" 講談社サイエンティフィック, 8 (1993)

[文献書誌] 阿久津秀雄: "植木・永井編著 嫌気微生物学 第4章 硝酸還元細菌の生理・生化学" 養賢堂, 25 (1993)

[文献書誌] 阿久津秀雄: "日本膜学会編 膜学実験シリーズ 第I巻 生体膜編 膜研究技術" 共立出版株式会社, 8 (1994)

[文献書誌] Watanabe,T.: "Spectroscopic and redox requirements for pigments constituting plantphotosystem I and II reaction centers.In Redox mechanisms and interfacial properties of molecules of biological interest." The Electrochemical Society,Inc.,Pennington,NJ, 9 (1993)

[文献書誌] Kakitani,T.: "Excited state dynamics of retinal proteins by ETDA method.In Frontiers of Photobiology,A.Shima et al.ed." Elsevier Science Publishers, 6 (1993)

[文献書誌] 岡田正: "日本化学会編 第4版実験化学講座11、反応と速度 液相光反応" 丸善, 14 (1993)

[文献書誌] 森島洋太郎: "高分子化学 第4章" 共立出版, (1993)

1993 年度実績報告書

豊島喜則京都大学, 総合人間学部, 教授 (60013166)

[文献書誌] 豊島喜則: "日本膜学会編膜学実験シリーズ第I巻生体膜編クロマトフォア" 共立出版株式会社, 6 (1994)

[文献書誌] 阿久津秀雄: "水島・宇井編最新生体膜システム物理的手段による生体膜の構造解析" 講談社サイエンティフィック, 8 (1993)

[文献書誌] 阿久津秀雄: "植木・永井編著嫌気微生物学第4章硝酸還元細菌の生理・生化学" 養賢堂, 25 (1993)

[文献書誌] 阿久津秀雄: "日本膜学会編膜学実験シリーズ第I巻生体膜編膜研究技術" 共立出版株式会社, 8 (1994)

[文献書誌] 岡田正: "日本化学会編第4版実験化学講座11、反応と速度液相光反応" 丸善, 14 (1993)

[文献書誌] 森島洋太郎: "高分子化学第4章" 共立出版, (1993)