膜蛋白質および関連高分子におけるエネジェテックスとダイナミクスの物理化学的基礎

1989 年度 実績報告書

• 研究課題/領域番号: 01300009
• 研究機関: 名古屋大学
• 研究代表者: 垣谷 俊昭 名古屋大学, 理学部, 助教授 (90027350)
• 研究分担者: 伊藤 繁 岡崎国立共同研究機構, 基礎生物学研究所, 助教授 (40108634) ; 三木 邦夫 大阪大学, 工学部, 助手 (10116105) ; 坂田 祥光 大阪大学, 産業科学研究所, 助教授 (60029874) ; 岡田 正 大阪大学, 基礎工学部, 助教授 (40029442) ; 豊島 喜則 広島大学, 総合科学部, 教授 (60013166)
• キーワード: 生体エネルギ-変換 / 生体情報変換 / 膜蛋白の構造と機能 / 電子移動 / 励起状態ダイナミクス / 熱発光 / 非熱平衡反応

研究概要

本年度は昨年7月と今年1月の2回にわたり班会議をもった。班員各自の研究内容を紹介していただく一方、当面集約されつつある問題点について、班員以外の専門家もお呼びしてテ-マ毎に2時間〜4時間の特別セッションを設け、十分な討論を行った。まず、電子移動反応のエネルギ-・ギャップ則が誘電媒体の誘電飽和の非線形効果によってどのように影響を受けるのかについて、厳しい議論がなされた。その結果、エネルギ-・ギャップ則は、非線形効果によって巾広くなったり(電荷分離反応)、狭くなったり(電荷再結合反応)するが、inverted regionはすべての場合に存在するという結論を得た。これは生体エネルギ-変換を支える酸化・還元反応の1つの基本法則になりうる。次に集中的に討論された課題は光合成系熱発光の機構である。熱発光は酸素発生系のS状態について極めて重要な情報をもたらすが、その発光の過程の詳細はいまだ十分に明らかにされていない。これまで、光化学系IIの電荷分離後の電子と空孔が互いに酸化還元電位のエネルギ-勾配を下って移動し、互いに遠く離れてしまうが、熱励起によって、互いにエネルギ-勾配を登ってPの位置で再結合し、P^*を生成し蛍光を出す機構が想像されている。しかし、そのkineticsとenergeticsについて、物理化学的に解析する余地のあることが議論され、次回もう一度集中討議することとなった。この他に、レチノイド・カロテノイドの三重項状態及び一重項第一励起状態の共鳴ラマン・スペクトルが測定され、励起状態における分子変形に関する精密な情報を得ることが出来たので、今後これを基にシス-トランス光異性化についての励起状態ダイナミクスの議論が進展するものと思われる。また、粘性溶媒中の酵素の非熱平衡反応の理論モデルが提案され、多くの実験家の注目を集めた。

研究成果

• [文献書誌] A.Yoshimori: "Transfer Coefficient in Electrochemical Reactions" J.Phys.Chem.93. 3694-3702 (1989)
• [文献書誌] A.Yoshimori: "Shapes of the Electron-Transfer Rate vs Energy Gap Relations in Polar Solutions" J.Phys.Chem.93. 8316-8323 (1989)
• [文献書誌] T.Kakitani: "Effect of freezing out protein vibrational modes on electron transfer kinetics in bacterial reaction centers" Photosynthesis Research. 22. 187-193 (1989)
• [文献書誌] S.Fukuhara: "Disintegration and reconstitution of PSII reaction center core complex.II.Reconstitution of QA function" J.Biol.Chem.
• [文献書誌] Y.Kobayashi: "Cyclic electron transport around PSII reaction center through Cyt b-559." Biochim.Biophys.Acta.
• [文献書誌] A.Miyazaki: "Stoichiometry of Cyt b-559 in photosystem II reaction center complex" Biochim.Biophys.Acta. 975. 142-147 (1989)
• [文献書誌] Y.Morishima: "Photoinduced Electron Transfer in Chromophores Rigidly Compartmentalized in a Microphase Structure of Amphiphilic Polyelectrolytes in Aqueour Solution" J.Phys.Chem.93. 1643-1648 (1989)
• [文献書誌] N.Mataga: "Picosecond Dynamics of Intramolecular Electron Transfer and Energy Transfer in Porphyrin Dimer Model Compounds" Chem.Phys.131. 473-480 (1989)
• [文献書誌] N.Mataga: "Charge-Transfer Rates in Symmetric and Symmetry-Disturbed Derivatives of 9.9´-Bianthryl" J.Phys.Chem.93. 3383-3386 (1989)
• [文献書誌] Y.Inoue: "Synchrotron Radiation Study of Weak Fluorescence from Neat Liquids of Simple Alkanes:Anomalous Excitation Spectra as Evidence for Wavelength-Dependent Photochemistry" J.Am.Chem.Soc.111. 5584-5586 (1989)
• [文献書誌] H.Kobashi: "Ion-Pair Formation Competing with Internal Conversion from the Second Excited State in the Chloranil-Diphenylamine Complex" Chem.Phys.Lett.160. 261-266 (1989)
• [文献書誌] N.Mataga: "Picosecond Laser Photolysis Studies on Dimer Model Systems in Relation to Photosynthetic Charge Separation Processes" Tetrahedron. 45. 4683-4692 (1989)
• [文献書誌] H.Yao: "Solvation Induced Charge Separation in the Excited State of Composite Systems with Identical Halves and Picosecond Laser Photolysis Studies on 1,2-Dianthrylethanes" J.Phys.Chem.93. 7388-7394 (1989)
• [文献書誌] Y.Sakata: "Synthesis of Completely Fixed Porphyrin-Quinone Compounds and the Mutual Orientation Effect on Electron Transfer" J.Am.Chem.Soc.111. 8979-8981 (1989)
• [文献書誌] S.Kinoshita: "Solvent Relaxation Effect on Transient Hole-Burning Spectra of Organic Dyes" Chem.Phys.Lett.
• [文献書誌] N.Mataga: "Femtosecond-Picosecond Laser Photolysis Studies on the Photoinduced Charge Separation and Charge Recombination of Produced Ion Pair State of Some Typical Intramolcular Exciplex Compounds in Alkanenitrile Solvents" J.Phys.Chem.
• [文献書誌] S.Itoh: "New herbicide-binding site in the photosynthetic electron-transport chain.Competitive herbicide binding at the photosystem I phylloguinone-(vitamin Kl)-binding site" FEBS Lett.250. 441-447 (1989)
• [文献書誌] Y.Takahashi: "Silicomolybdate substitute for the function of a primary electron acceptor and stabilizes charge separatation in the photosystem II reaction center complex" FEBS Lett.255. 1333-1338 (1989)
• [文献書誌] M.Iwaki: "Electron transfer in spinach photosystem I reaction center containing benzo-, naphtho- and anthraquinones in place of phylloquinone" FEBS Lett.256. 11-16 (1989)
• [文献書誌] S.Hoshina: "Selective destruction of iron sulfur centers by hear/ethylene glycol treatment and isolation of photosystem I core complex" Biochim.Biophys.Acta. 1015. 61-68 (1990)
• [文献書誌] S.Hoshina: "Characterization and N-terminal sequence of a 5 kDa polypeptide associated with photosystem I core complex from spinach" FEBS Lett.258. 305-308 (1989)
• [文献書誌] S.Itoh: "Vitamin K-l(phylloquinone)restores the turnover of FeS centers in the ether-extracted spinach PS I particles" FEBS Lett.243. 47-52 (1989)
• [文献書誌] T.Ono: "A marked upshift in threshold temperature for the S_1-to-S_2 transition induced by low pH treatment of PSII membranes" Biochim.Biophys.Acta.
• [文献書誌] T.Ono: "Abnormal redox reactions in photosynthetic O_2-evolving centers in NaCl/EDTA-washed PSII.A dark-stable EPR multiline signal and a new unknown positive charge accumulator" Biochim.Biophys.Acta.
• [文献書誌] M.Mitsue: "An improved procedure for photoactivation of photosynthetic oxygen evolution: Effect of 2.6-dichlorophenol indophenol on the photoactivation yield of NH_2OH-treated photosystem II membranes" Biochim.Biophys.Acta. (submitted)
• [文献書誌] M.Mimuro: "Excitation energy flow in chlorosome antennas of green photosynthetic bacteria" J.Phys.Chem.93. 7503-7509 (1989)
• [文献書誌] M.Mimuro: "Excitation energy transfer in phycobilisomes at -196ﾟC isolated from the cyanobacterium Anabaena variabilis(M-3):Evidence for the plural transfer pathways to the terminal emitters" Biochim.Biophys.Acta. 973. 153-162 (1989)
• [文献書誌] K.Shimada: "Excitation energy transfer in Rhodobacter sphaeroides analyzed by the time-resolved fluorescence spectrum" Biochim.Biophys.Acta. 975. 72-79 (1989)
• [文献書誌] D.Frackowiak: "Polarized time-resolved fluorescence spectra of phycobilisomes isolated from Tolypothrix tenuis embedded in poly(vinyl alcohol)" Photochem.Photobiol.50. 563-570 (1989)
• [文献書誌] T.Katoh: "Light harvesting particles isolated from a brown alga Dictyota dichotoma: A Supramolecular assembly of fucoxanthis-chlorophyll complex" Biochim.Biophys.Acta. 976. 233-240 (1989)
• [文献書誌] S.Tokutomi: "Orientation of the chromophore transition moment in the "four-leaved shape model"for phytochrome in the red- absorbing form and its rotation induced by the phototransformation to the far-red absorbing form" FEBS Lett.255. 350-353 (1989)
• [文献書誌] M.Mimuro: "Spatial arrangement of pigments and their interaction in the fucoxanthin-chl a/c protein assembly(FCPA)isolated from the brown alga Dictyota dichotoma:Analysis by means of polarized spectroscopy" Biochim.Biophys.Acta. 1015. 450-456 (1990)
• [文献書誌] M.Mimuro: "Characteristic fluorescence components in the pigment system of the marine dinoflagellate Protogonyaulax tamarensis and energy flow among them: Studies by means of steady-state and time-resolved fluorescence spectroscopy" Biochim.Biophys.Acta.
• [文献書誌] K.Shimada: "Excitation energy flow in a photosynthetic bacterium lacking B850: Fast energy transfer from B806 to B870 in Erythrobacter sp.strain OCh 114" Biochim.Biophys.Acta.
• [文献書誌] M.Mimuro: "Carotenoids in Photosynthesis-Absorption, transfer and dissipation of light energy" Pure Appl.Chem.
• [文献書誌] M.Mimuro: "Analysis of energy transfer mechanism in photosynthesis" Bot.Mag.Tokyo.
• [文献書誌] M.Mimuro: "Excitation energy flow in purple photosynthetic bacteria: Analysis by the timeresolved fluorescence spectroscopy. In: Molecular biology of membrane-bound complex in phototrophic bacteria(G.Drews ed.)" Plenum press.
• [文献書誌] H.Kandori: "Mechanism of isomerization of rhodopsin studied by use of 11-cis-locked rhodopsin analogs excited with picosecond" Biochemistry. 28. 6460-6467 (1989)
• [文献書誌] Y.Imamoto: "The effect of chloride ion on the thermal decay process of batho-intermediate of iodopsin at low temperature" Biochemistry. 28. 9412-9496 (1989)
• [文献書誌] Y.Shichida: "Effects of chloride on chicken iodopsin to scotopsin and B-photopsin" Biochemistry.
• [文献書誌] H.Hashimoto: "The c=c stretching Raman lines of β-caroten isomers in the S_1 state as detected by pump-probe resonance Raman" Chem.Phys.Lett.154. 321-325 (1989)
• [文献書誌] Y.Koyama: "'H NMR spectra of the all-trans,7-cis,9-cis,13-cis and 15-cis isomers of β-carotene:Elongation of the double bond and shortening of the single bond toward the center." J.Mol.Struct.193. 185-201 (1989)
• [文献書誌] H.Hashimoto: "Time-resolved absorption spectroscopy of the friplet state produced from the all-trans,7-cis,9-cis,13-cis and 15-cis isomers of β-carotene" Chem.Phys.Lett.162. 517-522 (1989)
• [文献書誌] H.Hashimoto: "Raman spectra of all-trans-β-apo-8´-carotenal in the S_1 and T_1 states:A picosecond pump-and-probe technique using ML-QS pulse trains" Chem.Phys.Lett.162. 523-527 (1989)
• [文献書誌] H.Hashimoto: "Raman spectra of all-trans-β-carotene in the S_1 and T_1 states produced by direct photoexcitation" Chem.Phys.Lett.163. 251-256 (1989)
• [文献書誌] E.Nishizawa: "Raman spectra of chlorophyll a in the T_1 state" Chem.Phys.Lett.164. 155-160 (1989)
• [文献書誌] T.Kouyama: "Correlation between internal motion and emission kinetics of tryptophan residues in proteins" Eur.J.Biochem.182. 517-521 (1989)
• [文献書誌] T.Kouyama: "Turnover rate of the proton pumping cycle of bacteriorhodopsin: pH and light-intensity dependences" Biochemistry. 28. 5963-5970 (1989)
• [文献書誌] S.Suzuki: "Independent flexible motion of submolecular domains of the Ca^<2+>,Mg^<2+>-ATPase of sarcoplasmicreticulum measured by time-resolved fluorescence depolarization of site-specifically attached probes" Biochemistry. 28. 7734-7740 (1989)
• [文献書誌] K.Fukuda: "Effect of partial delipidation of purple membrane on the photodynamics of bacteriorhodopsin" Biochemistry.
• [文献書誌] A.Nasuda-Kouyama: "Effect of a light-induced pH gradient on purple-to-blue and purple-to-red transitions of bacteriorhodopsin" Biochemistry.
• [文献書誌] K.Kaneko: "Gas Kinetic Approach for Electron-Ion Recombination Rate Constant in Dense Media" J.Phys.Soc.Japan. 59.
• [文献書誌] M.Nakamura: "Spin Depolarization on a Linear Chain with Quasiperiodic Larmor Frequencies" J.Phys.Soc.Japan. 59.
• [文献書誌] H.Sumi: "Two kinds of Excimers in α-perylens and pyrene crystals:Origin of Y and V emissions" Chemical Physics. 130. 433-449 (1989)
• [文献書誌] H.Sumi: "Coexistence of two types of self-trapping for two-dimensional excitons" Solid State Communications. 71. 789-792 (1989)
• [文献書誌] T.Noguti: "Structural Basis of Hierarchical Multiple Substates of a Protein.I:Introduction" PROTEINS. 5. 97-103 (1989)
• [文献書誌] T.Noguti: "Structural Basis of Hierarchical Multiple Substates of a protein.II:Monte Carlo Simulation of Native Thermal Fluctuations and Energy Minimization" PROTEINS. 5. 104-112 (1989)
• [文献書誌] T.Noguti: "Structural Basis of Hierarchical Multiple Substates of a Protein.III:Side Chain Local Conformations" PROTEINS. 5. 113-124 (1989)
• [文献書誌] T.Noguti: "Structural Basis of Hierarchical Multiple Substates of a Protein.IV:Rearrangements in Atom Packing and Local Deformations" PROTEINS. 5. 125-131 (1989)
• [文献書誌] T.Noguti: "Structural Basis of Hierarchical Multiple Substates of a Protein.V:Nonlocal Deformations" PROTEINS. 5. 132-138 (1989)
• [文献書誌] M.Nakasako: "Arginine remarkably prolongs the life time of the M-intermediate in the bacteriorhodopsin photocycle at room temperature" FEBS Lett.254. 211-214 (1989)
• [文献書誌] S.Tokutomi: "A model for the dimeric molecular structure of phytochrome based on small-angle X-ray scattering" FEBS Lett.247. 139-142 (1989)
• [文献書誌] 垣谷俊昭: "ロドプシンの構造と波長識別能との関連" 蛋白質・核酸・酵素. 34. 136-144 (1989)
• [文献書誌] 坂田祥光: "光合成モデル化合物による太陽エネルギ-の獲得" ペテロテック. 12. 1006-1011 (1989)
• [文献書誌] 三木邦夫: "紅色光合成細菌の反応中心複合体の立体構造" 蛋白質・核酸・酵素. 34. 726-740 (1989)
• [文献書誌] 伊藤繁: "光合成光化学系I反応中心の構造と内部電子移動過程" 蛋白質・核酸・酵素. 34. 755-767 (1989)
• [文献書誌] 七田芳則: "光受容物質の分子構造と動態" 細胞.
• [文献書誌] 吉沢雅幸: "超短パルスレ-ザ-による時間分解分光" 光学. 18. 477-478 (1989)
• [文献書誌] M.Mimuro: "Excitation energy flow in purple photosynthetic bacteria:Analysis by the timeresolved fluorescence spectroscopy.In:Molecular biology of membtane-bound complex in phototrophic bacteria(G.Drews ed.)" Plenum press,
• [文献書誌] 三木邦夫: "新基礎生化学実験法第5巻「高次構造・状態分析」(中島暉躬 他編)" 丸善, 350 (1989)
• [文献書誌] 木下一彦: "新基礎生化学実験法第5巻「高次構造・状態分析」(中島暉躬 他編)-蛍光・蛍光偏光-" 丸善, 350 (1989)
• [文献書誌] 神山勉: "分光技術ハンドブック「分光測定基礎技術」" 朝倉書店,