光合成系におけるカロテノイドの機能とその基礎としての反応動力学

1991 Fiscal Year Annual Research Report

• Project/Area Number: 02305014
• Research Institution: Okazaki National Research Institution, National Institute for Basic Biology
• Principal Investigator: 三室 守 岡崎国立共同研究機構, 基礎生物学研究所, 助手 (40142004)
• Co-Investigator(Kenkyū-buntansha): 長江 裕芳 神戸市外国語大学, 助教授 (50124871) ; 嶋田 敬三 東京都立大学, 理学部, 助教授 (80112473) ; 小山 泰 関西学院大学, 理学部, 教授 (90079666) ; 加藤 哲也 京都大学, 理学部, 講師 (30025308) ; 垣谷 俊昭 名古屋大学, 理学部, 助教授 (90027350)
• Keywords: カロテノイド / 光合成 / エネルギ-移動 / 光合成色素蛋白 / 時間分解分光法 / 分子動力学

Research Abstract

光合成系におけるカロテノイドの機能を、単離した色素、色素蛋白質について分子動力学的に解析し、次のような知見を得た。
(1)実験対象としての色素蛋白質について、生化学的な解析が飛躍的に進んだ。
(1)褐藻からエネルギ-転移能を完全に保持したカロテノイド蛋白質単量体の単離精製に世界で初めて成功した。(2)渦鞭毛藻の水溶性ペリディニン蛋白質の会合体が分離され、アンテナ色素蛋白質の細胞内での一般的性質が確認された。(3)従来、カロテノイド蛋白のモデルとなると考えられていた色素蛋白質の機能を再検討する必要があることが判明した。
(2)単離されたカロテノイドの性質の解析を進めた。
(1)共役系が非対称構造を持つカロテノイドの吸収特性の理論的考察、(2)カロテノイドの吸収帯の赤色移行に関する理論的考察、(3)時間分解ラマン法によるS0準位内での振動緩和の特異な性質、等を明らかにした。
(3)エネルギ-転移機構について考察した。
(1)色素蛋白質中でのカロテノイドからのエネルギ-転移時間は、2ピコ秒より短く、色素間の特異的な相対位置関係が示唆された。(2)カロテノイドの禁制の第一励起準位からの発光測定に成功し、分子構造、エネルギ-転移過程とし関連が明らかとなった。(3)エネルギ-転移機構について、理論的に定式化を行い、電子交換相互作用、ク-ロン相互作用について、遷移一重項間、また多重極間の速度を見積ることができた。ク-ロン相互作用の可能性が具体的に示唆された。
(4)新たな実験系の開発、特に(1)ストリ-クカメラの導入による蛍光測定の時間分解能の改善、(2)色素蛋白質の再構成法の確立を行った。
(5)上記の結果を総合的に討論し、今後の問題点の整理、それらの解析のため共同研究の継続を確認した。

Research Products

• [Publications] Mimuro,M.and T.Katoh: "Carotenoids in photosynthesisーAbsorption,transfer and dissipation of light energy." Pure&Appl.Chem.,. 63. 123-130 (1991)
• [Publications] Uehara,K.,M.Mimuro and M.Tanaka: "Spectroscopic studies of chlorophyll a aggregates formed by aqueous Dimethyl sulfoxide." Photochem.Photobiol.,. 53. 371-377 (1991)
• [Publications] Post A.F.,M.Mimuro and Y.Fujita: "Light 2 directed changes in the effective absorption crossーsection of photosystem II in Synechococcus 27170 are related to modified action on the donor side of the reaction center." Biochim.Biophys.Acta,. 1060. 67-74 (1991)
• [Publications] Mimuro,M.,U.Nagashima,S.Takaichi,Y.Nishimura,I.Yamazaki and T.Katoh: "Molecular structure and optical properties of carotenoids for the iu vivo energy transfer function in algal photosynthetic pigment system." Biochim.Biophys.Acta,. 1098. 271-274 (1992)
• [Publications] Mimuro,M.,Y.Nishimura,I.Yamazaki,T.Katoh and U.Nagashima: "Fluorescence properties of the allenic carotenoid fucoxanthin:Analysis of the effect of keto carbonyl group by using a model compound,allーtransーβーapoー8'ーcarotenal." J.Luminescence,.
• [Publications] Mimuro,M.,U.Nagashima,S.Nagaoka,Y.Nishimura,S.Takaichi,T.Katoh,I.Yamazaki: "Quantitative analysis of the solvent effect on the relaxaーtion processes of carotenoids showing dual emissive characteristics." Chem.Phys.Lett.,.
• [Publications] Iwaki,M.,M.Mimuro and S.Itoh: "Prompt and delayed fluorescence of P700 and antenna chlorophylls in photosystem I particles containing 11 chlorophylls/P700." Biochim.Biophys.Acta,.
• [Publications] Mimuro,M.,T.Nozawa,N.Tamai and I.Yamazaki: "Heterogeneity of antenna components and energy transfer pathways in a green photosynthetic bacterium Chloroflexus aurantiacus:Studies by the timeーresolved fluorescence spectra atー196℃." Biochim.Biophys.Acta.
• [Publications] Uehara,K.,Y.Hioki and M.Mimuro: "Selective formation of the chlorophyll a aggregate absorbing near 685 nm in aqueous tetrahydrofuran." Photochem.Photobiol.
• [Publications] Nakayama,K.,M.Mimuro and M.Okada: "Chlorophyll forms and light energy transfer in lightーharvesting chlorophyll a/b protein complexes from the siphonous green alga Bryopsis maxima." Biochim.Biophys.Acta,.
• [Publications] 三室 守,伊藤 繁,岩城 雅代: "光化学と分光計測 XI.生体系における光化学過程" 分光研究、. 40. 302-315 (1991)
• [Publications] 三室 守: "フェムト秒の生物学ー光合成の物理化学的側面" パリティ-. 6. 36-45 (1991)
• [Publications] 三室 守: "カロテノイドの蛍光特性とエネルギ-転移過程" 化学.
• [Publications] Y.Hatano,T.Kakitani,Y.Enomoto and A.Yoshimori: "Simulation study of free energy curves for electron transfor reaction in polar solutions by considering the electronic polarizability." Mol.Simu.6. 191-197 (1991)
• [Publications] Y.Enomoto,T.Kakitani,A.Yoshimori,Y.Hatano,M.Saito: "Monte Carlo Simulation study on reorganization energy of electron transfer reaction in polar solution." Chem.Phys.Lett.,. 178. 235-240 (1991)
• [Publications] Y.Enomoto,T.Kakitani,A.Yoshimori: "Monte Carlo simulation on energy gap dependence of electron transfer reaction in polar solution:Effect of electric polarizability of solvent." Chem.Phys.Lett.186. 366-371 (1991)
• [Publications] S.Nishikawa,T.Asahu,T.Okada,N.Mataga,T.Kakitani: "Determination of the bimolecular rate constan of photounduced charge separation in the energy gap region where the reaction diffusion controlled analysis of the transitient effect in the course of fluorescence quenching reaction." Chem.Phys.Lett.,. 185. 237-243 (1991)
• [Publications] A.Yoshimori and T.Kakitani: "Solvent dynamical effect on the energy gap law of electron transfer rection in nonーlinear response systems." J.Phys.Soc.Japan.
• [Publications] T.Kakitani,A.Yoshimori and N.Mataga: "Effect of the donorーacceptor distance distribution on the energy gap laws of charge separation and charge recombination reactions in polar solutions." J.Phys.Chem.
• [Publications] T.Kakitani: "On the energy gap law in electron transfer reaction." Proceeding of Yamada Conference XXIX on Dynamics and Mechanisms of photoiduced electron transfer and related phenomena.
• [Publications] M.Saito,T.Kakitani and Y.Hatano: "Monte Carlo simution study on solvation energy of ionic molecule,reorganization energy of electron transfer reaction and mean ionーpair potential." Proceeding of Yamada Conference XXIX on Dynamics and Mechanisms of photoiduced electron transfer and related phenomena.
• [Publications] M.Kuki,Y.Koyama and H.Nagae: "TripletーSensitized and Thermal Isomerization of AllーTrans,7ーCis,9ーCis,13ーCis,and 15ーCis Isomers of βーCarotene:Configurational Dependence of the Quantum Yield of Isomerization via the T1 State." J.Phys.Chem.95. 7171-7180 (1991)
• [Publications] H.Nagae,T.Kakitani,M.Mimuro and T.Katoh: "A theoretical study on the interaction between carotenoids and bacterioーchlorophyll:Calculation of the excitation transfer matrix elements between neurosporen S2 and S1 states and Bchlーa S2 and S1 states."
• [Publications] S.Tokutomi,T.Sugimoto and M.Mimuro: "A model for molecular structure and orientation of the chromophore in a dimeric phytochrome molecules." Photochem.Photobiol.
• [Publications] 西村 賢宣,山崎 トモ子,山崎 巌,渡辺 元之,小石 結: "光子計数型ストリ-クカメラによる蛍光分光測定システム" 分光研究. 40. 155-162 (1991)
• [Publications] M.Naruse,H.Hashimoto,M.Kuki and Y.Koyama: "Triplet Excitation of Precursors of Spirlloxanthin Bound to the Chromatoーphores of Rhodospirillum rubrum as Detected by Transsient Raman Spectroscopy." J.Mol.Struct.242. 15-26 (1991)
• [Publications] H.Hashimoto,Y.Koyama,Y.Hirata and N.Mataga: "The S1 and T1 Species of βーCarotene Generated by Direct PhotoーExcitation from the AllーTrans,9ーCis,13ーCis and 15ーCis Isomers of as Revealed by Picosecond Transient Absorption and Transient Raman Spectroscopies." J.Phys.Chem.95. 3072-3076 (1991)
• [Publications] H.Hashimoto and Y.Koyama: "The So and T1 States of Isomeric Canthaxanthin as Compared with those of βーCarotene:Effect of the Terminal Carbonyl Groups Detected by Raman Spectroscopy." Photochem.Photobiol.54. 67-73 (1991)
• [Publications] Y.Koyama: "Strucres and Functions of Carotemoids in Photosynthetic Systems." J.Photochem.Photobiol.9. 265-280 (1991)
• [Publications] R.J.Cogdell,H.Hashimoto and Y.Koyama: "Picosecond Raman Spectroscopy of the B830 LH2 Complex of Chromatium purpuratum BN 5500." Photosyn.Res.
• [Publications] T.Noguchi,H.Hayashi,M.Tasumi and G.H.Atkinson: "Solvent effects on the FrankーCondon active a_g C=C streshing mode in the 2^1A_g^ーstates of βーcarotene and its derivatives as studied by picosecond timeーresolved resonance Raman spectroscopy." J.Phys.Chem.,. 95. 3167-3172 (1991)
• [Publications] H.Hayashi,M.Tasumi and G.H.Atkinson: "Vibrationallyーexcited states in carotenoids:Picosecond timeーresolved antiーStokes resonance Raman spectroscopy." Chem.Phys.Lett.,. 178. 388-392 (1991)
• [Publications] H.Okamoto,H.Hayashi,K.Yoshihara and M.Tasumi: "Femtosecond timeーresolved coherent antiーStokes Raman scattering from carotenoids in vivo and in vitro:Comparison of vibrational relexation time of the “inーplane"C=C stretching bands." Chem.Phys.Lett.,. 181. 96-100 (1991)
• [Publications] H.Hayashi,T.Noguchi,M.Tasumi and G.H.Atkinson: "Vibrational spectroscopy of excited electronic state in vivo carotenoids:Picosecond timeーresolved resonance Reman sattering." Biophys.J.,. 60. 252-260 (1991)
• [Publications] H.Hayashi,T.Brack,T.Noguchi,M.Tasumi,G.H.Atkinson: "Vibrational relaxationin carotenoids in vivo and in vitro:Picosecond timeーresolved antiーStokes resonance Raman spectroscopy." J.phys.Chem.95. 6797-6802 (1991)
• [Publications] E.H.Morita,H.Hayashi and M.Tasumi: "Implication of the positive band at 1712 cmー1 in the lightーinduced infrared difference spectrum of the bacteriochlorophyllーa special pair in the photoーsynthetic reaction center of Chromatium vinosum." Chem.Lett.,. 1583-1586 (1991)
• [Publications] E.H.Morita,H.Hayashi and M.Tasumi: "Temperature dependecnce of the lightーinduced infrared difference spectra of chromatophores and reaction centers from Rhodobacter spharoidss." Chem.Lett.,. 1853-1856 (1991)
• [Publications] T.Noguchi,H.Hayashi,K.Shimada,S.Takaichi and M.Tasumi: "In.vivo states and functions of the carotenoids in the aerobic photosytnhetic bacterium,Erythrobacter longus." Photosynthe.Res.,.
• [Publications] Y.Watanabe,T.Kameyama,Y.Miki,H.Hashimoto and Y.Koyama: "Photoluminescence of allーtransーβーCarotene."
• [Publications] Y.Watanabe,T.Kameyama,Y.Miki and Y.Koyama: "Lifetimes of lowーlying excited state in allーtransーβーcarotene."
• [Publications] Y.Miki,T.Kameyama,Y.Koyama and T.Watanabe: "Spectroscopy of carotenoid excited state."
• [Publications] Katoh,T.,U.Nagashima and M.Mimuro: "Fluorescence properties of the allenic carotenoid fucoxanthin:Its implication for energy transfer in photosynthetic pigment systems." Photosynthesis Res.27. 231-236 (1991)
• [Publications] 加藤 哲也: "褐藻の光合成光捕捉装置" Plant Science Tomorrow.
• [Publications] M.Iwano,E,Yokomura and T.Katoh: "Photosynthetic vesicles isolated from a brown alga,Ectocarpus siliculsus."
• [Publications] K.Matsuura,M.Hirora,K.Shimada and M.Mimuro: "Spectral forms and orientation of bacteriochlorophylls c and a in chlorosomes of the green photosynthetic bacterium,Chloroflexus aurantiacus." Photochem.Photobiol.,.
• [Publications] M.Hirota,T.Moriyama,K.Shimada,M.Miller,J.M.Olson and K.Matuura: "High degree of organization of bacteriochlorophyll c in chlorosomeーlike aggregates spontaneously assembled in aqueous solution." Biochim.Biophys.Acta.
• [Publications] T.Ogata and M.Kodama: "Peridininーchlorophyll a protein contents of dinoflagelattes Alexandrim tamarense and catenella." J.Appl.Phycol.
• [Publications] T.Ogata and M.Kodama: "Peridininーchlorophyll a protein of toxic dinoflagellates.Proceedings of 5th International conference on toxic marine phytoplankton."
• [Publications] T.Ogata,M.Kodama,T.Katoh and M.Mimuro: "Association form of peridininーchlorophyll aーprotins(PCP)isolated from dinoflagellates Alexandrium cohorticula:The in vivo functional form."
• [Publications] K.Masamoto: "Zeaxanthin accumulation in a cell wall enriched fraction of the cyanoーbacterium Synechococcus PCC7942 grown under highーintensity illumination." Mem.Fac.Edu,Kumamoto Univ.,Nat.Sci.40. 25-30 (1991)
• [Publications] Mimuro,M.: "Dynamics and mechanisms of photoinduced electron transfer and related" Elsevier,Amsterdem,
• [Publications] T.Kakitani: "Trends in Photochemistry and Photobiology,"
• [Publications] T.Kakitani,A.Yoshimori and N.Mataga: "Electron transfer in Inorganic,and biological systems,Advances in Chemistry Series,(J.Bolton ed.)," American Chemistry Society,(1991)
• [Publications] Y.Koyama: "Methods in Enzymology" Academic Press,
• [Publications] Y.Koyama and H.Hashimoto: "In Carotenoids in Photosynthesis." Springer Verlag,
• [Publications] Y.Koyama: "Carotenoids.IB." Birkauser Verlag,
• [Publications] S.Takaichi and K.Shimada: "Methods in Enzymology" Academic Press,
• [Publications] S.Takaichi and J.Ishidsu: "Methods in Enzymology" Academie Press,
• [Publications] T.Katoh,A.Tanaka and M.Mimuro: "Methods in Enzymology" Academic Press,