2000 Fiscal Year Annual Research Report

酸素活性種の電子移動特性と制御

Research Project

Project/Area Number	11228205
Research Institution	Osaka University
Principal Investigator	福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)
Co-Investigator(Kenkyū-buntansha)	末延知義大阪大学, 大学院・工学研究科, 助手 (90271030) 今堀博大阪大学, 大学院・工学研究科, 助教授 (90243261)
Keywords	金属酸素錯体活性種 / 電子移動触媒作用 / スカンジウムイオン / スーパーオキシド / 電子スピン共鳴 / スーパーオキシド不均一化酵素 / SOD触媒サイクル / 人工光合成モデル
Research Abstract	本研究では酸素活性種の電子移動特性の解明とその制御を目的とし、酸素活性種特にスーパーオキシドイオンの金属錯体の電子移動特性とその制御法について研究を行った。その結果、活性酸素種のスーパーオキシド(O_2^-)が、スカンジウムイオン(Sc^<3+>)と錯形成することを見出し、溶液系で、しかも常温でのESR観測に初めて成功した。O_2^-はSc^<3+>のみならず各種金属イオンと錯形成し、その配位結合の強さはO_2^-金属錯体のESRのg因子(g_<zz>成分)から簡単かつ定量的に評価できることがわかった。これにより、各種金属イオンのルイス酸性の強さを定量的に評価でき、その結果は、O_2の電子移動還元反応の制御のみならず一般のルイス酸触媒反応の制御にも利用できる。また、イミダゾレート架橋し、かつ配位サイトを有するスーパーオキシド不均一化酵素(SOD)のモデル錯体を初めて合成することに成功し、世界最高のSOD活性を実現することができた。さらにSOD触媒サイクルにおけてZn(II)イオンはO_2^-と錯体を形成することにより、O_2^-の還元を活性化することがわかった。一方、人工光合成モデルとして亜鉛ポルフィリン-フラーレン連結分子などを合成し、その光電荷分離後の逆電子移動過程において、酸素が触媒として機能することを発見した。

Research Products

(32 results)

All Other

All Publications (32 results)

[Publications] Shunichi Fukuzumi et al.: "Light-Harvesting and Photocurrent Generation by Gold Electrodes Modified with Mixed Self-Assembled Monolayers of Boron-Dipyrrin and Ferrocene-Porphyrin-Fullerene Triad"J.Am.Chem.Soc.. 123・1. 100-110 (2000)
[Publications] Shunichi Fukuzumi et al.: "Photoactive Three-Dimensional Monolayers : Porphyrin-Alkanethiolate-Stabilized Gold Clusters"J.Am.Chem.Soc.. 123・2. 335-336 (2000)
[Publications] Shunichi Fukuzumi et al.: "Catalytic Effects of Dioxygen on Intramolecular Electron Transfer in Radical Ion Pairs of Zinc Porphyrin-Linked Fullerenes"J.Am.Chem.Soc.. 123・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Effects of Metal Ions on Physicochemical Properties and Redox Reactivity of Phenolates and Phenoxyl Radicals : Mechanistic Insight into Hydrogen Atom Abstraction by Phenoxyl Radical-Metal Complexes"J.Am.Chem.Soc.. 123・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Modulating Charge Separation and Charge Recombination Dynamics in Porphyrin-Fullerene Linked Dyads and Triads : Marcus-Normal versus Inverted Region,"J.Am.Chem.Soc.. 123・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Effects of Metal Ions on the Electronic, Redox, and Catalytic Properties of Cofactor TTQ of Quinoprotein Amine Dehydrogenases"J.Am.Chem.Soc.. 122・49. 12087-12097 (2000)
[Publications] Shunichi Fukuzumi et al.: "Photochemical Reactions of Coenzyme PQQ (Pyrroloquinolinequinone) and Analogues with Benzyl Alcohol Derivatives via Photoinduced Electron Transfer"J.Am.Chem.Soc.. 122・35. 8435-8443 (2000)
[Publications] Shunichi Fukuzumi et al.: "Hydride Transfer from 9-Substituted 10-Methyl-9,10-dihydroacridines to Hydride Acceptors via Charge-transfer Complexes and Sequential Electron-Proton-Electron Transfer. A Negative Temperature Dependence of the Rates"J.Am.Chem.Soc.. 122・18. 4286-4294 (2000)
[Publications] Shunichi Fukuzumi et al.: "Stepwise Bond Formation in Photochemical and Thermal Diels-Alder Reactions of C_<60> with Danishefsky's Dienes"J.Am.Chem.Soc.. 122・10. 2236-2243 (2000)
[Publications] Shunichi Fukuzumi et al.: "Resonance Raman Spectroscopy as a Probe of the Bis(μ-oxo) dicopper Core"J.Am.Chem.Soc.. 122・5. 792-802 (2000)
[Publications] Shunichi Fukuzumi et al.: "Synthesis and Characterization of Imidazolate-Bridged Dinuclear Complexes as Active Site Models of Cu, Zn-SOD"J.Am.Chem.Soc.. 122・24. 5733-5741 (2000)
[Publications] Shunichi Fukuzumi et al.: "Electrosynthesis and Structural Characterization of Two (C_6H_5CH_2)_4C_<60> Isomers"J.Am.Chem.Soc.. 122・4. 563-570 (2000)
[Publications] Shunichi Fukuzumi et al.: "Photoinduced energy transfer in mixed self-assembled monolayers of pyrene and porphyrin"Chem.Commun.. ・8. 661-662 (2000)
[Publications] Shunichi Fukuzumi et al.: "Catalytic effect of monovalent cations on the amine oxidation by cofactor TTQ of quinoprotein amine dehydrogenases"Chem.Commun.. ・5. 329-330 (2000)
[Publications] Shunichi Fukuzumi et al.: "Regioreversed Thermal and Photochemical Reduction of 10-Methylacridinium and 1-Methylquinolinium Ions by Organosilanes and Oraganostannanes"J.Phys.Chem.A. 105・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "An Extremely Small Reorganization Energy of Electron Transfer in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Solvent Dependence of Charge Separation and Charge Recombination Rates in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・2. 325-332 (2001)
[Publications] Shunichi Fukuzumi et al.: "Effects of Lowering Symmetry on the ESR Spectra of Radical Anions of Fullerene Derivatives and the Reduction Potentials"J.Phys.Chem.A. 104・46. 10688-10694 (2000)
[Publications] Shunichi Fukuzumi et al.: "Effect of Addition Pattern on the Electrochemical and Spectroscopic Properties of Neutral and Reduced 1,2- and 1,4-(C_6H_5CH_2)_2C_<60> Isomers"J.Phys.Chem.A. 104・17. 3878-3883 (2000)
[Publications] Shunichi Fukuzumi et al.: "Splitting of Degenerate Orbitals of Dibenzyl and Tetrabenzyl Adducts of C_<60> : ESR of the Radical Anions and the Rotation Barriers of Benzyl Groups"J.Phys.Chem.A. 104・13. 2908-2913 (2000)
[Publications] Shunichi Fukuzumi et al.: "Electrogeneration and Characterization of (C_6H_5CH_2)_2C_<70>"J.Phys.Chem.A. 104・13. 2902-2907 (2000)
[Publications] Shunichi Fukuzumi et al.: "Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles"J.Org.Chem.. 66・4. 1450-1454 (2000)
[Publications] Shunichi Fukuzumi et al.: "Photochemical Generation of Cyclopentadienyliron Dicarbonyl Anion by a Nicotinamide Adenine Dinucleotide Dimer Analogue"Inorg.Chem.. 40・(in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Model Complexes for the Active Form of Galactose Oxidase. Physicochemical Properties of Cu(II)- and Zn(II)-Phenoxyl Radical Complexes"Inorg.Chem.. 39・16. 3708-3711 (2000)
[Publications] Shunichi Fukuzumi et al.: "100% Selective Oxygenation of p-Xylene to p-Tolualdehyde via Photoinduced Electron Transfer"Org.Lett.. 2・23. 3647-3650 (2000)
[Publications] Shunichi Fukuzumi et al.: "Aliphatic Hydroxylation by a Bis (μ-oxo) dicopper (III) Complex"Angew.Chem.Int.Ed.. 39・2. 398-400 (2000)
[Publications] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Metal Ions Derived from the g Values of ESR Spectra of Superoxide : Metal Ion Complexes in Relation to the Promoting Effects in Electron Transfer Reactions"Chem.Eur.J. 6・24. 4532-4535 (2000)
[Publications] Shunichi Fukuzumi et al.: "The Essential Role of a Zn^<II> Ion in the Disproportionation of Semiquinone Radical Anion by an Imidazolate-Bridged Cu^<II>-Zn^<II> Model of Superoxide Dismutase"Angew.Chem.Int.Ed.. 39・24. 4537-4539 (2000)
[Publications] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-bridged Cu(II)-Zn(II) Heterodinuclear and Cu(II)-Cu(II) Homodinuclear Hydroperoxo Complexes as Reaction Intermediate Models of Cu, Zn-SOD"Chem.Commun.. ・12. 1051-1052 (2000)
[Publications] Shunichi Fukuzumi et al.: "Remarkable enhancement of photocurrent generation by ITO electrodes modified with a self-assembled monolayer of porphyrin"Chem.Commun.. ・19. 1921-1922 (2000)
[Publications] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry, Vol.2"Wiley-VCH (in press). (2001)
[Publications] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry, Vol.4"Wiley-VCH (in press). (2001)

2000 Fiscal Year Annual Research Report

酸素活性種の電子移動特性と制御

Principal Investigator

福住 俊一 大阪大学, 大学院・工学研究科, 教授 (40144430)

Research Products

[Publications] Shunichi Fukuzumi et al.: "Light-Harvesting and Photocurrent Generation by Gold Electrodes Modified with Mixed Self-Assembled Monolayers of Boron-Dipyrrin and Ferrocene-Porphyrin-Fullerene Triad"J.Am.Chem.Soc.. 123・1. 100-110 (2000)

[Publications] Shunichi Fukuzumi et al.: "Photoactive Three-Dimensional Monolayers : Porphyrin-Alkanethiolate-Stabilized Gold Clusters"J.Am.Chem.Soc.. 123・2. 335-336 (2000)

[Publications] Shunichi Fukuzumi et al.: "Catalytic Effects of Dioxygen on Intramolecular Electron Transfer in Radical Ion Pairs of Zinc Porphyrin-Linked Fullerenes"J.Am.Chem.Soc.. 123・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Effects of Metal Ions on Physicochemical Properties and Redox Reactivity of Phenolates and Phenoxyl Radicals : Mechanistic Insight into Hydrogen Atom Abstraction by Phenoxyl Radical-Metal Complexes"J.Am.Chem.Soc.. 123・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Modulating Charge Separation and Charge Recombination Dynamics in Porphyrin-Fullerene Linked Dyads and Triads : Marcus-Normal versus Inverted Region,"J.Am.Chem.Soc.. 123・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Effects of Metal Ions on the Electronic, Redox, and Catalytic Properties of Cofactor TTQ of Quinoprotein Amine Dehydrogenases"J.Am.Chem.Soc.. 122・49. 12087-12097 (2000)

[Publications] Shunichi Fukuzumi et al.: "Photochemical Reactions of Coenzyme PQQ (Pyrroloquinolinequinone) and Analogues with Benzyl Alcohol Derivatives via Photoinduced Electron Transfer"J.Am.Chem.Soc.. 122・35. 8435-8443 (2000)

[Publications] Shunichi Fukuzumi et al.: "Stepwise Bond Formation in Photochemical and Thermal Diels-Alder Reactions of C_<60> with Danishefsky's Dienes"J.Am.Chem.Soc.. 122・10. 2236-2243 (2000)

[Publications] Shunichi Fukuzumi et al.: "Resonance Raman Spectroscopy as a Probe of the Bis(μ-oxo) dicopper Core"J.Am.Chem.Soc.. 122・5. 792-802 (2000)

[Publications] Shunichi Fukuzumi et al.: "Synthesis and Characterization of Imidazolate-Bridged Dinuclear Complexes as Active Site Models of Cu, Zn-SOD"J.Am.Chem.Soc.. 122・24. 5733-5741 (2000)

[Publications] Shunichi Fukuzumi et al.: "Electrosynthesis and Structural Characterization of Two (C_6H_5CH_2)_4C_<60> Isomers"J.Am.Chem.Soc.. 122・4. 563-570 (2000)

[Publications] Shunichi Fukuzumi et al.: "Photoinduced energy transfer in mixed self-assembled monolayers of pyrene and porphyrin"Chem.Commun.. ・8. 661-662 (2000)

[Publications] Shunichi Fukuzumi et al.: "Catalytic effect of monovalent cations on the amine oxidation by cofactor TTQ of quinoprotein amine dehydrogenases"Chem.Commun.. ・5. 329-330 (2000)

[Publications] Shunichi Fukuzumi et al.: "Regioreversed Thermal and Photochemical Reduction of 10-Methylacridinium and 1-Methylquinolinium Ions by Organosilanes and Oraganostannanes"J.Phys.Chem.A. 105・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "An Extremely Small Reorganization Energy of Electron Transfer in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Solvent Dependence of Charge Separation and Charge Recombination Rates in Porphyrin-Fullerene Dyad"J.Phys.Chem.A. 105・2. 325-332 (2001)

[Publications] Shunichi Fukuzumi et al.: "Effects of Lowering Symmetry on the ESR Spectra of Radical Anions of Fullerene Derivatives and the Reduction Potentials"J.Phys.Chem.A. 104・46. 10688-10694 (2000)

[Publications] Shunichi Fukuzumi et al.: "Effect of Addition Pattern on the Electrochemical and Spectroscopic Properties of Neutral and Reduced 1,2- and 1,4-(C_6H_5CH_2)_2C_<60> Isomers"J.Phys.Chem.A. 104・17. 3878-3883 (2000)

[Publications] Shunichi Fukuzumi et al.: "Splitting of Degenerate Orbitals of Dibenzyl and Tetrabenzyl Adducts of C_<60> : ESR of the Radical Anions and the Rotation Barriers of Benzyl Groups"J.Phys.Chem.A. 104・13. 2908-2913 (2000)

[Publications] Shunichi Fukuzumi et al.: "Electrogeneration and Characterization of (C_6H_5CH_2)_2C_<70>"J.Phys.Chem.A. 104・13. 2902-2907 (2000)

[Publications] Shunichi Fukuzumi et al.: "Comparison between Electron Transfer and Nucleophilic Reactivities of Ketene Silyl Acetals with Cationic Electrophiles"J.Org.Chem.. 66・4. 1450-1454 (2000)

[Publications] Shunichi Fukuzumi et al.: "Photochemical Generation of Cyclopentadienyliron Dicarbonyl Anion by a Nicotinamide Adenine Dinucleotide Dimer Analogue"Inorg.Chem.. 40・(in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Model Complexes for the Active Form of Galactose Oxidase. Physicochemical Properties of Cu(II)- and Zn(II)-Phenoxyl Radical Complexes"Inorg.Chem.. 39・16. 3708-3711 (2000)

[Publications] Shunichi Fukuzumi et al.: "100% Selective Oxygenation of p-Xylene to p-Tolualdehyde via Photoinduced Electron Transfer"Org.Lett.. 2・23. 3647-3650 (2000)

[Publications] Shunichi Fukuzumi et al.: "Aliphatic Hydroxylation by a Bis (μ-oxo) dicopper (III) Complex"Angew.Chem.Int.Ed.. 39・2. 398-400 (2000)

[Publications] Shunichi Fukuzumi et al.: "Quantitative Evaluation of Lewis Acidity of Metal Ions Derived from the g Values of ESR Spectra of Superoxide : Metal Ion Complexes in Relation to the Promoting Effects in Electron Transfer Reactions"Chem.Eur.J. 6・24. 4532-4535 (2000)

[Publications] Shunichi Fukuzumi et al.: "The Essential Role of a Zn^<II> Ion in the Disproportionation of Semiquinone Radical Anion by an Imidazolate-Bridged Cu^<II>-Zn^<II> Model of Superoxide Dismutase"Angew.Chem.Int.Ed.. 39・24. 4537-4539 (2000)

[Publications] Shunichi Fukuzumi et al.: "Characterization of Imidazolate-bridged Cu(II)-Zn(II) Heterodinuclear and Cu(II)-Cu(II) Homodinuclear Hydroperoxo Complexes as Reaction Intermediate Models of Cu, Zn-SOD"Chem.Commun.. ・12. 1051-1052 (2000)

[Publications] Shunichi Fukuzumi et al.: "Remarkable enhancement of photocurrent generation by ITO electrodes modified with a self-assembled monolayer of porphyrin"Chem.Commun.. ・19. 1921-1922 (2000)

[Publications] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry, Vol.2"Wiley-VCH (in press). (2001)

[Publications] Shunichi Fukuzumi et al.: "Electron Transfer in Chemistry, Vol.4"Wiley-VCH (in press). (2001)

福住俊一大阪大学, 大学院・工学研究科, 教授 (40144430)