2003 年度実績報告書

光機能界面における有機物の反応機構の解明

研究課題

研究課題/領域番号	14050055
研究機関	大阪大学
研究代表者	真嶋哲朗大阪大学, 産業科学研究所, 教授 (00165698)
研究分担者	川井清彦大阪大学, 産業科学研究所, 助手 (50314422) 藤乗幸子(佐治幸子) 大阪大学, 産業科学研究所, 助手 (50197844) 藤塚守大阪大学, 産業科学研究所, 助教授 (40282040) 遠藤政幸大阪大学, 産業科学研究所, 助手 (70335389)
キーワード	TiO2光触媒反応 / 光機能界面 / ラジカルカチオン / 一電子酸化 / ヒドロキシラジカル / 過渡吸収測定 / レーザーフラッシュホトリシス / パルスラジオリシス
研究概要	酸化チタン(TiO2)光触媒は、自然のエネルギーである太陽光のみを利用して有機物を分解することができることから、近年、農業廃液などの浄化、脱臭、抗菌などに用いられている。TiO2光触媒による有機化合物の分解反応における重要な初期過程である一電子酸化反応の詳細について明らかにすることにより、高効率・高選択的な光触媒反応系の構築を目指している。時間分解拡散反射法を用いてTiO2粉末表面での基質の吸着と一電子酸化反応過程の関係について詳細に検討した。基質の吸着量は、懸濁溶液中のTiO2粉末を遠心分離機で完全に取り除いた後、UV吸収スペクトル測定により決定した。過渡吸収測定は、ナノ秒Nd:YAGレーザー(355nm)を用いてTiO2を選択的に励起することにより行った。4-メチルチオフェニルメタノール(MTPM)共存下でのTiO2光励起によって観測された過渡吸収スペクトルでは、レーザー照射直後に545nmに吸収極大があった。この吸収帯は、MTPMラジカルカチオンに帰属される。この信号強度の時間変化は、基質濃度の増加に伴い、信号強度は著しく増加した行基質吸着量の測定から、生成した基質ラジカルカチオンの濃度は基質吸着量と良い相関を示すことが明らかになった。一方、吸着活性基である水酸基やカルボキシル基を持たない基質では、TiO2への吸着量も少なく、また、ラジカルカチオンの生成量も少ないことがわかった。同様の結果は、他の芳香族化合物についても観測された。基質の置換基の性質によってTiO2への吸着量が変化し、TiO2ホールによる直接酸化反応過程では基質の吸着過程がラジカルカチオンの生成に大きく影響していることが明らかになった。また、基質のラジカルカチオンの生成量に対して、基質の酸化電位だけでなく、基質との電子的カップリグが重要であることがわかった。

研究成果
(38件)

すべてその他

すべて文献書誌 (38件)

[文献書誌] K.Kawai: "Formation of Pyrene Dimer Radical Cation in DNA Reflecting DNA Dynamics in the Time Range of 1 μs to 1 ms"J.Am.Chem.Soc.. 125・4. 912-915 (2003)
[文献書誌] A.Ouchi: "A Two-Color Laser Photolysis Methods for Determining Reaction Rates of Short-Lived Intermediates by Product Analysis : Application to the o-inodimethane Problem"J.Am.Chem.Soc.. 125・4. 1104-1108 (2003)
[文献書誌] X.Cai: "Naphthalene in the higher triplet excited state"Chem.Commun.. 2. 222-223 (2003)
[文献書誌] X.Cai: "Sensitized Reactions of Benzophenone in the Higher Triplet Excited State"Chem.Phys.Lett.. 371・1-2. 68-73 (2003)
[文献書誌] T.Takada: "Hole Transfer in DNA : DNA as a Scaffold for Hole Transfer between Two Organic Molecules"Tetrahedron Lett.. 44. 3851-3854 (2003)
[文献書誌] K.Kawai: "Kinetics of Weak Distance Dependent Hole Transfer in DNA by Adenine Hopping Mechanism"J.Am.Chem.Soc.. 125・23. 6842-6843 (2003)
[文献書誌] F.Takei: "Preparation and Photochemical Properties of Polyisocyanides with Regularly Arranged Porphyrin Pendants"Chem.Lett.. 32・6. 506-507 (2003)
[文献書誌] M.Hara: "Three-color three-laser photochemistry of di(p-methoxyphenyl)methyl chloride"J.Phys.Chem.. A107・24. 4778-4783 (2003)
[文献書誌] Hideo Harada: "Ionization and Fragmentation of Some Chlorinated Compounds and Dibenzo-p-dioxin with an Intense Femtosecond Laser Pulse at 800 nm"J.Phys.Chem.. A107・34. 6580-6586 (2003)
[文献書誌] X.Cai: "Transient Phenomena of Dibenz[a,h]anthracene in the Higher Triplet Excited States"Tetrahedron Lett.. 44・32. 6117-6120 (2003)
[文献書誌] M.Endo: "Photoisomerization of 2'-Deoxyribofuranosyl and Ribofuranosyl 2-Phenylazoimidazole"Tetrahedron Lett.. 44・36. 6903-6906 (2003)
[文献書誌] X.Cai: "Rapid cleavage of naphthylmethyl-O bond in the higher triplet excited states"Chem.Commun.. 2604-2605 (2003)
[文献書誌] Xichen Cai: "Benzophenones in the higher triplet excited states"Photochem.Photobiol.Sci.. 2. 1209-1214 (2003)
[文献書誌] Masayuki Endo, Tetsuro Majima: "Tandem Double Helix Nano-Structures Using Interstrand Crosslinked DNA with Maleimide Linkers"Angew.Chem.Int.Ed.Eng.. 5744-5747 (2003)
[文献書誌] Masayuki Endo, Tetsuro Majima: "Control of A Double Helix Assembly by Use of Crosslinked Oligonucleotides"J.Am.Chem.Soc.. 125・45. 13654-13655 (2003)
[文献書誌] Kiyohiko Kawai: "Long-lived Charge-Separated State Leading to DNA Damage through Hole Transfer"J.Am.Chem.Soc.. 125. 16198-16199 (2003)
[文献書誌] Kiyohiko Kawai: "Effects of base pairing on the one-electron reduction rate of cytosine"Chem.Commun.. 2840-2841 (2003)
[文献書誌] Takashi Tachikawa: "One-electron oxidation of aromatic sulfides adsorbed on the surface of TiO_2 particles studied by time-resolved diffuse reflectance spectroscopy"Chem.Phys.Lett.. 382. 618-625 (2003)
[文献書誌] Kiyohiko Kawai: "Excess Electron Transfer in DNA Studied by Pulse Radiolysis and γ-Radiolysis of Naphthalimide and Iodouridine Containing ODN"J.Phys.Chem.B. 107・46. 12838-12841 (2003)
[文献書誌] Tadao Takada: "Kinetics of multi-step hole transfer in DNA by Monitoring the Transient Absorption of Pyrene Radical Cation"J.Phys.Chem.. 107・50. 14052-14057 (2003)
[文献書誌] Sachiko Tojo: "Oxidation processes of aromatic sulfides by hydroxyl radicals in colloidal solution of TiO_2 during pulse radiolysis"Chem.Phys.Lett.. 384・4-6. 312-316 (2004)
[文献書誌] Tadao Takada: "Effects of interaction of photosensitizer with DNA and stacked G bases on photosensitized one-electron oxidation of DNA"J.Phys.Chem.B. 108・2. 761-766 (2004)
[文献書誌] Michihiro Hara: "Formation Efficiency of Radical Cations of Stilbene and Methoxy-substituted Stilbenes during Resonant Two-Photon Ionization with a XeCl Excimer Laser"J.Photochem.Photobiol.A. 162・1. 121-128 (2004)
[文献書誌] Tadao Takada: "Charge Separation in DNA via Consecutive Adenine Hoppings"J.Am.Chem.Soc.. 126・4. 1125-1129 (2004)
[文献書誌] Takumi Kimura: "One-electron Attachment Reaction of B- and Z-DNA Modified by 8-Bromo-2'-deoxyguanosine on"J.Org.Chem.. 69・4. 1169-1173 (2004)
[文献書誌] Michihiro Hara: "Photochemistry of Halogenated Anilines Studied by Time-variation of Micro-wave Dielectric Absorption"J.Photochem.Photobiol.A. 162・1. 121-128 (2004)
[文献書誌] Takumi Kimura: "Structural dependence of B- and Z-DNA modified by 2-aminopurine on the fluorescence intensity"Chem.Commun.. 268-269 (2004)
[文献書誌] Sachiko Tojo: "Direct observation of oxidation processes of aromatic sulfides in TiO_2 colloidal solution by laser flash photolysis"Phys.Chem.Chem.Phys. 6・5. 960-964 (2004)
[文献書誌] Michihiro Hara: "Inhibition of one-electron oxidation of 1-pyrenesulfonate included in cyclodextrin by sulfate radical anion"Chem.Phys.Lett.. (in press). (2004)
[文献書誌] Michihiro Hara: "Photochemistry of Halogenated Anilines Studied by Time-variation of Micro-wave Dielectric Absorption"J.Photochem.Photobiol.A. (in press). (2004)
[文献書誌] Takashi Tachikawa: "Photocatalytic One-electron Oxidation of Biphenyl Derivatives Strongly Coupled with TiO2 Surface"Langmuir. (in press). (2004)
[文献書誌] Michihiro Hara: "Inhibition of one-electron oxidation of 1-pyrenesulfonate included in cyclodextrin by sulfate radical anion"Chem.Phys.Lett.. (in press). (2004)
[文献書誌] Kiyohiko Kawai: "Two-color two-laser damaging DNA"Angew.Chem.Int.Ed.Eng.. (in press). (2004)
[文献書誌] Xichen Cai: "Quenching Processes of Aromatic Hydrocarbons in the Higher Triplet Excited States -Energy Transfer vs Electron Transfer"Phys.Chem.Chem.Phys.. (in press). (2004)
[文献書誌] Takashi Tachikawa: "Formation of dimer radical cation of 1,1-dianisylethylene through two-step hole transfer processes during TiO_2 photocatalytic reactions"Tetrahedron Lett.. (in press). (2004)
[文献書誌] Takashi Tachikawa: "Influence of Adsorption on TiO_2 Photocatalytic One-electron Oxidation Kinetics of Aromatic Sulfides Studied by Time-resolved Diffuse Reflectance Spectroscopy"J.Phys.Chem.B.. (in press). (2004)
[文献書誌] T.Majima: ""Applications to Reaction Mechanism Studies of Organic System"in"Charged Particle and Photon Interactions with Matter : Chemical, Physicochemical, and Biological Consequences with Applications""Marcel Dekker, Inc.. 645-696 (2004)
[文献書誌] K.Kawai, T.Majima: ""Hole Transfer through DNA by Monitoring the Transient Absorption of Radical Cations of Organic Molecules Conjugated to DNA"in"Electron Transfer in DNA for Topics in Current Chemistry""Springer-Verlag, Inc.(in press). (2004)

2003 年度 実績報告書

光機能界面における有機物の反応機構の解明

研究代表者

真嶋 哲朗 大阪大学, 産業科学研究所, 教授 (00165698)

研究成果

[文献書誌] K.Kawai: "Formation of Pyrene Dimer Radical Cation in DNA Reflecting DNA Dynamics in the Time Range of 1 μs to 1 ms"J.Am.Chem.Soc.. 125・4. 912-915 (2003)

[文献書誌] A.Ouchi: "A Two-Color Laser Photolysis Methods for Determining Reaction Rates of Short-Lived Intermediates by Product Analysis : Application to the o-inodimethane Problem"J.Am.Chem.Soc.. 125・4. 1104-1108 (2003)

[文献書誌] X.Cai: "Naphthalene in the higher triplet excited state"Chem.Commun.. 2. 222-223 (2003)

[文献書誌] X.Cai: "Sensitized Reactions of Benzophenone in the Higher Triplet Excited State"Chem.Phys.Lett.. 371・1-2. 68-73 (2003)

[文献書誌] T.Takada: "Hole Transfer in DNA : DNA as a Scaffold for Hole Transfer between Two Organic Molecules"Tetrahedron Lett.. 44. 3851-3854 (2003)

[文献書誌] K.Kawai: "Kinetics of Weak Distance Dependent Hole Transfer in DNA by Adenine Hopping Mechanism"J.Am.Chem.Soc.. 125・23. 6842-6843 (2003)

[文献書誌] F.Takei: "Preparation and Photochemical Properties of Polyisocyanides with Regularly Arranged Porphyrin Pendants"Chem.Lett.. 32・6. 506-507 (2003)

[文献書誌] M.Hara: "Three-color three-laser photochemistry of di(p-methoxyphenyl)methyl chloride"J.Phys.Chem.. A107・24. 4778-4783 (2003)

[文献書誌] Hideo Harada: "Ionization and Fragmentation of Some Chlorinated Compounds and Dibenzo-p-dioxin with an Intense Femtosecond Laser Pulse at 800 nm"J.Phys.Chem.. A107・34. 6580-6586 (2003)

[文献書誌] X.Cai: "Transient Phenomena of Dibenz[a,h]anthracene in the Higher Triplet Excited States"Tetrahedron Lett.. 44・32. 6117-6120 (2003)

[文献書誌] M.Endo: "Photoisomerization of 2'-Deoxyribofuranosyl and Ribofuranosyl 2-Phenylazoimidazole"Tetrahedron Lett.. 44・36. 6903-6906 (2003)

[文献書誌] X.Cai: "Rapid cleavage of naphthylmethyl-O bond in the higher triplet excited states"Chem.Commun.. 2604-2605 (2003)

[文献書誌] Xichen Cai: "Benzophenones in the higher triplet excited states"Photochem.Photobiol.Sci.. 2. 1209-1214 (2003)

[文献書誌] Masayuki Endo, Tetsuro Majima: "Tandem Double Helix Nano-Structures Using Interstrand Crosslinked DNA with Maleimide Linkers"Angew.Chem.Int.Ed.Eng.. 5744-5747 (2003)

[文献書誌] Masayuki Endo, Tetsuro Majima: "Control of A Double Helix Assembly by Use of Crosslinked Oligonucleotides"J.Am.Chem.Soc.. 125・45. 13654-13655 (2003)

[文献書誌] Kiyohiko Kawai: "Long-lived Charge-Separated State Leading to DNA Damage through Hole Transfer"J.Am.Chem.Soc.. 125. 16198-16199 (2003)

[文献書誌] Kiyohiko Kawai: "Effects of base pairing on the one-electron reduction rate of cytosine"Chem.Commun.. 2840-2841 (2003)

[文献書誌] Takashi Tachikawa: "One-electron oxidation of aromatic sulfides adsorbed on the surface of TiO_2 particles studied by time-resolved diffuse reflectance spectroscopy"Chem.Phys.Lett.. 382. 618-625 (2003)

[文献書誌] Kiyohiko Kawai: "Excess Electron Transfer in DNA Studied by Pulse Radiolysis and γ-Radiolysis of Naphthalimide and Iodouridine Containing ODN"J.Phys.Chem.B. 107・46. 12838-12841 (2003)

[文献書誌] Tadao Takada: "Kinetics of multi-step hole transfer in DNA by Monitoring the Transient Absorption of Pyrene Radical Cation"J.Phys.Chem.. 107・50. 14052-14057 (2003)

[文献書誌] Sachiko Tojo: "Oxidation processes of aromatic sulfides by hydroxyl radicals in colloidal solution of TiO_2 during pulse radiolysis"Chem.Phys.Lett.. 384・4-6. 312-316 (2004)

[文献書誌] Tadao Takada: "Effects of interaction of photosensitizer with DNA and stacked G bases on photosensitized one-electron oxidation of DNA"J.Phys.Chem.B. 108・2. 761-766 (2004)

[文献書誌] Michihiro Hara: "Formation Efficiency of Radical Cations of Stilbene and Methoxy-substituted Stilbenes during Resonant Two-Photon Ionization with a XeCl Excimer Laser"J.Photochem.Photobiol.A. 162・1. 121-128 (2004)

[文献書誌] Tadao Takada: "Charge Separation in DNA via Consecutive Adenine Hoppings"J.Am.Chem.Soc.. 126・4. 1125-1129 (2004)

[文献書誌] Takumi Kimura: "One-electron Attachment Reaction of B- and Z-DNA Modified by 8-Bromo-2'-deoxyguanosine on"J.Org.Chem.. 69・4. 1169-1173 (2004)

[文献書誌] Michihiro Hara: "Photochemistry of Halogenated Anilines Studied by Time-variation of Micro-wave Dielectric Absorption"J.Photochem.Photobiol.A. 162・1. 121-128 (2004)

[文献書誌] Takumi Kimura: "Structural dependence of B- and Z-DNA modified by 2-aminopurine on the fluorescence intensity"Chem.Commun.. 268-269 (2004)

[文献書誌] Sachiko Tojo: "Direct observation of oxidation processes of aromatic sulfides in TiO_2 colloidal solution by laser flash photolysis"Phys.Chem.Chem.Phys. 6・5. 960-964 (2004)

[文献書誌] Michihiro Hara: "Inhibition of one-electron oxidation of 1-pyrenesulfonate included in cyclodextrin by sulfate radical anion"Chem.Phys.Lett.. (in press). (2004)

[文献書誌] Michihiro Hara: "Photochemistry of Halogenated Anilines Studied by Time-variation of Micro-wave Dielectric Absorption"J.Photochem.Photobiol.A. (in press). (2004)

[文献書誌] Takashi Tachikawa: "Photocatalytic One-electron Oxidation of Biphenyl Derivatives Strongly Coupled with TiO2 Surface"Langmuir. (in press). (2004)

[文献書誌] Michihiro Hara: "Inhibition of one-electron oxidation of 1-pyrenesulfonate included in cyclodextrin by sulfate radical anion"Chem.Phys.Lett.. (in press). (2004)

[文献書誌] Kiyohiko Kawai: "Two-color two-laser damaging DNA"Angew.Chem.Int.Ed.Eng.. (in press). (2004)

[文献書誌] Xichen Cai: "Quenching Processes of Aromatic Hydrocarbons in the Higher Triplet Excited States -Energy Transfer vs Electron Transfer"Phys.Chem.Chem.Phys.. (in press). (2004)

[文献書誌] Takashi Tachikawa: "Formation of dimer radical cation of 1,1-dianisylethylene through two-step hole transfer processes during TiO_2 photocatalytic reactions"Tetrahedron Lett.. (in press). (2004)

[文献書誌] Takashi Tachikawa: "Influence of Adsorption on TiO_2 Photocatalytic One-electron Oxidation Kinetics of Aromatic Sulfides Studied by Time-resolved Diffuse Reflectance Spectroscopy"J.Phys.Chem.B.. (in press). (2004)

[文献書誌] T.Majima: ""Applications to Reaction Mechanism Studies of Organic System"in"Charged Particle and Photon Interactions with Matter : Chemical, Physicochemical, and Biological Consequences with Applications""Marcel Dekker, Inc.. 645-696 (2004)

[文献書誌] K.Kawai, T.Majima: ""Hole Transfer through DNA by Monitoring the Transient Absorption of Radical Cations of Organic Molecules Conjugated to DNA"in"Electron Transfer in DNA for Topics in Current Chemistry""Springer-Verlag, Inc.(in press). (2004)

2003 年度実績報告書

真嶋哲朗大阪大学, 産業科学研究所, 教授 (00165698)