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2003 Fiscal Year Annual Research Report

修飾DNAの機能化による分子デバイス

Research Project

Project/Area Number 13305058
Research InstitutionOsaka University

Principal Investigator

真嶋 哲朗  大阪大学, 産業科学研究所, 教授 (00165698)

Co-Investigator(Kenkyū-buntansha) 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)
KeywordsDNA / DNA分子ワイヤ / 修飾DNA / DNAの機能化 / 分子デバイス / 核酸塩基 / ホール移動 / パルスラジオリシス
Research Abstract

DNAは多数の核酸塩基のナノスケールの配列制御によって遺伝情報を司っていると言う意味で、DNAはナノサイズの情報デバイスである。ナノサイエンス、ナノテクノロジーとの関係からDNA分子デバイスの創製は、学問的のみならず社会的要請の強い研究課題となっている。本研究では、種々の光機能性クロモファを共有結合によって導入した修飾DNAを用いることによって、クロモファ独自の光機能性を利用して修飾DNAに様々な機能性を賦与し、その機能を自由にコントロールすることによって、光機能化修飾DNAの特に生体系での分子デバイスとしての可能性を明らかにすることを目的としている。本年度に得られた成果として、まず、DNA中のホール移動はG-hoppingに比較して、アデニン間の連続的なホッピング(A-hopping)が非常に速いことを(>10^9 s^<-1>)見出した。この高速A-hoppingによる電荷移動を利用することで、DNA上において高効率・長寿命電荷分離状態の生成が可能であると考えた。そこで、DNA内電荷分離状態生成のモデル系として、電子受容体naphthaldiimide(NDI)および電子供与体phenothiazine(PTZ)を修飾したDNAを合成し、その電荷分離・再結合過程を過渡吸収法により観測した。NDIの励起一重項状態は隣接する核酸塩基との間で電荷分離状態を形成し、その後、連続的なA-hoppingを経てPTZ部位へとホールが移動して、NDIとPTZとの間で電荷分離状態を生じた。次に、naphthalimide (NI)とPTZを修飾した二本鎖DNAを合成し、NIの光励起により隣接Aとの間で電荷分離を起こさせ、その後A-hoppingして、NIに最も近いGにホールを注入した。生成したNI^<・->とG^<・+>間の距離は長く、数百マイクロ秒程度までのホール移動過程の観測が可能となった。もう一方の末端にホール移動によって生じるPTZ^<・+>の生産過程を観測することで、長距離ホール移動の速度を直接決定することができた。また電荷分離状態の寿命は数100μs以上であること見出した。

  • Research Products

    (38 results)

All Other

All Publications (38 results)

  • [Publications] 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)

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

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

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

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

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

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

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

  • [Publications] 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)

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

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

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

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

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

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

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

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

  • [Publications] 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)

  • [Publications] 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)

  • [Publications] 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)

  • [Publications] 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)

  • [Publications] 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)

  • [Publications] 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)

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

  • [Publications] 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)

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

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

  • [Publications] 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)

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

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

  • [Publications] Takashi Tachikawa: "Photocatalytic One-electron Oxidation of Biphenyl Derivatives Strongly Coupled with TiO_2 Surface"Langmuir. (in press). (2004)

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

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

  • [Publications] 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)

  • [Publications] 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)

  • [Publications] 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)

  • [Publications] 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)

  • [Publications] 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)

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Published: 2005-04-18   Modified: 2016-04-21  

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