ポルフィリン金属錯体による分子表面認識とナノサイズ反応場の構築

• Project/Area Number: 17750156
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Chemistry related to living body
• Research Institution: Kyoto University
• Principal Investigator: 人見 穣 Kyoto University, 工学研究科, 講師 (20335186)
• Project Period (FY): 2005 – 2007
• Project Status: Completed (Fiscal Year 2007)
• Budget Amount: ¥3,600,000 (Direct Cost: ¥3,600,000); Fiscal Year 2007: ¥1,000,000 (Direct Cost: ¥1,000,000); Fiscal Year 2006: ¥1,000,000 (Direct Cost: ¥1,000,000); Fiscal Year 2005: ¥1,600,000 (Direct Cost: ¥1,600,000)
• Keywords: ポルフィリン / 反応 / ナノ / 金属表面 / 錯体 / 金属酸化物 / エポキシ化 / 吸着 / ナノ粒子 / 金属錯体 / 分子表面 / ナノサイズ / 反応場 / 触媒 / 分子認識 / 酸化反応

Research Abstract

十分に設計された配位子を用いれば、生成される金ナノ粒子の粒子径だけでなく、その形状、電子状態、反応性の制御、反応空間の構築も可能であり、その先に豊かな金ナノクラスター科学を展開できるのではないかという着想の基に、『ポルフィリン金属錯体による分子表面認識とナノサイズ反応場の構築』を目指して、金ナノ粒子表面を認識する強固に認識する表面保護配位子Por_ClSを設計、合成した。本表面保護配位子Por_ClSは、ポルフィリン骨格から同一方向に4つのアセチル基によって保護された硫黄原子を提示しており、金表面を認識することが可能である。当初の分子設計通り、表面保護配位子Por_ClSの存在下、HAuCl4を還元することで、Por_ClSによって表面が保護された極めて安定な金ナノクラスターが調製可能であることを見出した。また、ポルフィリン表面保護配位子のHAuCl4に対する仕込み比を増加させることによって、粒子径分布の狭い金ナノクラスターを調製することにも成功した(2.0±0.2nm)。この知見を基に、アセチル基によって保護された硫黄原子ではなく、ジスルフィド結合を有するポルフィリン表面保護配位子を設計、合成した結果、ポルフィリン表面保護配位子のHAuCl4に対する仕込み比に関係なく、粒子径分布の狭い金ナノクラスターが得られることを見いだした。また、得られたポルフィリン保護金ナノクラスターが自己組織化し、超格子を形成することも判明した。

Research Products

• [Journal Article] Promotion effect of tungsten oxide on photo-assisted selective catalytic reduction of NO with NH3 over TiO2 (2008)
  • Author(s): Seiji Yamazoe, Yasuyuki Masutani, Kentaro Teramura, Yutaka, Hitomi, Tetsuya Shishido, Tsunehiro Tanaka
  • Journal Title: Applied Catalysis B: Environmental (in press)
  • Peer Reviewed
• [Journal Article] Kinetic study of photo-oxidation of NH3 over TiO2 (2008)
  • Author(s): Seiji Yamazoe, Yutaka, Hitomi, Tetsuya Shishido, Tsunehiro Tanaka
  • Journal Title: Applied Catalysis B: Environmental (in press)
  • Peer Reviewed
• [Journal Article] XAFS Study of Tungsten L1-and L3-Edges: Structural Analysis of WO3 Species Loaded on TiO2 as a Catalyst for Photo-oxidation of NH3 (2008)
  • Author(s): Seiji Yamazoe, Yutaka, Hitomi, Tetsuya Shishido, Tsunehiro Tanaka
  • Journal Title: The Journal of Physical Chemistry C (in press)
  • Peer Reviewed
• [Journal Article] Identification of a Copper (I) Intermediate in the Conversion of 1-Aminocyclopropane Carboxylic Acid (ACC) into Ethylene by Cu(II)-ACC Complexes and Hydrogen Peroxide (2008)
  • Author(s): Wadih Ghattas, M. Giorgi, Y. Mekmouche, Isunehiro Tanaka, A. Rockenbauer, Marius Reglier, Yutaka Hitomi, A. I. Simaan
  • Journal Title: Inorganic Chemistry (in press)
  • Peer Reviewed
• [Journal Article] Alkane hydroxylation catalyzed by a series of mononuclear nonheme iron complexes containing 4-nitropyridine ligands (2008)
  • Author(s): Yutaka Hitomi, Shinya Furukawa, Masakazu Higuchi, Shishido Tetsuya, Tsunehiro Tanaka
  • Journal Title: Journal of Molecular Catalysis A: Chemical (in press)
  • Peer Reviewed
• [Journal Article] Visible light absorbed NH2 species derived from NH3 adsorbed on TiO2 for photoassisted selective catalytic reduction (2007)
  • Author(s): Seiji Yamazoe, Taro Okumura, Yutaka Hitomi, Tetsuya Shishido, and Tsunehiro Tanaka
  • Journal Title: The Journal of Physical Chemistry C 111 Pages: 14189-14197
  • Peer Reviewed
• [Journal Article] Mechanism of Photo-Oxidation of NH3 over TiO2: Fourier Transform Infrared Study of the Intermediate Species (2007)
  • Author(s): Seiji Yamazoe, Taro Okumura, Yutaka Hitomi, Tetsuya Shishido, and Tsunehiro Tanaka
  • Journal Title: The Journal of Physical Chemistry C 111 Pages: 11077-11085
  • Peer Reviewed
• [Journal Article] Adsorption of Manganese Porphyrin on Metal Oxides and Its Enhanced Catalytic Activity on Epoxidation Reaction (2007)
  • Author(s): Yutaka Hitomi, Hidefumi Mukai, Junya Ohyama, Masashi Shinagawa, Tetsuya Shishido, and Tsunehiro Tanaka
  • Journal Title: Chemistry Letters 36 Pages: 660-661
  • NAID: 10019936160
  • Peer Reviewed
• [Journal Article] Adsorption of Manganese Porphyrin on Metal Oxides and Its Enhanced Catalytic Activity on Epoxidation Reaction (2007)
  • Author(s): 人見穣, 向井英史, 大山順也, 品川正志, 宍戸徹也, 田中庸裕
  • Journal Title: Chemistry Letters (in press)
  • NAID: 10019936160
• [Journal Article] Chemical Approach to Catecholdioxygenases Based on Homogeneous Catalysis and Bioinoranic Chemistry (2006)
  • Author(s): 人見穣, 船引卓三
  • Journal Title: Bulletin of Japan Society of Coordination Chemistry 48 Pages: 17-17
• [Journal Article] Mechanistic study on regioselective oxygenation reaction of 1,2-quinones with peroxybenzoic acids : Relevant to mechanisms of catecholdioxygenases (2006)
  • Author(s): 人見 穣, 吉田裕志, 田中庸裕, 船引卓三
  • Journal Title: Journal of Molecular Catalysis A : Chemical (印刷中)
• [Journal Article] Non-covalent modification of the heme-pocket of apomyoglobin by a 1,10-phenanthroline derivative (2005)
  • Author(s): 人見 穣, 向井英史, 吉村英哲, 田中庸裕, 船引卓三
  • Journal Title: Bioorganic&Medicinal Chemistry Letters 16 Pages: 248-251
• [Journal Article] Correlation of spin states and spin delocalization with the dioxygen reactivity of catecholatoiron(III)complexes (2005)
  • Author(s): 樋口雅一, 人見 穣, 南久貴, 田中庸裕, 船引卓三
  • Journal Title: Inorganic Chemistry 44 Pages: 8810-8821
• [Journal Article] Catalytic oxygenative degaradaton of 4-chlorocatechol by a nonheme iron(III)complex-mechanism and prevention of catechol ester formation (2005)
  • Author(s): 人見 穣, 樋口雅一, 田中庸裕, 船引卓三
  • Journal Title: Journal of Molecular Catalysis : A, Chemical 240 Pages: 207-213
• [Journal Article] Electron spray ionization mass study on dioxygenation process in the reaction of catecholatoiron(III)complexes with molecular oxygen (2005)
  • Author(s): 人見 穣, 樋口雅一, 田中庸裕, 船引卓三
  • Journal Title: Inorganica Chimica Acta 358 Pages: 3465-3470
• [Journal Article] Aerobic catechol oxidation catalyzed by a bis(mu-oxo)dimanganese(III,III)complex via a manganese(II)-semiquinonate complex (2005)
  • Author(s): 人見 穣, 安藤明, 松井元, 伊藤朋和, 田中庸裕, 小郷誠司, 船引卓三
  • Journal Title: Inorganic Chemistry 44 Pages: 3473-3478
• [Journal Article] Tuning of spin crossover equilibrium in catecholatoiron(III)complexes by supporting ligands. (2005)
  • Author(s): 人見 穣, 樋口雅一, 田中庸裕, 船引卓三
  • Journal Title: Chemical Communications 13 Pages: 1758-1760
• [Journal Article] A linear correlation between energy of LMCT band and oxygenation reaction rate of a series of catecholatoiron(III)complexes : initial oxygen binding during intradiol catechol oxygenation. (2005)
  • Author(s): 人見 穣, 吉田将人, 樋口雅一, 南久貴, 田中庸裕, 船引卓三
  • Journal Title: Journal of Inorganic Biochemistry 99 Pages: 755-763
• [Presentation] Substituent Effects on the Reactivity of Oxygen Active Species of Mononuclear Nonheme Iron Complexes (2007)
  • Author(s): Shinya Furukawa, Yutaka Hitomi, Tetsuya Shishido and Tsunehiro
  • Organizer: Internatinal Symposium on Catalysis and Fine Chemical 2007
  • Place of Presentation: Singapore
  • Year and Date: 2007-12-18
• [Presentation] Oxigen Active Species of Mononuclear Iron (III) Complexes with Amidate-Based Ligand (2007)
  • Author(s): Takashi Sugimoto, Yutaka Hitomi, Takamasa Itoh, Tetsuya Shishido, and
  • Organizer: Internatinal Symposium on Catalysis and Fine Chemical 2007
  • Place of Presentation: Singapore
  • Year and Date: 2007-12-17
• [Presentation] キノリン骨格とアミド配位を有する単核鉄錯体の酸化反応と蛍光特性 (2007)
  • Author(s): 人見 穣・杉本貴志・伊東孝真・田甲庸裕
  • Organizer: 第22回生体機能関連化学シンポジウム
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-28
• [Presentation] Dioxygen reactivity of low spin iron (III) catechol complexes (2007)
  • Author(s): Shinichi Okuoka, Yutaka Hitomi, Masakazu Higuchi, Hisataka Minami, Tsunihiro Tanaka, Takuzo Funabiki
  • Organizer: China-Japan Symposium on Selective Oxidation Catalysis
  • Place of Presentation: Xiamne, Chania
  • Year and Date: 2007-04-22