Development of Reaction Systems using Highly Functionalized Metal Complexes

• Project/Area Number: 18350035
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Doshisha University
• Principal Investigator: 小寺 政人 Doshisha University, 理工学部, 教授 (00183806)
• Co-Investigator(Kenkyū-buntansha): MIZUTANI Tadashi 同志社大学, 理工学部, 教授 (40229696) ; FUNABIKI Takuzo 同志社大学, 理工学部, RCAST研究員 (70026061)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥15,320,000 (Direct Cost: ¥13,700,000、Indirect Cost: ¥1,620,000); Fiscal Year 2008: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2007: ¥5,330,000 (Direct Cost: ¥4,100,000、Indirect Cost: ¥1,230,000); Fiscal Year 2006: ¥8,300,000 (Direct Cost: ¥8,300,000)
• Keywords: 二核金属錯体 / 酸素活性化 / 酸素運搬 / 加水分解反応 / リン酸エステル / APモデル / 二核亜鉛錯体 / リン酸ジエステルの取り込み / リン酸ジエステルの加水分解 / 反応活性種 / ビスインターカレーター配位子 / DNAの分子認識 / 二核銅(II)錯体 / メタンモノオキシゲナーゼ / 二核鉄酵素 / O_2活性化 / パーオキソニ核鉄(III)中間体 / トリオキソニ核鉄(IV)錯体 / 高機能性金属錯体 / DNAの位置特異的加水分解 / 制限酵素モデル / 酸素分子活性化 / ヘモシアニン / 酸素分子の可逆的結合 / 酸素親和性

Research Abstract

本研究では金属錯体の機能モデル化合物としての高機能性金属錯体を合成し、これを機能中心として用いて、ヘモシアニン機能モデル化合物としての二核銅錯体によるによる酸素分子の可逆的結合反応、メタンモノオキシゲナーゼ機能モデル化合物としての二核鉄錯体による酸素活性化による基質酸素化触媒反応、アルカリホスファターゼ機能モデル化合物としてのリン酸ジエステルの加水分解反応およびDNAと結合できるビスインターカレータ部位を持つ二核銅錯体によるDNAとの特異的結合などの様々な反応システムを開発した。

Research Products

• [Journal Article] Synthesis and Characterization of a Binuclear Iron(III) Complex Bridged by 1 -Aminocyc lopropane-1 -carboxylic Acid EthyleneProduction in the Presence of Hydrogen Peroxide (2009)
  • Author(s): W. Ghattas, Z. Serhan, N. E. Bakkali-Taheri, M. Reglier, M. Kodera, Y. Hitomi, and A. J. Simaan
  • Journal Title: Inorg. Chem. 48 Pages: 3910-3912
• [Journal Article] Molecular Recognition in Anisotropic Media Binding of Alkylpyridines to Amphiphilic Zinc Porphyrins Incorporated in Liposomal Bilayer Membranes (2009)
  • Author(s): Murakami, R. ; Minami, A. ; Mizutani, T.
  • Journal Title: Org. Biomol. Chem. 7,(7) Pages: 1437-1444
• [Journal Article] Selective Adsorption of Biladien-ab-one and Zinc Biladien-ab-one to Mesoporous Silica (2009)
  • Author(s): Akasaka, H. ; Yukutake, H. ; Nagata, Y. ; Funabiki, T. ; Mizutani, T. ; Takagi, H. ; Fukushima, Y. ; Juneja, L. R. ; Kitahata, K
  • Journal Title: Microporous Mesoporous Mater. 120,(3) Pages: 331-338
• [Journal Article] Allosteric Binding of Amino Alcohols and Diamines by Dimeric Zinc Biladienone (2009)
  • Author(s): Shimizu, T. ; Asano, N.; Mizutani, T. ; Chang, H.-C. ; Kitagawa, S.
  • Journal Title: Tetrahedron Letters 50(5) Pages: 536-539
• [Journal Article] Spectroscopic and Computational Studies of (u-oxo)(u-1,2-Peroxo)diiron(III) Complexes of Relevance to Nonheme Diiron Oxygenase Intermediates (2008)
  • Author(s): A. T. Fiedler, X. Shan, M. P. Mehn, J. Kaizer, S. Torelli, J. R. Frisch, M. Kodera, L. Que, Jr.
  • Journal Title: J. Phys Chem. A 112 Pages: 13037-13044
• [Journal Article] One-Phase Synthesis of Small Gold Nanoparticles Coated by a Horizontal Porphyrin Monolayer (2008)
  • Author(s): J. Ohyama, Y. Hitomi, Y. Higuchi,M. Shinagawa, H. Mukai, M. Kodera, K. Teramura, T. Shishido, T. Tanaka
  • Journal Title: Chem. Commun. Pages: 6300-6302
• [Journal Article] Homohelicity-enriched zinc bilinone dimers with chiral aliphatic spacers. Synthesis and application to chiral induction of a nematic liquid crystal (2008)
  • Author(s): Yagi, S. ; Hamakubo, K. ; Ikawa, S. ; Nakazumi, H. ; Mizutani, T.
  • Journal Title: Tetrahedron 64,(46) Pages: 10598-10604
• [Journal Article] Syntheses, structural characterization and photophysical properties of 4-(2-pyridy1)-1,2,3- triazole rhenium (I) complexes (2008)
  • Author(s): M. Obata, A. Kitamura, A. Mori, C. Kameyama, J. A. Czaplewska, R. Tanaka, I. Kinoshita, T. Kusumoto, H. Hashimoto, M. Harada, Y. Mikata, T. Funabiki, S. Yano, J. Chem. Soc
  • Journal Title: Dalton Trans. Pages: 3292-3300
• [Journal Article] Spectroscopic and Computational Studies of (μ-oxo)(μ-1, 2-Peroxo) diiron (III) Complexes of Relevance to Nonheme Diiron Oxygenase Intermediates (2008)
  • Author(s): A. T. Fiedler, X. Shan, M. P. Mehn, J. Kaizer, S. Torelli, J. R. Frisch, M. Kodera, L. Que, Jr
  • Journal Title: J. Phys. Chem. A 112 Pages: 13037-13044
  • Peer Reviewed
• [Journal Article] One-phase Synthesis of Small Gold Nanoparticles Coated by a Horizontal Porphyrin Monolayer (2008)
  • Author(s): J. Ohyama, Y. Hitomi, Y. Higuchi, M. Shinagawa, H. Mukai, M. Kodera, K. Teramura, T. Shishido, T. Tanaka
  • Journal Title: Chem. Commun. Pages: 6300-6301
  • Peer Reviewed
• [Journal Article] Reversible O_2-binding and activation with dicopper and diiron complexes stabilized by various hexapyridine ligands stability, modulation, and flexibility of the dinuclear structure as key aspects for the dimetal/O_2 chemistry (2007)
  • Author(s): M. Kodera, K. Kano
  • Journal Title: Bull. Chem. Soc. Jpn. 80 Pages: 662-76
  • NAID: 10019937703
• [Journal Article] High Utility of Electro- and Cold-Spray Ionization Time-of-Flight Mass Spectra in Development of Functional Metalloenzyme Models : Detection of Labile Metal Complexes and Reactive Intermediates (2007)
  • Author(s): M. Kodera
  • Journal Title: JEOL new 42 Pages: 21-30
• [Journal Article] 金属酵素の機能を再現する高機能性金属錯体の開発とElectro-and Cold-Spray Ionization Time-of-Flight Mass Spectrometerの利用 : 置換活性金属錯体および不安定錯種の検出 (2007)
  • Author(s): M. Kodera
  • Journal Title: JEOL News 39 Pages: 8-18
• [Journal Article] Synthesis of Biladienone and Bilatrienone by Coupled Oxidation of Tetraarylporphyrins (2007)
  • Author(s): Asano, N. ; Uemura, S.; Kinugawa, T. ; Mizutani, T.
  • Journal Title: J Org. Chem Chem. 72,(14) Pages: 5320-5326
• [Journal Article] Thermodynamics of Hydrophobic Interactions : Entropic Recognition of Hydrophobic Moiety by Poly(Ethylene Oxide)-Zinc Porphyrin Conjugates (2007)
  • Author(s): H. ; Mizutani, T. ; Kano, K.
  • Journal Title: Chem. Asian J. 2,(10) Pages: 1267-1275
• [Journal Article] Optical oxygen-sensing properties of porphyrin derivatives anchored on ordered porous aluminium oxide plates (2007)
  • Author(s): N. Araki, Y. Amao, T. Funabiki, M. Kamitakahara, C. Ohtsuki, K. Mitsuo, K. Asai, M. Obata, S. Yano
  • Journal Title: Photochem. Photobiol. Sci. 6 Pages: 794-803
• [Journal Article] High Utility of Electro-and Cold-Spray Inonization Time-of-Flight Mass Spectra in Development of Functional Metalloenzyme Models:Detection of Labile Metal Complexes and Reactive Intermediates (2007)
  • Author(s): Masahito Kodera
  • Journal Title: JEOL news 42 Pages: 21-30
• [Journal Article] 金属酵素の機能を再現する高機能性金属錯体の開発とElectr-and Cold-Spray Ionozation Time-of-Flight Mass Spectrometerの利用 (2007)
  • Author(s): 小寺 政人
  • Journal Title: 日本電子news 39 Pages: 8-18
• [Journal Article] Reversible O_2-Binding and Activation with Dicopper and Diiron Complexes Stabilized by Various Hexapyridine Ligands : Stability, Modulation, and Flexibility of the Dinuclear Structures as Key Aspects for the Dimetal/O_2 Chemistry (2007)
  • Author(s): M.Kodera, K.Kano
  • Journal Title: Bull.Chem.Soc.Jpn.Accounts 80(in press)
  • NAID: 10019937703
• [Journal Article] Preparation and X-ray structure of a (catecholato)copper(II) complex with a Schonberg adduct (2006)
  • Author(s): B. Tapodi, G. Speier, M. Giorgi, M. Reglier, T. Funabiki, L. Korecz, A
  • Journal Title: Rockenbauer, Inorg. Chem. Comm. 9 Pages: 367-70
• [Journal Article] Structure and Photochemical Properties of (μ-Alkoxo)bis([t -carboxylato)- diruthenium Complexes with Naphthylacetate Ligands (2006)
  • Author(s): R. Tanaka, I. Kinoshita, M. Mikuriya, H. Benten, H. Ohkita, S. Ito, M. Obata, S. Yano
  • Journal Title: Inorg. Chem. 45 Pages: 3048-56
• [Journal Article] Chemical Approach to Catecholdioxygenases based on Homogeneous Catalysis and Bioinorganic Chemistry (2006)
  • Author(s): Y. Hitomi, T. Funabiki
  • Journal Title: Bull. Jpn. Coord. Chem. 48 Pages: 17-32
  • NAID: 40021107125
• [Journal Article] Mechanistic study on regioselective oxygenation reaction of 1,2-quinones with peroxybenzoic acids : Relevant to mechanisms of catechol dioxygenases (2006)
  • Author(s): Y. Hitomi, H. Yoshida, T. Tanaka, T. Funabiki,
  • Journal Title: J. Mol. Catal. A : Chemical 251 Pages: 239-45
• [Journal Article] Non-covalent modification of the heme-pocket of apomyoglobin by a 1,10-phenanthroline derivative (2006)
  • Author(s): Y. Hitomi, H. Mukai, H. Yoshimura, T. Tanaka, T. Funabiki
  • Journal Title: Bioinorg. Med. Chem. Lett. 16 Pages: 8810-21
• [Journal Article] Homohelicity induction of propylene-linked zinc bilinone dimers by complexation with chiral amine and a-amino esters. Preorganization of structurally coupled homohelical subunits (2006)
  • Author(s): Hamakubo, K. ; Yagi, S. ; Nakazumi, H. ; Mizutani, T. ; Kitagawa S.
  • Journal Title: Tetrahedron 62(15) Pages: 3619-3628
• [Journal Article] Thermochromic and solvatochromic zinc biladienones : dynamic equilibria of a metal complex having a flexible framework sensitive to environment (2006)
  • Author(s): K. ; Tokuoka, T. ; Monno, E.; Yagi, S. ; Nakazumi, H. ; Mizutani, T.
  • Journal Title: Tetrahedron Letters 47(10) Pages: 1533-1536
• [Journal Article] A New Molecular Switch Based on Helical Biladienone, Matsui, M. ; Matsuzawa (2006)
  • Author(s): M. ; Matsuzawa, N. N. ; Harnack, O. ; Yamauchi, T. ; Hatazawa, T. ; Yasuda, A. ; Mizutani, T.
  • Journal Title: Adv. Mater. 18(19) Pages: 2523-2528
• [Journal Article] N-Methylporphyrin as a Binding Motif for the Recognition of a Phenolic Hydroxy Group, Kotomari (2006)
  • Author(s): S. ; Yoshikawa, T. ; Mizutani, T .; Takagi, H.
  • Journal Title: Chem. Lett. 35(9) Pages: 1020-1021
• [Journal Article] Peroxodiiron complexes of polypyridine ligands : syntheses, physicochemical properties, and thermal stability markedly enhanced by hexapyridine dinucleating ligand (2006)
  • Author(s): M. Kodera, M. Itoh, K. Kano, T. Funabiki
  • Journal Title: Bull. Chem. Soc. Jpn. 79 Pages: 252-61
  • NAID: 10017271433
• [Journal Article] Redox behavior of a manganese porphyrin complexed with per-O-methylated beta-Cyclodextrin in aqueous solution (2006)
  • Author(s): K. Kano, H. Kitagishi, Y. Sone, N. Nakazawa, M. Kodera, Eur. J.
  • Journal Title: Inorg. Chem. Pages: 4043-53
• [Journal Article] A myoglobin functional model composed of a ferrous porphyrin and a cyclodextrin dimer with an imidazole linker (2006)
  • Author(s): K. Kano, H. Kitagishi, T. Mabuchi, M. Kodera, S. Hirota
  • Journal Title: Chem Asian J. Pages: 358-6
• [Journal Article] Iron porphyrin-cyclodextrin supramolecular complex as a functional model of myoglobin in aqueous solution (2006)
  • Author(s): K. Kano, H. Kitagishi, C. Dagallier, M. Kodera, T. Matsuo, T. Hayashi, Y. Hisaeda, S. Hirota
  • Journal Title: Inorg. Chem. 45 Pages: 4448-60
• [Journal Article] Redox Behavior of a Manganese Porphyrin Complexed with Per-O-methylated β-Cyclodextrin in Aqueous Solution (2006)
  • Author(s): K.Kano, H.Kitagishi, Y.Sone, N.Nakazawa, M.Kodera
  • Journal Title: Eur.J.Inorg.Chem Pages: 4043-4053
• [Journal Article] Iron Porphyrin-Cyclodextrin Supramolecular Complex as a Functional Model of Myoglobin in Aqueous Solution (2006)
  • Author(s): K.Kano, H.Kitagishi, C.Dagellier, M.Kodera, T.Matsuo, T.Hayashi, Y.Hisaeda, S.Hirota
  • Journal Title: Inorg.Chem 45 Pages: 4448-4460
• [Journal Article] A Myoglobin functional Model Composed of a Ferrous Porphyrin and a Cyclodextrin dimer with an Imidazole Linder (2006)
  • Author(s): K.Kano, H.Kitagishi, T.Mabuchi, M.Kodera, S.Hirota
  • Journal Title: Chem.Asian J 1 Pages: 358-366
• [Presentation] 多電子酸化反応を触媒する四核銅錯体の合成 (2009)
  • Author(s): 中川智之, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第89回日本化学会春季年会
  • Place of Presentation: 日本大学船橋キャンパス
• [Presentation] デオキシヘモシアニンの構造を模倣した新規モデル錯体の合成と機能 (2009)
  • Author(s): 岸本和浩, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第89回日本化学会春季年会
  • Place of Presentation: 日本大学船橋キャンパス
• [Presentation] PSII OECのマンガンクラスターと類似の構造を持つ5核銅錯体の合成と反応性能 (2009)
  • Author(s): 宇佐勇貴, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第89回日本化学会春季年会
  • Place of Presentation: 日本大学船橋キャンパス
• [Presentation] Bis-tpa型配位子(6-hpa)を用いた二核ルテニウム錯体の合成と酸素発生 (2009)
  • Author(s): 杉山亮子, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第89回日本化学会春季年会
  • Place of Presentation: 日本大学船橋キャンパス
• [Presentation] sMMO機能モデルの構築を目的とした新規カルボン酸含有八座二核化配位子の開発およびその二核鉄(III)錯体の合成と酸素活性化 (2009)
  • Author(s): 山田修平, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第89回日本化学会春季年会
  • Place of Presentation: 日本大学船橋キャンパス
• [Presentation] 非ヘム二核金属タンパクの機能を再現する高機能性金属錯体の構築 (2008)
  • Author(s): 小寺政人
  • Organizer: 第4回筑波大学学際物質科学研究センター機能性分子シンポジウム
  • Place of Presentation: 筑波大学
  • Year and Date: 2008-12-20
• [Presentation] Dinuclear metal complexes of a bis-intercalater ligand as a strong DNA-binder (2008)
  • Author(s): M. Kodera, K. Hamada, T. Nakamura, Y. Hitomi, T. Funabiki, K. Kano
  • Organizer: European Biological Inorganic Chemistry Conference
  • Place of Presentation: Aveiro, Portugal
• [Presentation] Dioxygen Activation by a Diiron Complex of 6-hpa Ligand : Synthesis, Characterization, and Functions of Trioxodiiron (IV) Complex (2008)
  • Author(s): M. Kodera, S. Yamada, K. Kondo, Y. Hitomi, T. Funabiki
  • Organizer: Asian Biological Inorganic Chemistry Conference
  • Place of Presentation: Jeju, Korea
• [Presentation] Dioxygen activation by a diiron complex of 6-hpa ligand : synthesis, characterization, and functions of diiron(IV)-oxo complex (2008)
  • Author(s): M. Kodera, S. Yamada, K. Kondo, Y. Hitomi, T. Funabiki
  • Organizer: 第19回金属の関与する生体関連反応シンポジウム
  • Place of Presentation: 名古屋市立大学
• [Presentation] Bis-tpa型二核化配位子を用いたトリオキソ二核鉄(IV)錯体 (2008)
  • Author(s): 小寺政人, 山田修平, 近藤慶一, 人見穣
  • Organizer: 平成20年度分子研研究会「配位子場制御に基づく機能性錯体の創成と応用〜生体から触媒およびデバイスまで〜」
  • Place of Presentation: 愛知県岡崎市岡崎コンファレンスセンター
• [Presentation] Bis-tpa型配位子(6-hpa)を用いた二核ルテニウム錯体の合成と酸素発生 (2008)
  • Author(s): 杉山亮子, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
• [Presentation] 二核鉄錯体の酸素活性化 : 酸化活性種μ-オキソ-ジオキソ二核鉄(IV)錯体の反応性、分光学的性質、DFT計算 (2008)
  • Author(s): 山田修平, 近藤慶一, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
• [Presentation] 新規bis-bipyridine型配位子の開発とこれを用いた二核金属錯体の合成と構造 (2008)
  • Author(s): 中村拓真, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
• [Presentation] 光合成酸素発生中心のマンガンクラスターに類似したキュバン型骨格を持つ5核銅錯体の合成と構造 (2008)
  • Author(s): 宇佐勇貴, 人見穣, 船引卓三, 加納航, 小寺政人
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢大学
• [Presentation] sMMO機能モデルの構築 : カルボン酸含有八座二核化配位子DPGly-Meとその二核鉄(III)錯体の合成およびこれを用いた酸素活性化 (2008)
  • Author(s): 山田修平, 人見穣, 船引卓三, 加納航治, 小寺政人
  • Organizer: 第41回酸化反応討論会
  • Place of Presentation: 九州大学
• [Presentation] Determination of P_<1/2> Values with Room Temperature Stable Peroxodicopper(II) Complexes as Models of Oxyhemocyanin and O_2 Affinity Control by Structural Modulation (2007)
  • Author(s): Masahito Kodera, M.Fujii, Y.Kajita, Y.Okano, K.Kano and T.Funabiki
  • Organizer: 13th International Conference on Bioinorganic Chemistry
  • Place of Presentation: Wien,Austria