ISHIHARA, Koji

写真a

Affiliation

Faculty of Science and Engineering, School of Advanced Science and Engineering

Job title

Professor

Concurrent Post 【 display / non-display

  • Faculty of Commerce   School of Commerce

  • Faculty of Science and Engineering   Graduate School of Advanced Science and Engineering

  • Affiliated organization   Global Education Center

Research Institute 【 display / non-display

  • 2020
    -
    2022

    理工学術院総合研究所   兼任研究員

Education 【 display / non-display

  •  
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    1983

    Nagoya University   Graduate School, Division of Natural Science  

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    1983

    Nagoya University   Graduate School, Division of Natural Science  

Degree 【 display / non-display

  • Saitama University   Bachelor of Science

  • 埼玉大学   理学士

  • 名古屋大学   理学修士

  • Nagoya University   Doctor of Science

  • 名古屋大学   理学博士

Research Experience 【 display / non-display

  • 1995
    -
     

    Waseda University, Professor

  • 1995
     
     

    The University of Victoria, Visiting Researcher (5 months)

  • 1990
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    1995

    Waseda University, Associate Professor

  • 1990
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    1995

    Waseda University, Associate Professor

  • 1988
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    1990

    Waseda University, Assistant Professor

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Professional Memberships 【 display / non-display

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    ACS

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    JSHPST

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    JSAC

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    JSAC

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    CSJ

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Research Areas 【 display / non-display

  • Analytical chemistry

  • Inorganic/coordination chemistry

Research Interests 【 display / non-display

  • 物質変換

Papers 【 display / non-display

  • Highly Selective Aluminum(III) Ion Sensing with Luminescent Iridium(III) Complexes Bearing a Distorted 2,2′-Bipyridine-3,3′-diol Moiety Utilizing a Rigidified Seven-Membered Chelate Ring

    Yota Suzuki, Ibuki Mizuno, Yui Tabei, Yuri Fujioka, Kazuteru Shinozaki, Tomoaki Sugaya, Koji Ishihara

    Inorg. Chem.   58   9663 - 9671  2019  [Refereed]

  • Detailed Reaction Mechanisms of 4-Pyridylboronic Acid and (N-Methyl)-4-Pyridinium Boronic Acid with D-Sorbitol in Aqueous Solution

    Daisuke Kusuyama, Yuta Samukawa, Tomoaki Sugaya, Satoshi Iwatsuki, Masahiko Inamo, Hideo D. Takagi, Koji Ishihara

    ChemistrySelect   4   4944 - 4951  2019  [Refereed]

  • Axial ligand substitution reactions of head-to-head α-pyridonato-bridged Pt(III) binuclear complexes bearing various equatorial ligands with chloride ion and olefin

    Shintaro Kusuhara, Kaori Kojima, Yota Suzuki, Yuki Morita, Tomoaki Sugaya, Satoshi Iwatsuki, Koji Ishihara, Kazuko Matsumoto

    Journal of Molecular Liquids   262   556 - 564  2018.07  [Refereed]

     View Summary

    In this study, axial ligand-substitution reactions of head-to-head (HH) α-pyridonato-bridged platinum(III) binuclear complexes bearing equatorial amine ligands (L = MeNH2, EtNH2, and L–L = ethylenediamine (en), and N,N′-dimethylethylenediamine (Me2en)) [(Cl)(NH3)2Pt(μ-α-pyridonato)2Pt(L)2(Cl)]2+ are synthesized, and the axial ligand substitution on these complexes with chloride ions are kinetically investigated in acidic aqueous solution. For these complexes, the formation reactions of the dichloro complexes from the monochloro complexes proceeded through three parallel reaction pathways, in contrast to those for the HH tetraammine amidato-bridged platinum (III) binuclear complexes. The effects of equatorial amine ligands as well as the bridging ligands on the axial ligand substitution are discussed. The reaction of [(H2O)(NH3)2Pt(μ-α-pyridonato)2Pt(en)(OH2)]2+ with p-styrenesulfonate is also kinetically investigated.

    DOI

  • Behavior of Ionic Liquids Around Charged Metal Complexes: Investigation of Homogeneous Electron Transfer Reactions Between Metal Complexes in Ionic Liquids

    Takuya Mabe, Fumiaki Doseki, Takeyoshi Yagyu, Koji Ishihara, Masahiko Inamo, Hideo D. Takagi

    Journal of Solution Chemistry   47   993 - 1020  2018  [Refereed]

  • Axial-ligand substitution reactions of a head-to-head pivalamidato-bridged Pt(III) binuclear complex bearing equatorial bromide ligands: A mechanistic study

    Takaaki Terada, Yu Kamezaki, Ryota Nakamura, Tomoaki Sugaya, Satoshi Iwatsuki, Koji Ishihara, Kazuko Matsumoto

    Inorganica Chimica Acta   467   391 - 399  2017.10

     View Summary

    Axial ligand-substitution reactions of head-to-head (HH) a binuclear pivalamidato-bridged platinum(III) complex bearing equatorial bromide ligands, [(H2O)(NH3)2Pt(μ-pivalamidato)2Pt(Br)2(OH2)]2+ (1), with chloride and bromide ions were thermodynamically and kinetically investigated in acidic aqueous solutions. Reactions of 1 with p-styrenesulfonate and 4-penten-1-ol were also kinetically investigated in order to clarify the reaction mechanisms involving olefins. In contrast to the reactions of the HH tetraammine pivalamidato-bridged platinum(III) binuclear complex, [(H2O)(NH3)2Pt(μ-pivalamidato)2Pt(NH3)2(OH2)]4+ (2′), all substitution processes on 1 involve single-step reactions. The effect of the equatorial halide ligands on the axial ligand substitution reactions of 1 is discussed in relation to 2′
    the rate-determining first substitution of H2O by X− at the Pt(Br2O2) site in 1 is followed by a fast second substitution of H2O by X− at Pt(N4). In contrast, axial ligand substitution on 2′ by X− proceeds in two consecutive steps. Reactions of 1 with p-styrenesulfonate or 4-penten-1-ol proceed in one step to form only mono-π complexes that are in rapid equilibrium with σ complexes, whereas reactions of 2′ with these olefins proceed in three consecutive steps via di-π complexes. These mechanistic differences are interpreted in terms of enhanced charge localization in the mono-π complexes of 1 ([PtII(NH3)2(μ-pivalamidato)2PtIV(Br)2(p-styrenesulfonate or 4-penten-1-ol)]2+).

    DOI

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Books and Other Publications 【 display / non-display

  • 錯体化学会選書8「錯体の溶液化学」

    横山, 田端編著, 共同執筆

    三共出版  2012.04

  • スワドル「無機化学」基礎・産業・環境

    石原, 高木, 矢野 共訳

    東京化学同人  1999.02

Awards 【 display / non-display

  • 日本分析化学会奨励賞

    1988  

Research Projects 【 display / non-display

  • Basic study on the reaction of boronic acid with glucose-Specific determination with a metal complex bearing a boronic acid moiety-

    Project Year :

    2017.04
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    2020.03
     

  • Development and improvement of boron-selective separation methods using multi-functional resins

    Project Year :

    2015.04
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    2018.03
     

     View Summary

    Novel hybrid (bifunctional) resins having both chelating ligand and counter cation moieties were investigated to establish effective aqueous boron separation. The hybrid resins having N-methyl-D-glucamine ligand and ammonium parts showed high chemosorption ability of boric acid at pH > ca. 10, whose ability was comparable to or more than that of commercially available boron-removing resins. In contrast, these resins desorbed almost quantitatively at pH 2. The results strongly suggest that the chelating ligand-cation hybrid resins is useful for a “gently pH-controlled” adsorption-desorption process of aqueous boron compounds, where weakly basic (pH 10)/acidic (pH 2) conditions are needed

  • A funadamental study on the reaction of boronic acid with saccharide-determination of saccharide with metal complexes having boronic acid moiety-

    Project Year :

    2013.04
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    2016.03
     

     View Summary

    A number of luminescent boronic acid-based sensors for sugars, which utilize a reversible reaction between boronic acid and diol, have been exploited so far. However, a fundamental study on how efficiently progresses the sensing reaction is lacking. In this study, we have performed at first equilibrium and kinetic study on the reactions of some boronic acids with diols in aqueous solution in order to get fundamental information for their reactions, which resulted in proposing an universal reaction mechanism of boronic acid with diol. Then, we have performed similar study on the reactions of boronic acid with sugars to identify the reactive species of boronic acid and a sugar in the sensing reaction, and proposed a comprehensive sensing mechanism. Based on the mechanism, we have designed and synthesized highly luminescent metal complexes with boronic acid moiety, and tried to determine a sugar with monitoring the change in luminescence due to its reactions with these complexes

  • 分子設計による機能性新素材開発

    ハイテク・リサーチ・センター整備事業

    Project Year :

    1996
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    2000
     

  • Thermodynamic and Mechanistic Studies on Reactions of Metal Complexes in Solution

     View Summary

    The purpose of this research is to study reactions of metal complexes in solution by thermodynamic and kinetic approaches.(1) Characterization of metal complexes in solution: On the basis of stability constants and reaction heats of complexation for phDTA as a ligand, energetic relations for complexation were clarified. Possible structures of the phDTA complexes in solution were discussed.(2) Studies on mechanisms of metal complex formation: Activation volumes for rapid complex formation in various solvents were obtained by using the high-pressure stopped-flow technique. The reaction mechanism has been related with the bulkiness of solvents and ligands.(3) Studies on mechanisms of solvent exchange on metal(II) ions: On the basis of activation volumes for solvent exchange determined by using high-pressure multinuclear NMR, discussions have been made on the relation between mechanisms and the solvent bulkiness.The special feature of the present research is to consider thermodynamic and kinetic behaviors of metal complexes in solution on the basis of reaction volumes and activation volumes. For this purpose we developed a high-pressure stopped-flow apparatus, high-pressure multinuclear NMR probes, a high-pressure ultrasonic absorption cell, automatization of a system for calorimetry and high precision dilatometers. All these have gained international recognition

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Specific Research 【 display / non-display

  • メチレン鎖で架橋したオルトアミノメチルジボロン酸のグルコースに対する反応性の検討

    2020  

     View Summary

     長さの異なる三種類のメチレン鎖リンカー(メチレン鎖の数 n = 4, 6, 8)で架橋したオルトアミノメチルジボロン酸を合成し、D-グルコースに対する反応の速度論的および平衡論的測定と解析を行うことにより、D-グルコースの選択的センシングに適した架橋炭素鎖の長さを検討した。解析結果より、ジボロン酸に対してD-グルコースの濃度が過剰の条件で、n = 4のジボロン酸はD-グルコースと1:1で反応するが、n = 6 および n = 8 のジボロン酸は1:2で反応することがわかった。すなわち、n = 4 のジボロン酸のみがD-グルコース分子中の2カ所のジオール部位と結合し、D-グルコース選択性を発現する可能性が高いことがわかった。

  • ボロン酸の反応に関する基礎研究に基づく糖類のセンシング

    2020  

     View Summary

     5-ヒドロキシ-オルトアゾフェニルボロン酸とN-メチルピリジルボロン酸、および5-エチルアミノ-オルトアゾフェニルボロン酸とN-メチルピリジルボロン酸をそれぞれp-キシレンで架橋した2種類のジボロン酸を合成し、キャラクタリゼーションを行い、D-グルコースおよびD-フルクトースとの条件平衡定数の測定を行った。後者のジボロン酸では、青色から赤紫への明瞭な色調変化が観測された。また、後者の条件平衡定数は、pKaが同程度のモノボロン酸の約40倍の値であり、D-グルコースおよびD-フルクトースとの条件平衡定数の値はほぼ等しかった。そのため、後者のジボロン酸は血液中のD-グルコースの定量に利用できる可能性が高い。

  • ボロン酸とボロン酸イオンの反応性の逆転に関する速度論的研究

    2019  

     View Summary

     ボロン酸(RB(OH)2)とボロン酸イオン(RB(OH)3–)の反応性を正しく理解することは、より優れたボロン酸型糖センサーの開発の基礎となる。しかし、両者の反応性を同時に評価できる反応系は、限定的である。我々はこれまで、反応系を適切に設計し、精密測定・解析を行うことにより、両者の反応性の評価を行ってきた。本研究では、アリザリンレッドSとフェニルボロン酸誘導体の反応系を用いることにより、ボロン酸のpKaが高くなるにつれ両者の反応性に差がなくなり、遂には反応性が逆転することを実験的に確かめた。また、なぜこのような現象が起こるのかを、両者の反応機構の違いに基づいて解釈した。

  • ベンゾオキサボロールとアリザリン レッド Sの反応に関する再研究

    2018  

     View Summary

     ベンゾオキサボロール(BxB)は、糖類に対する反応性の高さから再注目されている化合物であり、BxBを骨格とする糖センサーが多く報告されている。BxBとアリザリンレッドSの反応機構は既に他の研究者により報告されているが、議論の前提の基礎データの解釈に根本的な誤りがあるため、本研究において反応機構の詳細な再研究を行った。 様々な条件で測定したデータを詳しく解析した結果、反応機構は既報のものとは全く異なり, 如何に基礎データの正しい解釈が重要性であるかを例示することができた。 本研究成果は、化学的に正当な解析方法の例示となり、当該分野に対して適切な解析方法を浸透・徹底させる効果があると期待される。

  • フェニルボロン酸とアリザリン レッドSの反応に関する再研究

    2017  

     View Summary

     ボロン酸型糖センサーの基本骨格であるフェニルボロン酸(PhB)とアリザリンレッドS (ARS)との反応のメカニズムは, 既に報告されており, 広く受け入れられている。しかし, その論文には議論の前提となっている基礎データの解釈に根本的な誤りがある。そのため本研究では, キレート滴定の基本的な考え方である条件平衡定数の考え方を適用し, 基礎データの正しい解釈を例示するとともに, 反応速度論的測定により反応活性種を特定し, 詳細な反応機構の解明を行った。その結果, PhBとARSの反応の詳細な反応機構を構築することができた。また付随して, 酢酸緩衝液による当該反応の促進効果を定量的に説明することができた。

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Syllabus 【 display / non-display

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