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Development of model systems for highly reactive amino-acid derivatives by taking advantage of nano-sized molecular cavities

Research Project

Project/Area Number 15H03776
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionTokyo Institute of Technology

Principal Investigator

Goto Kei  東京工業大学, 理学院, 教授 (70262144)

Research Collaborator Block Eric  
George Graham  
Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥17,160,000 (Direct Cost: ¥13,200,000、Indirect Cost: ¥3,960,000)
Fiscal Year 2017: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2016: ¥3,640,000 (Direct Cost: ¥2,800,000、Indirect Cost: ¥840,000)
Fiscal Year 2015: ¥9,880,000 (Direct Cost: ¥7,600,000、Indirect Cost: ¥2,280,000)
Keywords有機化学 / 酵素モデル / 活性中間体 / アミノ酸 / 合成化学 / セレノシステイン / セレネン酸 / ヨウ化セレネニル / 抗酸化酵素
Outline of Final Research Achievements

At the active site of enzymes, reactive species that are very unstable in artificial systems sometimes play crucial roles in chemical transformations. Such fabulous features of enzymatic reactions are highly associated with the geometrically isolated environments at the active sites. For modeling such an isolated environment of enzymes with synthetic systems, novel nano-sized molecular cavities incorporating highly reactive amino-acid derivatives have been developed and applied to stabilization of reactive intermediates of biological reactions. By utilizing the novel model system, chemical processes that have been proposed for the catalytic mechanism of selenoenzymes such as glutathione peroxidase have been demonstrated experimentally.

Academic Significance and Societal Importance of the Research Achievements

セレンは生体必須超微量元素でありppbオーダーの含有量で高い生理活性を示すが、その機能を司る含セレン酵素の作用機序については、活性中間体の不安定性のために間接的な情報しか得られず、解明が困難であった。本研究で明らかになった活性中間体の化学的挙動に関する実験的エビデンスは、抗酸化酵素などの作用機序の化学的解明、引いては老化や細胞死などの機構研究の基盤になると期待される。

Report

(4 results)
  • 2018 Final Research Report ( PDF )
  • 2017 Annual Research Report
  • 2016 Annual Research Report
  • 2015 Annual Research Report
  • Research Products

    (48 results)

All 2019 2018 2017 2016 2015 Other

All Int'l Joint Research (2 results) Journal Article (5 results) (of which Int'l Joint Research: 2 results,  Peer Reviewed: 5 results,  Open Access: 2 results,  Acknowledgement Compliant: 2 results) Presentation (41 results) (of which Int'l Joint Research: 14 results,  Invited: 7 results)

  • [Int'l Joint Research] State University of New York/Stanford University(米国)

    • Related Report
      2017 Annual Research Report
  • [Int'l Joint Research] University of Saskatchewan(カナダ)

    • Related Report
      2017 Annual Research Report
  • [Journal Article] Model study on trapping of protein selenenic acids by utilizing a stable synthetic congener2019

    • Author(s)
      Shohei Sase, Ryutaro Kimura, Ryosuke Masuda, Kei Goto
    • Journal Title

      New Journal of Chemistry

      Volume: 18 Issue: 18 Pages: 6830-6833

    • DOI

      10.1039/c9nj01072f

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ajothiolanes: 3,4-Dimethylthiolane Natural Products from Garlic (Allium sativum)2018

    • Author(s)
      Eric Block, Berenice Dethier, Benjamin Bechand, Julien J. H. Cotelesage, Graham N. George, Kei Goto, Ingrid J. Pickering, Emerita Mendoza Rengifo, Robert Sheridan, Eileen Y. Sneeden, and Linda Vogt
    • Journal Title

      Journal of Agricultural and Food Chemistry

      Volume: 66 Issue: 39 Pages: 10193-10204

    • DOI

      10.1021/acs.jafc.8b03638

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Photochemically Generated Thiyl Free Radicals Observed by X-ray Absorption Spectroscopy2017

    • Author(s)
      Sneeden Eileen Y.、Hackett Mark J.、Cotelesage Julien J. H.、Prince Roger C.、Barney Monica、Goto Kei、Block Eric、Pickering Ingrid J.、George Graham N.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 139 Issue: 33 Pages: 11519-11526

    • DOI

      10.1021/jacs.7b05116

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Modeling of the Bioactivation of an Organic Nitrate by a Thiol to Form a Thionitrate Intermediate2017

    • Author(s)
      Tsukasa Sano, Keiichi Shimada, Yohei Aoki, Takayuki Kawashima, Shohei Sase, Kei Goto
    • Journal Title

      Molecules

      Volume: 22 Issue: 1 Pages: 19-19

    • DOI

      10.3390/molecules22010019

    • Related Report
      2016 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Synthesis of a Stable Primary-Alkyl-Substituted Selenenyl Iodide and Its Hydrolytic Conversion to the Corresponding Selenenic Acid2015

    • Author(s)
      Shohei Sase, Ryo kakimoto, Ryutaro Kimura, Kei Goto
    • Journal Title

      Molecules

      Volume: 20 Issue: 12 Pages: 21415-21420

    • DOI

      10.3390/molecules201219773

    • Related Report
      2015 Annual Research Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Presentation] セレノペプチド含有分子クレードルを活用したGPx由来セレネン酸失活抑制機構のモデル研究2019

    • Author(s)
      増田涼介,佐瀬祥平,後藤 敬
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 分子クレードルを活用したシステイン由来N-ヒドロキシスルフェンアミドの合成研究2019

    • Author(s)
      山口美涼,佐瀬祥平,後藤 敬
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 内部セレノシステインモデルを活用したセレノシステイン由来セレネン酸の観測および反応性に関する検討2018

    • Author(s)
      増田涼介,佐瀬祥平,後藤 敬
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Annual Research Report
  • [Presentation] クレードルドセレノシステインを活用した内部セレノシステイン由来セレネン酸の反応性に関するモデル研究2018

    • Author(s)
      増田涼介,佐瀬祥平,後藤 敬
    • Organizer
      第16回ホスト・ゲスト化学シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] Model Study of a GPx-derived Selenenic Acid with Thiols by Utilizing a Cradled Selenocysteine2018

    • Author(s)
      Ryosuke Masuda, Shohei Sase, Kei Goto
    • Organizer
      28th International Symposium on the Organic Chemistry of Sulfur
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 巨大分子キャビティを活用したセレノシステインセレネン酸に関するモデル研究2018

    • Author(s)
      佐瀬祥平,増田涼介,木村龍太郎,後藤 敬
    • Organizer
      第29回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Modeling of Selenoprotein-derived Reactive Intermediates by Utilizing Cradled Selenocysteins2018

    • Author(s)
      Kei Goto, Ryutaro Kimura, Ryosuke Masuda, Takafumi Karasaki, and Shohei Sase
    • Organizer
      The 7th International Selenium Conference
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Modeling of Reactive Intermediates of Selenoenzymes by Utilizing Nano-sized Molecular Cavities2018

    • Author(s)
      Kei Goto, Ryosuke Masuda, Ryutaro Kimura, Takafumi Karasaki, and Shohei Sase
    • Organizer
      International Congress on Pure & Applied Chemistry (ICPAC Langkawi) 2018
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] セレノシステイン含有ペプチドモデル系を活用したGPx由来セレネン酸の反応性に関するモデル研究2018

    • Author(s)
      増田涼介,木村龍太郎,唐崎貴史,佐瀬祥平,後藤 敬
    • Organizer
      第45回有機典型元素化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 分子キャビティを活用した安定なペルチオスルフェン酸(R-SSOH)の合成2018

    • Author(s)
      佐藤有理紗,佐瀬祥平,後藤 敬
    • Organizer
      第45回有機典型元素化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Modeling of Biological Reaction Processes Involving Cysteine Sulfenic Acids and Related Species by Utilizing Nano-sized Molecular Cavities2017

    • Author(s)
      Kei Goto, Nozomu Watanabe, Ryutaro Kimura, Tsukasa Sano, and Shohei Sase
    • Organizer
      The 12th International Conference on Heteroatom Chemistry
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] セレノシステイン由来酵素反応活性中間体の合成モデル研究2017

    • Author(s)
      後藤 敬
    • Organizer
      第3回日本セレン研究会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 巨大分子キャビティを活用したセレノシステイン由来セレネン酸に関するモデル研究2017

    • Author(s)
      佐瀬祥平,木村龍太郎,唐崎貴史,後藤 敬
    • Organizer
      第15回ホスト・ゲスト化学シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] 分子クレードルに内包されたセレノシステインセレネン酸の直接観測2017

    • Author(s)
      佐瀬祥平,佐野 司,唐崎貴史,渡邊 望,木村龍太郎,後藤 敬
    • Organizer
      第28回基礎有機化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] Elucidation of Biological Reaction Processes Involving Cysteine Sulfenic Acids and Related Species by Utilizing Cavity-Shaped Model Systems2017

    • Author(s)
      Kei Goto, Nozomu Watanabe, Ryutaro Kimura, and Shohei Sase
    • Organizer
      The 2nd International Symposium on Stimuli-responsive Chemical Species for the Creation of Functional Molecules
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] 巨大分子キャビティを活用したCys-Serジペプチド由来高反応性化学種のモデル研究2017

    • Author(s)
      渡邊 望,佐瀬祥平,後藤 敬
    • Organizer
      日本化学会第97春季年会
    • Related Report
      2016 Annual Research Report
  • [Presentation] 巨大分子キャビティを活用したセレノシステイン由来セレネン酸の安定性および反応性の解明2017

    • Author(s)
      木村龍太郎,佐瀬祥平,後藤 敬
    • Organizer
      日本化学会第97春季年会
    • Related Report
      2016 Annual Research Report
  • [Presentation] 巨大分子キャビティを活用した第一級アルキル置換セレネン酸の反応性の解明2016

    • Author(s)
      木村龍太郎,佐瀬祥平,後藤 敬
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      京田辺
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] 「クレードルドセレノシステイン」を活用した抗酸化酵素反応過程のモデル研究2016

    • Author(s)
      唐崎貴史,佐瀬祥平,布施新一郎,田中浩士,後藤 敬
    • Organizer
      日本化学会第96春季年会
    • Place of Presentation
      京田辺
    • Year and Date
      2016-03-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] Modeling of Cysteine-Derived Reactive Intermediates by Taking Advantage of Cavity-Shaped Molecular Cradles2016

    • Author(s)
      Kei Goto, Tsukasa Sano, Nozomu Watanabe, and Shohei Sase
    • Organizer
      The 70th Fujihara Seminar
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Modeling of Reactive Intermediates Derived from Selenocysteines by Utilizing Cavity-Shaped Molecular Cradles2016

    • Author(s)
      Kei Goto, Takafumi Karasaki, and Shohei Sase
    • Organizer
      13th International Conference on the Chemistry of Selenium and Tellurium
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Synthesis and Reactivity of a Primary-Alkyl-Substituted Selenenic Acid Stabilized by a Large Cavity-Shaped Molecular Framework2016

    • Author(s)
      Ryutaro Kimura, Shohei Sase, and Kei Goto
    • Organizer
      13th International Conference on the Chemistry of Selenium and Tellurium
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Syntheses and Reacivity of Cysteine- and Selenocysteine-Derived Reactive Species by Utilizing Cavity-Shaped Molecular Cradles2016

    • Author(s)
      Kei Goto
    • Organizer
      The 7th Heron Island Conference on Reactive Intermediates and Unusual Molecules
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] yntheses of Cysteine-Derived Reactive Intermediates by Taking Advantage of Cradled Cysteines2016

    • Author(s)
      Kei Goto, Tsukasa Sano, Nozomu Watanabe, and Shohei Sase
    • Organizer
      27th International Symposium on Organic Chemistry of Sulfur
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Stabilization of a Primary-alkyl-substituted Sulfenic Scid and Its Anion by Utilizing a Cavity-shaped Molecular Framework2016

    • Author(s)
      Shohei Sase, Michihiro Ishihara, Noriaki Abe, Ryutaro Kimura, and Kei Goto
    • Organizer
      27th International Symposium on Organic Chemistry of Sulfur
    • Related Report
      2016 Annual Research Report
    • Int'l Joint Research
  • [Presentation] クレードルドシステインおよびセレノシステインを活用した生体反応モデル系の構築2016

    • Author(s)
      佐瀬祥平,佐野 司,唐崎貴史,後藤 敬
    • Organizer
      第14回ホスト・ゲスト化学シンポジウム
    • Related Report
      2016 Annual Research Report
  • [Presentation] 巨大分子キャビティを活用した第一級アルキル置換セレネン酸の反応性の解明2016

    • Author(s)
      木村龍太郎,佐瀬祥平,後藤 敬
    • Organizer
      第14回ホスト・ゲスト化学シンポジウム
    • Related Report
      2016 Annual Research Report
  • [Presentation] 巨大キャビティ型分子骨格を活用した内部システイン由来スルフェン酸モデル化合物の合成と反応2016

    • Author(s)
      渡邊 望,佐瀬祥平,後藤 敬
    • Organizer
      第14回ホスト・ゲスト化学シンポジウム
    • Related Report
      2016 Annual Research Report
  • [Presentation] クレードルドシステインおよびセレノシステインの開発と生体反応過程のモデル化への応用2016

    • Author(s)
      佐瀬祥平,佐野 司,唐崎貴史,後藤 敬
    • Organizer
      第109回有機合成シンポジウム
    • Related Report
      2016 Annual Research Report
  • [Presentation] 巨大分子キャビティを活用した甲状腺ホルモン活性化酵素中間体のモデル化合物の開発2016

    • Author(s)
      後藤 敬,木村龍太郎,唐崎貴史,佐瀬祥平
    • Organizer
      第19回ヨウ素学会シンポジウム
    • Related Report
      2016 Annual Research Report
  • [Presentation] 巨大分子空孔を活用した生体反応活性種のモデル研究2016

    • Author(s)
      後藤 敬
    • Organizer
      第3回次世代の有機化学・広島シンポジウム
    • Related Report
      2016 Annual Research Report
    • Invited
  • [Presentation] 巨大分子キャビティを活用した含硫黄ペプチドモデル化合物の開発2016

    • Author(s)
      渡邊 望,佐瀬祥平,後藤 敬
    • Organizer
      第43回有機典型元素化学討論会
    • Related Report
      2016 Annual Research Report
  • [Presentation] 巨大分子キャビティを活用したセレノシステイン由来セレネン酸および関連化学種の反応性に関するモデル研究2016

    • Author(s)
      木村龍太郎,唐崎貴史,佐瀬祥平,後藤 敬
    • Organizer
      第43回有機典型元素化学討論会
    • Related Report
      2016 Annual Research Report
  • [Presentation] Synthesis of a stable selenoaldehyde by unprecedented C=Se double bond formation through β-dehydration2015

    • Author(s)
      Kei Goto, Ryo Kakimoto, Ryutaro Kimura, Shohei Sase
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies
    • Place of Presentation
      Honolulu (USA)
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Synthesis, structure, and reactivity of a primary-alkyl-substituted sulfenic acid and its anion2015

    • Author(s)
      Kei Goto, Michihiro Ishihara, Noriaki Abe, Shohei Sase
    • Organizer
      The 2015 International Chemical Congress of Pacific Basin Societies
    • Place of Presentation
      Honolulu (USA)
    • Year and Date
      2015-12-15
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research
  • [Presentation] クレードルドセレノシステインを活用した安定なセレノシステインヨウ化セレネニルの合成2015

    • Author(s)
      唐崎貴史,佐瀬祥平,後藤 敬
    • Organizer
      第42回有機典型元素化学討論会
    • Place of Presentation
      名古屋
    • Year and Date
      2015-12-03
    • Related Report
      2015 Annual Research Report
  • [Presentation] デンドリマー型分子骨格を有する第一級アルキル置換含セレン化学種を活用した生体反応過程に関するモデル研究2015

    • Author(s)
      木村龍太郎,佐瀬祥平,後藤 敬
    • Organizer
      第26回基礎有機化学討論会
    • Place of Presentation
      松山
    • Year and Date
      2015-09-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] 巨大分子キャビティを活用した甲状腺ホルモン活性化酵素触媒部位モデルの開発2015

    • Author(s)
      唐崎貴史,佐瀬祥平,後藤 敬
    • Organizer
      第26回基礎有機化学討論会
    • Place of Presentation
      松山
    • Year and Date
      2015-09-24
    • Related Report
      2015 Annual Research Report
  • [Presentation] Self-catalyzed β-dehydration of a Primary-alkyl-substituted Selenenic Acid to Form a Stable Selenoaldehyde2015

    • Author(s)
      Kei Goto, Ryo Kakimoto, Shohei Sase
    • Organizer
      The 11th International Conference on Heteroatom Chemistry
    • Place of Presentation
      Caen (France)
    • Year and Date
      2015-06-14
    • Related Report
      2015 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] 巨大分子キャビティを活用した含セレン高反応性化学種の安定化と新規反応性の開拓2015

    • Author(s)
      後藤 敬,柿本 涼,木村龍太郎,佐瀬祥平
    • Organizer
      第13回ホスト・ゲスト化学シンポジウム
    • Place of Presentation
      仙台
    • Year and Date
      2015-06-06
    • Related Report
      2015 Annual Research Report
  • [Presentation] キャビティ型分子骨格を活用した安定な第一級アルキル置換ヨウ化セレネニルの合成2015

    • Author(s)
      木村龍太郎,柿本 涼,佐瀬祥平,後藤 敬
    • Organizer
      第18回ヨウ素学会シンポジウム
    • Place of Presentation
      千葉
    • Related Report
      2015 Annual Research Report

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Published: 2015-04-16   Modified: 2025-01-30  

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