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Elucidating hydration effect on potassium ion selectivity of valinomycin

Research Project

Project/Area Number 19K23624
Research Category

Grant-in-Aid for Research Activity Start-up

Allocation TypeMulti-year Fund
Review Section 0501:Physical chemistry, functional solid state chemistry, organic chemistry, polymers, organic materials, biomolecular chemistry, and related fields
Research InstitutionTokyo Institute of Technology

Principal Investigator

Hirata Keisuke  東京工業大学, 理学院, 助教 (80845777)

Project Period (FY) 2019-08-30 – 2022-03-31
Project Status Completed (Fiscal Year 2021)
Budget Amount *help
¥2,860,000 (Direct Cost: ¥2,200,000、Indirect Cost: ¥660,000)
Fiscal Year 2020: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2019: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Keywordsイオン選択性 / バリノマイシン / 赤外分光法 / 冷却イオントラップ分光法 / 気相分光法 / 水和効果 / 赤外分光 / エレクトロスプレーイオン化 / 質量分析
Outline of Research at the Start

親水-疎水界面でカリウムイオンのみを選択的に内包する生体分子であるバリノマイシンのK選択性の起源を水和効果の観点から明らかにする。溶液中での分光測定では困難であった親水-疎水界面のモデル化を実現するため、バリノマイシン-金属イオンの錯合体を気相(疎水環境)中に取り出し水分子を段階的に付加する。赤外分光法を用いて錯合体の水和構造を決定し、K選択性の原理に水和の微視的な構造論から迫る。

Outline of Final Research Achievements

In this study, to clarify the origin of the potassium selectivity of valinomycin, the molecular structures of valinomycin-metal complexes and their hydrated clusters were investigated by gas-phase infrared spectroscopy. It was found that the highly symmetric conformation of the complex with the high-affinity ion potassium is retained after hydration, whereas the molecular structure is distorted in the complex with the low-affinity sodium by the addition of a single water molecule. This strongly suggests that the hydration effect is an important factor in other molecules that exhibit ion selectivity.

Academic Significance and Societal Importance of the Research Achievements

本研究では,水和効果が分子のイオン選択性に大きな影響を及ぼしていることが示された。これは気相環境下で分子の組成・水分子の個数を精密に規定したことにより初めて示されたものであり、気相赤外分光法の威力を物語っている。精密な分光測定に裏打ちされたイオン選択性の構造論を展開した本研究は、イオン選択性を示す多様な分子の原理を解明するだけでなく、イオン選択性分子の創出にも寄与するものと考えられ、イオン分離や創薬にも展開されることが期待される。

Report

(4 results)
  • 2021 Annual Research Report   Final Research Report ( PDF )
  • 2020 Research-status Report
  • 2019 Research-status Report
  • Research Products

    (16 results)

All 2022 2021 2020 Other

All Int'l Joint Research (3 results) Journal Article (9 results) (of which Int'l Joint Research: 9 results,  Peer Reviewed: 9 results,  Open Access: 2 results) Presentation (4 results) (of which Int'l Joint Research: 2 results)

  • [Int'l Joint Research] イリノイ大/パシフィックノースウェスト国立研究所(米国)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] パリ大学(フランス)

    • Related Report
      2021 Annual Research Report
  • [Int'l Joint Research] ベルリン工科大学(ドイツ)

    • Related Report
      2021 Annual Research Report
  • [Journal Article] Collision-assisted stripping for determination of microsolvation-dependent protonation sites in hydrated clusters by cryogenic ion trap infrared spectroscopy: the case of benzocaineH<sup>+</sup>(H<sub>2</sub>O)<sub><i>n</i></sub>2022

    • Author(s)
      Hirata Keisuke、Haddad Fuad、Dopfer Otto、Ishiuchi Shun-ichi、Fujii Masaaki
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 24 Issue: 10 Pages: 5774-5779

    • DOI

      10.1039/d1cp05762f

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Gas phase protonated nicotine is a mixture of pyridine- and pyrrolidine-protonated conformers: implications for its native structure in the nicotinic acetylcholine receptor2022

    • Author(s)
      Takeda Naoya、Hirata Keisuke、Tsuruta Kazuya、Santis Garrett D.、Xantheas Sotiris S.、Ishiuchi Shun-ichi、Fujii Masaaki
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 24 Issue: 10 Pages: 5786-5793

    • DOI

      10.1039/d1cp05175j

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Hydration-controlled excited-state relaxation in protonated dopamine studied by cryogenic ion spectroscopy2021

    • Author(s)
      Hirata Keisuke、Kasai Ken-ichi、Gregoire Gilles、Ishiuchi Shun-ichi、Fujii Masaaki
    • Journal Title

      The Journal of Chemical Physics

      Volume: 155 Issue: 15 Pages: 151101-151101

    • DOI

      10.1063/5.0066919

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Open Access / Int'l Joint Research
  • [Journal Article] Double Ion Trap Laser Spectroscopy of Alkali Metal Ion Complexes with a Partial Peptide of the Selectivity Filter in K<sup>+</sup> Channels─Temperature Effect and Barrier for Conformational Conversions2021

    • Author(s)
      Suzuki Yukina、Hirata Keisuke、Lisy James M.、Ishiuchi Shun-ichi、Fujii Masaaki
    • Journal Title

      The Journal of Physical Chemistry A

      Volume: 125 Issue: 44 Pages: 9609-9618

    • DOI

      10.1021/acs.jpca.1c06440

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Potassium and sodium ion complexes with a partial peptide of the selectivity filter in K+ channels studied by cold ion trap infrared spectroscopy: the effect of hydration2021

    • Author(s)
      Negoro Takumi、Hirata Keisuke、Lisy James M.、Ishiuchi Shun-ichi、Fujii Masaaki
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: - Issue: 21 Pages: 12045-12050

    • DOI

      10.1039/d1cp00936b

    • Related Report
      2021 Annual Research Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Rethinking Ion Transport by Ionophores: Experimental and Computational Investigation of Single Water Hydration in Valinomycin-K+ Complexes2021

    • Author(s)
      Sato Eiko、Hirata Keisuke、Lisy James M.、Ishiuchi Shun-ichi、Fujii Masaaki
    • Journal Title

      The Journal of Physical Chemistry Letters

      Volume: 12 Issue: 6 Pages: 1754-1758

    • DOI

      10.1021/acs.jpclett.0c03372

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Chiral discrimination between tyrosine and β-cyclodextrin revealed by cryogenic ion trap infrared spectroscopy2020

    • Author(s)
      Hirata Keisuke、Mori Yuta、Ishiuchi Shun-ichi、Fujii Masaaki、Zehnacker Anne
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 22 Issue: 43 Pages: 24887-24894

    • DOI

      10.1039/d0cp02968h

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Alkali and Alkaline Earth Metal Ions Complexes with a Partial Peptide of the Selectivity Filter in K+ Channels Studied by a Cold Ion Trap Infrared Spectroscopy2020

    • Author(s)
      Otsuka Remina, Hirata Keisuke, Yuta Sasaki, Lisy James M., Ishiuchi Shun-ichi, Fujii Masaaki
    • Journal Title

      Chemphyschem

      Volume: 21 Issue: 8 Pages: 712-724

    • DOI

      10.1002/cphc.202000033

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Excited-state proton transfer in protonated adrenaline revealed by cryogenic UV photodissociation spectroscopy2020

    • Author(s)
      Dezalay Jordan、Broquier Michel、Soorkia Satchin、Hirata Keisuke、Ishiuchi Shun-ichi、Fujii Masaaki、Gregoire Gilles
    • Journal Title

      Physical Chemistry Chemical Physics

      Volume: 22 Issue: 20 Pages: 11498-11507

    • DOI

      10.1039/d0cp01127d

    • Related Report
      2020 Research-status Report
    • Peer Reviewed / Int'l Joint Research
  • [Presentation] Vibrational spectroscopy of hydrated clusters of valinomycin-metal complexes: Watching single water hydration2021

    • Author(s)
      Keisuke Hirata, Eiko Sato, Shun-ichi Ishiuchi, Masaaki Fujii
    • Organizer
      Pacifichem 2021
    • Related Report
      2021 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Cold ion trap infrared spectroscopy of Beauvericin metal complexes - Ionic radius dependence of conformations2021

    • Author(s)
      Kien Vo, Keisuke Hirata, James M. Lisy, Shun-ichi Ishiuchi, Masaaki Fujii
    • Organizer
      第15回分子科学討論会
    • Related Report
      2021 Annual Research Report
  • [Presentation] Cryogenic Ion Spectroscopy of Valinomycin-Metal Complexes: Effect of Water on Potassium Selectivity2020

    • Author(s)
      Keisuke Hirata
    • Organizer
      Gordon Research Conferences: Molecular and Ionic Clusters 2020
    • Related Report
      2019 Research-status Report
    • Int'l Joint Research
  • [Presentation] 冷却イオントラップ法によるバリノマイシンーアルカリ金属イオン水和クラスターの赤外分光2020

    • Author(s)
      佐藤映虹
    • Organizer
      第13回分子科学討論会
    • Related Report
      2019 Research-status Report

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Published: 2019-09-03   Modified: 2023-01-30  

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