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Probe for bio-oligomers and elucidation of their function

Research Project

Project/Area Number 21550160
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field Chemistry related to living body
Research InstitutionNagasaki University

Principal Investigator

MAKI Toshihide  長崎大学, 産学官連携戦略本部, 准教授 (10291535)

Project Period (FY) 2009 – 2011
Project Status Completed (Fiscal Year 2011)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2011: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2010: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2009: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords質量分析用分子標識剤 / 光開裂性分子 / エーテル結合形成 / ベンジル化 / 光開裂性 / カチオン / 糖 / ホルミル基 / αジケトン / 生命鎖 / 糖鎖 / ペプチド / Fries反応 / α-ヨードケトン / 撰択的エーテル化
Research Abstract

General procedures for derivatization of multi functionalized bio-oligomers and exploitation of new function to capture a target molecules connecting photocleavable molecular tag were achieved in this research.
Along with the experiment, a new synthetic route for the photocleavable molecular tag for laser desorption ionization mass spectrometry(LDI-MS) was achieved using Fries reaction of 2, 6-dimethylphenyl ester as its key reaction. Zirconium chloride was found as uniquely efficient adjuvant to promote the reaction. The molecular tag was obtained in 5 steps without chromatographic purification.
And, the Benzylation of hydroxyl groups in the presence of tertiary amines is established. A mixture of an alcohol and a benzyl halide afforded the corresponding benzyl ether in good to excellent yields in the presence of diisopropylethylamine. The importance of solventless conditions was observed. The reaction showed high tolerance to many functional groups including benzoate, even at a reaction temperature of 150°C. Sodium iodide was found to be an efficient catalyst to accelerate the reaction. The simple operation was successfully applied for pre-treatment of LDI-MS analysis.
Then, new trapping agent for sugars targeting 1, 2-diol motif by mean of ketal formation reaction. Photocleavable molecular tag bearing alpha diketone functioality was designed and synthesized. Since the compound does not have redundant tether substructure, high sensitivity is comparable with compounds previously prepared.

Report

(4 results)
  • 2011 Annual Research Report   Final Research Report ( PDF )
  • 2010 Annual Research Report
  • 2009 Annual Research Report
  • Research Products

    (13 results)

All 2012 2011 2010 2009 Other

All Journal Article (3 results) (of which Peer Reviewed: 3 results) Presentation (7 results) Remarks (1 results) Patent(Industrial Property Rights) (2 results)

  • [Journal Article] Benzylation of hydroxy groups with tertiary amine as a base2012

    • Author(s)
      Jeremiah W. Gathirwa, Toshihide Maki
    • Journal Title

      Tetrahedron

      Volume: 68巻 Pages: 370-375

    • NAID

      120006985210

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] Concise Synthesis of Photocleavable Molecular Tag for Laser Desorption Ionization Mass Spectrometry via Fries Reaction2012

    • Author(s)
      Jeremiah W. Gathirwa, Toshihide Maki
    • Journal Title

      Synthetic Communications

      Volume: (印刷中)

    • NAID

      120006985483

    • Related Report
      2011 Final Research Report
    • Peer Reviewed
  • [Journal Article] Benzylation of hydroxy groups with tertiary amine as a base2012

    • Author(s)
      Jeremiah W.Gathirwa, Toshihide Maki
    • Journal Title

      Tetrahedron

      Volume: 68 Issue: 1 Pages: 370-375

    • DOI

      10.1016/j.tet.2011.10.016

    • NAID

      120006985210

    • Related Report
      2011 Annual Research Report
    • Peer Reviewed
  • [Presentation] Bebzylation of hydroxy groups under weak basic conditions2011

    • Author(s)
      Jeremiah W.Gathirwa, Toshihide Maki
    • Organizer
      The 2^<nd> International Symposium on Process Chemistry
    • Place of Presentation
      京都国際会館
    • Year and Date
      2011-08-11
    • Related Report
      2011 Annual Research Report
  • [Presentation] 触媒的エーテル結合形成反応2011

    • Author(s)
      Jeremiah Gathirwa, 真木俊英
    • Organizer
      2011年日本化学会西日本大会要旨集
    • Place of Presentation
      徳島
    • Related Report
      2011 Final Research Report
  • [Presentation] Bebzylation of hydroxy groups under weark basic conditions2011

    • Author(s)
      Jeremiah Gathirwa, 真木俊英
    • Organizer
      The 2nd International Symposium on Process Chemistry要旨集
    • Place of Presentation
      京都
    • Related Report
      2011 Final Research Report
  • [Presentation] Fries reactionを鍵反応とするレーザー脱離イオン化質量分析用光開裂性分子タグの効率的合成2010

    • Author(s)
      Jeremiah Gathirwa, 真木俊英
    • Organizer
      2010日本化学会西日本大会
    • Place of Presentation
      熊本大学黒髪南キャンパス
    • Year and Date
      2010-11-06
    • Related Report
      2010 Annual Research Report
  • [Presentation] Fries reactionを鍵反応とするレーザー脱離イオン化質量分析用光開裂性分子タグの効率的合成2010

    • Author(s)
      Jeremiah Gathirwa, 真木俊英
    • Organizer
      2010年日本化学会西日本大会講演要旨集
    • Place of Presentation
      熊本大学(熊本)
    • Related Report
      2011 Final Research Report
  • [Presentation] 質量分析のための光イオン化デバイスの探索2009

    • Author(s)
      真木俊英
    • Organizer
      有機合成化学協会九州山口支部第21回若手研究者のためのセミナー要旨集
    • Place of Presentation
      福岡
    • Year and Date
      2009-12-19
    • Related Report
      2011 Final Research Report
  • [Presentation] 質量分析のための光イオン化デバイスの探索2009

    • Author(s)
      真木俊英
    • Organizer
      有機合成化学協会九州山口支部 第21回若手研究者のためのセミナー
    • Place of Presentation
      九州大学
    • Year and Date
      2009-12-19
    • Related Report
      2009 Annual Research Report
  • [Remarks]

    • URL

      http://www.jrc.nagasaki-u.ac.jp/sentan/kouzou/index.html

    • Related Report
      2011 Final Research Report
  • [Patent(Industrial Property Rights)] エーテルまたはエステルの製造方法 平成23年3月28日2011

    • Inventor(s)
      真木俊英
    • Industrial Property Rights Holder
      長崎大学
    • Industrial Property Number
      2011-007067
    • Filing Date
      2011-03-28
    • Related Report
      2010 Annual Research Report
  • [Patent(Industrial Property Rights)] エーテル、エステルおよびチオエーテルの製造方法2010

    • Inventor(s)
      真木俊英
    • Industrial Property Rights Holder
      長崎大学
    • Industrial Property Number
      2010-273923
    • Filing Date
      2010-12-08
    • Related Report
      2010 Annual Research Report

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Published: 2009-04-01   Modified: 2016-04-21  

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