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New Development in Chemistry of Hypervalent Radicals Approach from the Gas-phase

Research Project

Project/Area Number 18350009
Research Category

Grant-in-Aid for Scientific Research (B)

Allocation TypeSingle-year Grants
Section一般
Research Field Physical chemistry
Research InstitutionKobe University

Principal Investigator

FUKE Kiyokazu  Kobe University, GRADUATE SCHOOL OF SCIENCE, PROFESSOR (00111766)

Co-Investigator(Kenkyū-buntansha) ISHIKAWA Haruki  KOBE UNIVERSITY, GRADUATE SCHOOL OF SCIENCE, ASSOCIATE PROFESSOR (80261551)
Project Period (FY) 2006 – 2007
Project Status Completed (Fiscal Year 2007)
Budget Amount *help
¥16,010,000 (Direct Cost: ¥14,900,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2007: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000)
Fiscal Year 2006: ¥11,200,000 (Direct Cost: ¥11,200,000)
KeywordsHypervalent Radical / Ammonium Radicals / Oxisonium Radical / Ionization Energy / Femtosecond Spectroscopy / Dipeptide / Cluster / Infrared Spectroscopy / イオン化エネルギー / NH_4ラジカル / 光イオン化 / 赤外スペクトル / 反応中間体
Research Abstract

In order to reveal the role of hypervalent radicals in chemical reactions including those in biological chemistry, we have studied on the following three subjects.
1. The electronic structures of Na-2^-(H_2O)_n (n〓6), which have a similar loosely-bounded electron to NH_4 have been investigated by a photoelectron spectroscopy (PES) to examine the solvation of sodium aggregates in small water clusters, From the analysis of the PES bands for the transitions from the anion to the neutral ground and first excited states derived from Na_2 (1^1Σ_g^+) and Na_2(1^3Σ_u^+) it is found that the Na_2-Na^+(H_2O)_n^-type electronic state grows with increasing cluster size, which can be regarded as a sign of the solvation of Na_2 with ionization of the hydrated Na.
2. Ionization potentials (IPs) of NR_4(CH_3OH)_m (NH_3)_n radicals produced by an ArF excimer laser photolysis of ammonia-methanol mixed clusters are determined by the photoionization threshold measurements. The observed IPs show the different evolutions with increasing the number of ammonia and methanol solvents. We have also examined the formation and relaxation dynamics of NH_4(CH_3OH)_m(NH_3)_n clusters produced by photolysis of ammonia-methanol mixed neutral clusters using a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ion, NH_4(CH_3OH)_m(NH_3)_n, the kinetic model is constructed.
3. A photodissociation spectrometer, containing a spray ionization source and a temperature-variable multipoleion trap, has been constructed to examine the structure and reactivity of gas phase biological molecular ionsat various temperatures. Ultraviolet (UV) and infrared (IR) photodissociation spectra of protonatedalanyltryptophan (Ala-TrpH+) and tryptophanylglycine (Trp-GlyH+) have been investigated to examine the effect of proton on the electronic structure and reactivity of the dipeptides.

Report

(3 results)
  • 2007 Annual Research Report   Final Research Report Summary
  • 2006 Annual Research Report
  • Research Products

    (44 results)

All 2008 2007 2006

All Journal Article (11 results) (of which Peer Reviewed: 6 results) Presentation (32 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] Hydratlon Process of Na_2 in Small Water Clusters : Photoelectron Spectroscopy and Theoretical Study of Na_2-(H_2O)_n2008

    • Author(s)
      藤原 亮正
    • Journal Title

      J. Phys. Chem. A 111

      Pages: 7364-7373

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Photodissociation and Spectroscopic Study of Cold Protonated Dipeptides.2008

    • Author(s)
      藤原 亮正
    • Journal Title

      J. Phys. Chem. A 112

      Pages: 1457-1463

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Solvation Structure and Stability of Hypervalent NH_4(CH_3OH)_m(NH_3)_n clusters2008

    • Author(s)
      山田 勇治
    • Journal Title

      Chem. Phys. Lett. 459

      Pages: 65-69

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Photodissociation and Spectroscopic Study of Cold Protonated Dipeptides2008

    • Author(s)
      A. Fujihara, H. Matsumoto, Y. Shibata, H. Ishikawa, K. Fuke
    • Journal Title

      J. Phys. Chem. A, 112

      Pages: 1457-1463

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Solvation structure and stability of hypervalent NH_4(CH_3OH)_m(NH_3)_n clusters2008

    • Author(s)
      Y. Yamada, Y. Nishino, A. Fujihara, H. Ishikawa, K. Fuke
    • Journal Title

      Chem. Phys. Lett. 459

      Pages: 65-69

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Solvation Structure and Stability of Hypervalent NH_4(CH_3OH)_m(NH_3)_n clusters2008

    • Author(s)
      山田 勇治
    • Journal Title

      Chem. Phys. Lett. (in press)

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Construction of a Temperature-Variable Photodissociation Spectrometer for Gas-Phase Cluster Ions and Its Application to Peptides2007

    • Author(s)
      藤原 亮正
    • Journal Title

      The Bulletin of the Nano Science and Technolog 6

      Pages: 29-34

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
    • Peer Reviewed
  • [Journal Article] Hydration Process of Na_2 in Small Water Clusters: Photoelectron Spectroscopy and Theoretical Study of Na_2(H_2O)_n2007

    • Author(s)
      A. Fujihara, C. Miyata, A. Maekawa, K. Fuke, K. Daigoku, N. Murata, K. Hashimoto
    • Journal Title

      J. Phys. Chem. A 111

      Pages: 7364-7373

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] "Construction of a Temperature-Variable Photodissociation Spectrometer for Gas-Phase Cluster Ions and Its Application to Peptides.2007

    • Author(s)
      A. Fujihara, H. Ishikawa, K. Fuke
    • Journal Title

      The Bulletin of the Nano Science and Technology 6

      Pages: 29-34

    • NAID

      40015753036

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Journal Article] Hydration Process of Na_2 in Small Water Clusters: Photoelectron Spectroscopy and Theoretical Study of Nat_2-(H_2O)_n2007

    • Author(s)
      藤原 亮正
    • Journal Title

      J. Phys. Chem. A 111

      Pages: 7364-7373

    • Related Report
      2007 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Spontaneous Ionization and Disslution of Na_2 in Small Water Clusters: Photoelectron Spectroscopy and Theoretical Study of Na_2 (H_2O)_n2007

    • Author(s)
      藤原 亮正
    • Journal Title

      J. Phys. Chem. (in press)

    • Related Report
      2006 Annual Research Report
  • [Presentation] Solvation Structure and Ultra-fast Dynamics of Hypervalent Radical in Ammonia-methanol Clusters2008

    • Author(s)
      山田勇治, 他
    • Organizer
      Gordon Research Conference
    • Place of Presentation
      オズワ(フランス)
    • Year and Date
      2008-09-10
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Solvation Structure and Ultra-fast Dynamics of Hypervalent Radical in Ammonia-methanol Clusters2008

    • Author(s)
      Y. Yamada, et al.
    • Organizer
      Gordon Conference
    • Place of Presentation
      France
    • Year and Date
      2008-09-10
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Photodissociation Spectroscopy of Cold Protonated Dipeptides and its solvated clusters2008

    • Author(s)
      冨宅喜代一, 他
    • Organizer
      Gordon Research Conference
    • Place of Presentation
      オズワ(フランス)
    • Year and Date
      2008-09-08
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Photodis sociation Spectroscopy of Cold Protonated Dipeptides and its solvated clusters2008

    • Author(s)
      K. Fuke, et al.
    • Organizer
      Gordon Conference
    • Place of Presentation
      France
    • Year and Date
      2008-09-08
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] NH_3・CH_3OHクラスター中での超原子価ラジカルの溶媒和構造と超高速ダイナミックス2008

    • Author(s)
      山田勇治, 他
    • Organizer
      化学反応討論会
    • Place of Presentation
      札幌
    • Year and Date
      2008-06-03
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 光電子分光法を用いたポリアラニンの構造の研究2008

    • Author(s)
      石川春樹, 他
    • Organizer
      化学反応討論会
    • Place of Presentation
      札幌
    • Year and Date
      2008-06-03
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] クラスター化学を支える実験と理論の共同研究2007

    • Author(s)
      冨宅喜代一
    • Organizer
      実在系分子理論研究会
    • Place of Presentation
      東京
    • Year and Date
      2007-11-17
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Spectroscopy of cooled molecular ions in gas-phase2007

    • Author(s)
      冨宅喜代一
    • Organizer
      Asian CORE Symposium on Advanced Laser Spectroscopy
    • Place of Presentation
      神戸
    • Year and Date
      2007-09-25
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] 赤外分光法を用いた7-アザインドールニ量体の基底状態二重プロトン移動反応の研究2007

    • Author(s)
      石川春樹, 他
    • Organizer
      分子科学討論会
    • Place of Presentation
      仙台
    • Year and Date
      2007-09-25
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] アンモニア・メタノールクラスター中での超原子価ラジカルの生成及び緩和機構の解明2007

    • Author(s)
      山田勇治, 他
    • Organizer
      分子科学討論会
    • Place of Presentation
      仙台
    • Year and Date
      2007-09-25
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] 「Spectroscopy of cooled molecular ions in gas-phase2007

    • Author(s)
      K. Fuke
    • Organizer
      Asian CORE Symposium on Advanced Laser Spectroscopy
    • Place of Presentation
      Kobe.
    • Year and Date
      2007-09-25
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] "Formation and Relaxation Mechanism of Hypervalent Radicals in Ammonia-Methanol Clusters2007

    • Author(s)
      Y. Yamada, et al.
    • Organizer
      Annual Meeting of Japan Society for Molecular Science
    • Place of Presentation
      Sendai.
    • Year and Date
      2007-09-25
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 赤外分光法を用いた7-アザインドール二量体の基底状態二重プロトン移動反応の研究2007

    • Author(s)
      石川春樹
    • Organizer
      分子科学討論会
    • Place of Presentation
      仙台
    • Year and Date
      2007-09-25
    • Related Report
      2007 Annual Research Report
  • [Presentation] 気体核磁気共鳴法の開発2007

    • Author(s)
      冨宅喜代一
    • Organizer
      日本質量分析学会イオン反応研究会
    • Place of Presentation
      大阪
    • Year and Date
      2007-08-04
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 極低温冷却したプロトン化ジペプチドの構造と反応性2007

    • Author(s)
      藤原亮正, 他
    • Organizer
      第23回化学反応討論会
    • Place of Presentation
      神戸
    • Year and Date
      2007-06-13
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] NH_3・ CH_3OHクラスター中での超原子価ラジカルの溶媒和と安定性2007

    • Author(s)
      西野曜子, 他
    • Organizer
      第23回化学反応討論会
    • Place of Presentation
      神戸
    • Year and Date
      2007-06-13
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] NH_3・CH_3OHクラスター中での超原子価ラジカルの溶媒和と安定性2007

    • Author(s)
      西野曜子
    • Organizer
      第23回化学反応討論会
    • Place of Presentation
      神戸
    • Year and Date
      2007-06-13
    • Related Report
      2007 Annual Research Report
  • [Presentation] 気相クラスターイオンの温度可変光解離分光装置の製作2007

    • Author(s)
      藤原亮正, 他
    • Organizer
      ナノ学会第5回大会
    • Place of Presentation
      筑波
    • Year and Date
      2007-05-21
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Annual Research Report 2007 Final Research Report Summary
  • [Presentation] Dissolution Process of Na2 in Water Clusters2007

    • Author(s)
      A. Maekawa, et al.
    • Organizer
      87^<TH> Chemical Society Meeting
    • Place of Presentation
      Osaka.
    • Year and Date
      2007-03-28
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Temperature-Variable Ultraviolet Photodissociation Spectroscopy of Protonated Peptide Ions2007

    • Author(s)
      A. Fujihara, et al.
    • Organizer
      87^<TH> Chemical Society Meeting
    • Place of Presentation
      Osaka.
    • Year and Date
      2007-03-27
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 水クラスター中でのNa_2の溶解過程2007

    • Author(s)
      前川亜耶子
    • Organizer
      第87日本化学会春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2007-03-26
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 気相溶媒和金属イオンの温度可変分光解析装置の開発と生体分子への応用2007

    • Author(s)
      冨宅喜代一
    • Organizer
      第87日本化学会春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2007-03-26
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] プロトン化したジペプチドイオンの温度可変紫外光解離分光2007

    • Author(s)
      藤原亮正, 他
    • Organizer
      第87日本化学会春季年会
    • Place of Presentation
      大阪
    • Year and Date
      2007-03-26
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 金属クラスターの溶媒和構造と溶解過程2007

    • Author(s)
      冨宅喜代一
    • Organizer
      分子科学研究所研究会
    • Place of Presentation
      岡崎
    • Year and Date
      2007-03-19
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Structure and Reactivity of Ultracold Dipeptides2007

    • Author(s)
      A. Fujihara, et al.
    • Organizer
      23th Symposium on Chemical Reaction Dynamics
    • Place of Presentation
      Klobe.
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 温度可変分光解析装置の開発と生体分子への応用」2006

    • Author(s)
      冨宅喜代一, 石川春樹
    • Organizer
      分子科学研究所研究会
    • Place of Presentation
      岡崎
    • Year and Date
      2006-12-21
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Microscopic solvation and reaction processes of metal atoms/ions in small gas-phase clusters2006

    • Author(s)
      冨宅 喜代一
    • Organizer
      Indo-Japan Joint Workshop
    • Place of Presentation
      神戸
    • Year and Date
      2006-09-25
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] Microscopic solvation and reaction processes of metal atoms/ions in small gas-phase clusters2006

    • Author(s)
      K. Fuke
    • Organizer
      Indo-Japan Joint Workshop
    • Place of Presentation
      Kobe.
    • Year and Date
      2006-09-25
    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] プロトン化したジペプチドイオンの光解離過程2006

    • Author(s)
      松本浩幸, 他
    • Organizer
      分子構造総合討論会
    • Place of Presentation
      静岡
    • Year and Date
      2006-09-21
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] エレクトロスプレーイオン源を備えた温度可変分光解析装置の製作2006

    • Author(s)
      藤原亮正
    • Organizer
      分子構造総合討論会
    • Place of Presentation
      静岡
    • Year and Date
      2006-09-21
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] クラスター内での水素原子反応のダイナミックス2006

    • Author(s)
      冨宅喜代一
    • Organizer
      強光子場研究会
    • Place of Presentation
      東京
    • Year and Date
      2006-09-14
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Presentation] 溶媒和Mg原子の構造と反応性2006

    • Author(s)
      西野曜子
    • Organizer
      第22回化学反応討論会
    • Place of Presentation
      岡崎
    • Year and Date
      2006-06-07
    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2007 Final Research Report Summary
  • [Patent(Industrial Property Rights)] 気体核磁気共鳴装置2007

    • Inventor(s)
      冨宅喜代一
    • Industrial Property Rights Holder
      神戸大学
    • Filing Date
      2007-01-09
    • Related Report
      2006 Annual Research Report

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Published: 2006-04-01   Modified: 2016-04-21  

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