New Insights into the Vacuum UV Photodissociation of Peptides.

Vacuum ultraviolet laser photodissociation (UVPD) of peptide ions leads to unusual dissociation channels involving backbone C-C bond breaking. However, the molecular basis for the observed behavior is not clearly understood. We now report theoretical investigations using ab initio/density functional...

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Publicado en:Journal of the American Chemical Society Vol. 132; no. 5; pp. 1606 - 1611
Autores principales: Parthasarathi, Ramakrishnan, Yi He, Reilly, James P., Raghavachari, Krishnan
Formato: Artículo
Publicado: American Chemical Society 2/10/2010
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Acceso en línea:Ver este registro en EBSCOhost
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        atl: New Insights into the Vacuum UV Photodissociation of Peptides.
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        au:
          Parthasarathi, Ramakrishnan
          Yi He
          Reilly, James P.
          Raghavachari, Krishnan
        affil: Department of Chemistry, Indiana University, Bloomington, Indiana 47405, USA
      su:
        Far ultraviolet radiation
        Peptides
        Photodissociation
        Density functionals
        Fragmentation reactions
      sug:
        subj:
          Far ultraviolet radiation
          Peptides
          Photodissociation
          Density functionals
          Fragmentation reactions
      ab: Vacuum ultraviolet laser photodissociation (UVPD) of peptide ions leads to unusual dissociation channels involving backbone C-C bond breaking. However, the molecular basis for the observed behavior is not clearly understood. We now report theoretical investigations using ab initio/density functional theory (DFT) techniques on neutral and protonated dipeptides undergoing vacuum ultraviolet (VUV) induced fragmentation via a Rydberg excitation (and/or electron detachment) and subsequent C-C bond cleavage. New experimental results on VUV photodissociation of dipeptides (protonated Ala̱Arg and Arg̱Ala) provide strong support for our proposed model. Our mechanism also provides a natural explanation for the presence of immonium ions that are sometimes observed in such experiments.
      pubtype: Academic Journal
      doctype: Article
      src: R
    language: English
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