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Dynamique de photofragmentation de molécules d'intérêt biologique protonées

Abstract : The Arc-En-Ciel experiment allows the investigation of UV photo-fragmentation dynamics of protonated biomolecules produced by an electrospray ion source. The specificity of the set-up is based on the detection in coincidence of ionic and neutral photo-fragments coming from the same fragmentation event. The study of simple charged molecules allows the identification of each fragmentation channel by the mass of the emitted ionic fragment. With the time and spatial correlation of the information of detected photo-fragments we identify:- the number of neutral fragments as well as their masses associated with each ionic fragment- the number of fragmentation steps of each channel as well as their fragmentation times (20 ns ≤ τ < 1 μs)This information provides a comprehensive understanding of the photo-fragmentation dynamics.The photo-fragmentation dynamics of protonated Tryptophan is driven by concerted electron and proton transfers in the excited state. When protonated Tryptophan is complexed witha crown-ether, proton transfers are inhibited and dynamics is modified.The excited state dynamics of small protonated peptides containing Tryptophan is governed by the position of Tryptophan in the peptide chain. The specific fragmentation channels involved are explained by concerted electron and proton transfers. We show how these mechanisms change with the composition of peptides.
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Submitted on : Monday, February 6, 2012 - 4:23:17 PM
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Marie Perot Pérot-Taillandier. Dynamique de photofragmentation de molécules d'intérêt biologique protonées. Autre [cond-mat.other]. Université Paris Sud - Paris XI, 2011. Français. ⟨NNT : 2011PA112204⟩. ⟨tel-00667013⟩

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