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Processus intrinsèques radio-induits dans des complexes non-covalents d'intérêt biologique et pharmaceutique

Abstract : Non-covalent bonds play a crucial role in many processes involving molecular systems of biological and pharmaceutical interest, in particular in molecular recognition between a ligand and its receptor. However, their response upon ionizing radiation has scarcely been investigated for understanding radio induced processes. In the first part of this thesis, we present results of photo-absorption experiments of non-covalent complexes containing the vancomycin antibiotic, carried out by means of a mass spectrometer coupled to synchrotron beamlines producing photons in the X and VUV energy range. First, we show that the fragmentation of molecular systems after absorption of one VUV photon is partly correlated with the geometrical structure of the complex. In addition, the processes induced strongly depend on the charge state of the vancomycin/receptor complexes (protonated or deprotonated). For the protonated complex, the cleavage of non-covalent bonds is much more probable than for the deprotonated complex, in which the native interactions are conserved in the gas phase. Moreover, the absorption of one X-Ray photon by vancomycin leads to fragments that can be considered as a spectral signature of its post-translational modifications. This signature is robust not only in terms of photon energy but also of the molecular environment of vancomycin. The second part deals with the study of a protonated tri-peptid in the gas phase by mass and ion mobility spectrometry, and more particularly the effects of nano-solvation by the presence of one or more molecules of crown-ether. We are interested in the fragmentation induced by collision with a rare gas, or by electron transfer or capture, and we have shown that crown ether is not always spectator since it can lower the charge state of protonated peptides by abstracting a proton or a protonated molecule from it, and can even change binding site after electron transfer.
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  • HAL Id : tel-03124892, version 1

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Marwa Abdelmouleh. Processus intrinsèques radio-induits dans des complexes non-covalents d'intérêt biologique et pharmaceutique. Physique [physics]. Normandie Université, 2020. Français. ⟨NNT : 2020NORMC219⟩. ⟨tel-03124892⟩

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