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Chemical Processes Involving 18-Crown-6-Ether in Activated Noncovalent Complexes with Protonated Peptides
Authors:Dr Marwa Abdelmouleh  Dr Mathieu Lalande  Edith Nicol  Dr Gilles Frison  Prof?Dr Guillaume van der Rest  Dr Jean-Christophe Poully
Institution:1. CIMAP UMR 6252, CEA/CNRS/ENSICAEN/Université de Caen Normandie, Bd Becquerel, 14070 Caen, France;2. Laboratoire de Chimie Moléculaire, Ecole Polytech, Inst Polytech Paris, CNRS, 91128 Palaiseau, France;3. Laboratoire de Chimie Moléculaire, Ecole Polytech, Inst Polytech Paris, CNRS, 91128 Palaiseau, France

Laboratoire de Chimie Théorique, Sorbonne Université and CNRS, 75005 Paris, France;4. Institut de Chimie Physique, Université Paris Saclay, CNRS, Bâtiment 349, 91405 Orsay, France

Abstract:These last decades, it has been widely assumed that 18-crown-6-ether (CE) plays a spectator role during the chemical processes occurring in isolated host-guest complexes between peptides or proteins and CE after activation in mass spectrometers. Our present experimental and theoretical results challenge this hypothesis by showing that CE can abstract a proton or a protonated molecule from protonated peptides after activation by collisions in argon or electron capture/transfer. Furthermore, thanks to comparison between experimental and calculated values of collision cross-sections, we demonstrate that CE can change binding site after electron transfer. We also propose detailed mechanisms for these processes.
Keywords:18-crown-6-ether  peptides  mass spectrometry  ion mobility spectrometry  electron transfer/capture
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