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Structural characterization of poly(amino)ester dendrimers and related impurities by electrospray tandem mass spectrometry
Authors:Aura Tintaru  Valérie Monnier  Camille Bouillon  Rémi Giordanengo  Gilles Quéléver  Ling Peng  Laurence Charles
Affiliation:1. Universités Aix‐Marseille I, II & III – CNRS, UMR 6264: Laboratoire Chimie Provence, Spectrométries Appliquées à la Chimie Structurale, F‐13397 Marseille Cedex 20, France;2. Fédération des Sciences Chimiques, Spectropole, FR1739, Universités d'Aix‐Marseille I, II et III‐CNRS, Av. Escadrille Normandie‐Niemen, 13397 Marseille Cedex 20, France;3. Centre Interdisciplinaire de Nanosciences de Marseille, Université de la Méditerranée, Faculté des Sciences de Luminy, UPR CNRS 3118, 13288 Marseille Cedex 9, France
Abstract:An acid‐terminated poly(amino)ester dendrimer was studied by electrospray ionization tandem mass spectrometry to establish its fragmentation pathways, with the aim of using them to investigate the structure of any defective molecules generated during the dendrimer synthesis. This poly(amino)ester dendrimer could be ionized in both polarities but the most structurally relevant dissociation pathways were found from the deprotonated molecule in negative ion mode. The dissociation pattern of this dendrimer is fully described and supported by accurate mass measurements. The main dissociation reactions of the negatively charged polyacidic dendrimer were shown to consist of (i) the release of carbon dioxide and ethene within a branch, which proceeds as many times as intact neutral branches are available; and (ii) the elimination of an entire dendrimer arm. Monitoring the occurrence of these reactions together with any deviation from these two main routes allowed six major dendritic impurities to be structurally characterized. Copyright © 2010 John Wiley & Sons, Ltd.
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