Multidimensional mass spectrometry methods for the structural characterization of cyclic polymers

Several synthetic methods have been developed for the tailored preparation of cyclic macromolecules due to their unique physical and chemical properties. Unequivocal characterization of the macrocyclic architectures has remained challenging, however, because isomeric linear structures often exist, or the spectral features of linear vs. cyclic chains are similar. To address this problem, multidimensional mass spectrometry (MS) techniques have been evaluated for the separation and identification of polymeric macrocycles. Tandem mass spectrometry (MS2) is found to be ideally suitable for the differentiation of linear and cyclic architectures whose molecular ions exhibit distinct fragmentation characteristics. Conversely, differences in macromolecular sizes and shapes can be exploited to identify the correct architecture by ion mobility mass spectrometry (IM-MS). A third option, chromatographic separation (LC) before MS analysis, is available for the detection of cyclics in complex mixtures. The capabilities of these techniques and combinations thereof are demonstrated with specific covalent or supramolecular (co)polymers. (C) 2014 Elsevier Ltd. All rights reserved.