Mass spectrometry of polymers: A tutorial review

Abstract

Ever since the inception of synthetic polymeric materials in the late 19th century, the number of studies on polymers as well as the complexity of their structures have only increased. The development and commercialization of new polymers with properties fine‐tuned for specific technological, environmental, consumer, or biomedical applications requires powerful analytical techniques that permit the in‐depth characterization of these materials. One such method with the ability to provide chemical composition and structure information with high sensitivity, selectivity, specificity, and speed is mass spectrometry (MS). This tutorial review presents and exemplifies the various MS techniques available for the elucidation of specific structural features in a synthetic polymer, including compositional complexity, primary structure, architecture, topology, and surface properties. Key to every MS analysis is sample conversion to gas‐phase ions. This review describes the fundamentals of the most suitable ionization methods for synthetic materials and provides relevant sample preparation protocols. Most importantly, structural characterizations via one‐step as well as hyphenated or multidimensional approaches are introduced and demonstrated with specific applications, including surface sensitive and imaging techniques. The aim of this tutorial review is to illustrate the capabilities of MS for the characterization of large, complex polymers and emphasize its potential as a powerful compositional and structural elucidation tool in polymer chemistry.

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“…The use of mass spectrometry methods for supramolecular complexes ,− and polymers ,− has been regularly reviewed, however usually from the perspective of mass spectrometrists with a particular interest in these systems. Here, we focus on recent developments and their implications for synthetic chemists, highlighting the opportunities of IM as an analytical tool of the future.…”

Ion Mobility Mass Spectrometry for Synthetic Molecules: Expanding the Analytical Toolbox

“…The use of mass spectrometry methods for supramolecular complexes 2,[14][15][16][17][18][19] and polymers 14,[20][21][22] has been regularly reviewed, however usually from the perspective of mass spectrometrists with a particular interest in these systems. Here, we focus on recent developments and their implications for synthetic chemists, particularly highlighting the opportunities of ion mobility as an analytical tool of the future.…”