Contemporary Mass Spectrometry and the Analysis of Synthetic Polymers: Trends, Techniques and Untapped Potential

Abstract

For many decades, the capacity for mass spectrometry (MS) to analyse matter in all of its forms was shackled by an inability to ionise large molecules into the gas phase. It was only in the late 1980s, when the capabilities of the ‘soft’ ionisation protocols of matrix‐assisted laser desorption/ionisation (MALDI) and electrospray ionisation (ESI) became apparent, that these shackles were effectively removed. The emergence of soft ionisation methodologies acted as a driving force for significant advances in MS instrumentation; as a result, MS now represents one of the most potent means by which insights into the structural details of synthetic polymer samples can be obtained. However, despite MS being acknowledged to be a mainstream analytical tool in the field of polymer chemistry, the number of MS‐based studies into polymer systems remains significantly limited when compared to other analytical methods, and it would thus appear that MS is still being severely underutilised. In this Trend article, important fundamental concepts of soft ionisation MS are presented in a tutorial style fashion within the context of the analysis of polymer systems, and the remarkable breadth, power and versatility of these techniques is illustrated using selected examples. We suggest that MS‐based analyses represent one of the most promising areas of research in polymer science, and that the polymer chemistry community would be well served by utilising this analytical discipline in a more intensive manner.magnified image

Elucidation of Reaction Mechanisms: Conventional Radical Polymerization

“…Hart-Smith and Barner-Kowollik recently opined that MS remains of untapped potential in the polymer field [2]. They are correct!…”

“…However, it may be anticipated that improving MS technology will overcome this problem [2]. This is especially so with regard to determination of transfer constants, but also applies for the seemingly simpler task of identifying transfer reactions that occur.…”

Makromolekulare Chemie 2010

“…Die matrixunterstützte Laser‐Desorption‐Ionisation‐Massenspektrometrie gewinnt in der Polymeranalytik weiter an Bedeutung und wird allmählich zu einer Standardmethode wie die Gelpermeationschromatographie. Hart‐Smith und Barner‐Kowollik umrissen in einem Übersichtsartikel diesen Trend und zeigen das noch ungenutzte Potenzial 17.…”

A Snapshot of Thermo‐Oxidative Degradation Products in Poly(bisphenol A carbonate) by Electrospray Ionization Mass Spectrometry and Matrix‐Assisted Laser Desorption Ionization Time of Flight Mass Spectrometry

“…Therefore, new, simple, and fast, analytical methods to identify low molecular weight compounds are welcome. Soft ionization mass spectrometry (MS) techniques such as matrix‐assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) have numerous advantages for analyzing several classes of compounds even in complex mixtures, including high sensitivity, selectivity, and speed 5–7. ESI is the primary ion source for today's liquid chromatography–mass spectrometry (LC‐MS) instruments due to its easy online coupling with LC8–13 allowing the quantitative analysis.…”