The Kendrick analysis for polymer mass spectrometry

• Published in: Journal of mass spectrometry. 2019-12, Vol.54 (12), p.933-947
• Main Author: Fouquet, Thierry N.J.
• Format: Article
• Language: English
• Subjects: Adducts; Analysis; Contaminants; Data analysis; Data processing; Filtration; Ions; Lipids; Mass spectra; Mass spectrometry; Mass spectroscopy; Oils & fats; Pollutants; Polymers; Termination (polymerization)
• ISSN: 1076-5174; 1096-9888
• DOI: 10.1002/jms.4480

The mass spectrum of a polymer often displays repetitive patterns with peak series spaced by the repeating unit(s) of the polymeric backbones, sometimes complexified with different adducts, chain terminations, or charge states. Exploring the complex mass spectral data or filtering the unwanted signal is tedious whether performed manually or automatically. In contrast, the now 60‐year‐old Kendrick (mass defect) analysis, when adapted to polymer ions, produces visual two‐dimensional maps with intuitive alignments of the repetitive patterns and favourable deconvolution of features overlaid in the one‐dimensional mass spectrum. This special feature article reports on an up‐to‐date and theoretically sound use of Kendrick plots as a data processing tool. The approach requires no prior knowledge of the sample but offers promising dynamic capabilities for visualizing, filtering, and sometimes assigning congested mass spectra. Examples of applications of the approach to polymers are discussed throughout the text, but the same tools can be readily extended to other applications, including the analysis of polymers present as pollutants/contaminants, and to other analytes incorporating a repetitive moiety, for example, oils or lipids. In each of these instances, data processing can benefit from the application of an updated and interactive Kendrick analysis.