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Matrix-assisted Laser Desorption/Ionization Mass Spectrometry of Polymers

Polymers and Rubbers

  1. Harald Pasch1,
  2. Nare Alpheus Mautjana2

Published Online: 15 MAR 2011

DOI: 10.1002/9780470027318.a9223

Encyclopedia of Analytical Chemistry

Encyclopedia of Analytical Chemistry

How to Cite

Pasch, H. and Alpheus Mautjana, N. 2011. Matrix-assisted Laser Desorption/Ionization Mass Spectrometry of Polymers. Encyclopedia of Analytical Chemistry. .

Author Information

  1. 1

    University of Stellenbosch, SASOL Chair of Analytical Polymer Science, Department of Chemistry and Polymer Science, Matieland, South Africa

  2. 2

    University of Stellenbosch, Department of Chemistry and Polymer Science, Matieland, South Africa

Publication History

  1. Published Online: 15 MAR 2011

Abstract

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) has proved to be one of the best methods for identification and determination of the number of monomer units of simple polymers, including their end-groups. However, most man-made polymers are complex materials with numerous macromolecules (oligomers) of different chain lengths and different chemical compositions in one sample. Since MALDI MS primarily produces singly charged ions of each molecule in the sample, its mass spectra are easy to interpret and therefore useful for polymer characterization. Different oligomers of interesting polymers can be isolated in tandem mass spectrometry (MS/MS) for analysis of their monomer sequence to relate properties of the polymer to its molecular structure. Furthermore, the polymerization mechanism responsible for a given polymer can often be deduced from the oligomer structure. MALDI MS-based methods have been used for the determination of molar mass distributions of complex polymers. However, to obtain meaningful data, proper understanding of polymer complexity as well as good insight of MALDI MS instrumentation and sample preparation protocol is necessary. Since the introduction of MALDI, different types of mass analyzers have been used. Each type has its advantages while other mass analyzers are simply not suitable for MALDI or for the targeted mass range.