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Keywords:

  • matrix-assisted laser desorption/ionisation mass spectrometry (MALDI-MS);
  • nitroxide;
  • polystyrene;
  • radical polymerisation

Abstract

Summary: A suitable method to synthesize well defined polymers with different architectures is the application of functionalized alkoxyamines in the controlled radical polymerization. The analysis of such nitroxide capped polymers by MALDI- TOF-MS is complex. Unexpected results of the mass analysis of our polymers lead us to study the influence of the structure of the analyte and the experimental conditions of the measurements in detail. In addition to common nitroxides like TEMPO, TEMPO-derivates, TIPNO and BIPNO, other alkoxyamines with special structure requirements were synthesized. These alkoxyamines were tested in different MALDI experiments. Supported by a comparison with other methods we postulate a fragmentation mechanism inside the nitroxide-group which takes place during the MALDI measurement. To the best of our knowledge such a fragmentation of the nitroxide-group itself during a MALDI-TOF experiment has not been described before.