Changes in post-source decay fragmentation behavior of poly(methyl methacrylate) polymers with increasing molecular weight studied by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry.

In order to investigate the systematic changes in fragmentation behavior of poly(methyl methacrylate) (PMMA) with increasing molecular weight, alkali-metal cationized PMMA 20-mer, 60-mer and 100-mer were selected for post-source decay (PSD) fragmentation study by matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry. PMMA polymers were cationized with lithium, potassium and cesium cations to explore the influence of the cation size on the fragmentation behavior of the polymers. All PMMA polymers could be fragmented by MALDI-PSD and fragmentation of the MALDI ionized synthetic polymer of molecular weight 10 kDa is reported here for the first time. It was shown that an increasing molecular weight of the PMMA chain required an increase in the size of the cation to improve the intensity and the number of the fragments in the PSD spectrum. Some instrumental parameters had to be optimized prior to a successful PSD analysis of the largest PMMA polymers.