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Matrix-assisted and polymer-assisted laser desorption/ionization time-of-flight mass spectrometric analysis of low molecular weight polystyrenes and polyethylene glycols
KTH, Superseded Departments, Chemistry.
2004 (English)In: Rapid Communications in Mass Spectrometry, ISSN 0951-4198, E-ISSN 1097-0231, Vol. 18, no 23, 2904-2912 p.Article in journal (Refereed) Published
Abstract [en]

Recently, matrices based on oligomers of dioxin and thiophene (polymer-assisted laser desorption/ionization (PALDI) have been described for mass spectrometric (MS) analysis of low molecular weight compounds (Woldegiorgis A, von Kieseritzky F, Dahlstedt E, Hellberg J, Brinck T, Roeraade J. Rapid Commun. Mass Spectrom. 2004; 18: 841-852). In this paper, we report the use of PALDI matrices for low molecular weight polymers. An evaluation with polystyrene and polyethylene glycol showed that no charge transfer ionization occurs. Ionization is mediated through metal ion adduction. Comparison of matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF) data for two very low molecular weight polymers with data obtained from size-exclusion chromatography (SEC) revealed a systematic difference regarding mean molecular weight and dispersity. Further, the mass spectra obtained with PALDI matrices had a higher signal-to-noise ratio than the spectra obtained with conventional matrices. For polymers with higher molecular weights (>1500 Da), the conventional matrices gave better performance. For evaluation of the MALDI spectra, three non-linear mathematical models were evaluated to model the cumulative distributions of the different oligomers and their maximal values of M-w, M-n and PDI. Models based on sigmoidal or Boltzmann equations proved to be most suitable. Objective modeling tools are necessary to compare different sample and instrumental conditions during method optimization of MALDI analysis of polymers, since the bias between MALDI and SEC data can be misleading.

Place, publisher, year, edition, pages
2004. Vol. 18, no 23, 2904-2912 p.
Keyword [en]
size-exclusion chromatography, polydisperse polymers, desorption ionization, universal calibration, synthetic-polymers, delayed extraction, metal-ions, gas-phase, maldi, discrimination
URN: urn:nbn:se:kth:diva-23930DOI: 10.1002/rcm.1707ISI: 000225489200017ScopusID: 2-s2.0-9644287951OAI: diva2:342629
QC 20100525Available from: 2010-08-10 Created: 2010-08-10Bibliographically approved

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