Abundance correction for mass discrimination effects in polymer mass spectra.

RATIONALE

Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is frequently used to analyze homo- and copolymers, i.e. for computing copolymer fingerprints. However, the oligomer abundances are influenced by mass discrimination, i.e. mass- and composition-dependent ionization. We have developed a computational method to correct the abundance bias caused by the mass discrimination.

METHODS

MALDI-TOFMS in combination with computational methods was used to investigate three random copolymers with different ratios of styrene and isoprene. Furthermore, equimolar high- and low-mass styrene and isoprene homopolymers (2500 and 4200 Da) were mixed and also analyzed by MALDI-TOFMS. The abundances of both copolymers and homopolymers were corrected for mass discrimination effects with our new method.

RESULTS

The novel computational method was integrated into the existing COCONUT software. The method was demonstrated using the measured styrene and isoprene co- and homopolymers. First, the method was applied to homopolymer spectra. Subsequently, the copolymer fingerprint was computed from the copolymer MALDI mass spectra and the correcting function applied. The changes in the composition are plausible, indicating that correction of copolymer abundances was reasonable.

CONCLUSIONS

Our computational method may help to avoid erroneous conclusions when analyzing copolymer MS spectra. The software is freely available and represents a step towards comprehensive computational support in polymer science. Copyright © 2016 John Wiley & Sons, Ltd.