Abundance correction for mass discrimination effects in polymer mass spectra

Area of Science:

• Polymer Chemistry
• Analytical Chemistry
• Computational Chemistry

Background:

• Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) is widely used for analyzing polymer composition.
• Oligomer abundances in MALDI-TOFMS data can be skewed by mass discrimination, affecting ionization efficiency based on mass and composition.
• Accurate determination of copolymer composition is crucial for understanding material properties.

Purpose of the Study:

• To develop and validate a computational method for correcting mass discrimination in MALDI-TOFMS analysis of copolymers.
• To improve the accuracy of copolymer fingerprints derived from mass spectrometry data.
• To provide enhanced computational tools for polymer characterization.

Main Methods:

• MALDI-TOFMS was employed to analyze random copolymers of styrene and isoprene, as well as mixtures of homopolymers.
• A novel computational method was developed to correct for mass- and composition-dependent ionization biases.
• The correction method was integrated into the COCONUT software and applied to experimental data.

Main Results:

• The computational method successfully corrected abundance biases in both copolymer and homopolymer MALDI-TOFMS spectra.
• Application of the correction method to copolymer spectra yielded plausible changes in composition.
• The corrected copolymer fingerprints provided a more accurate representation of the polymer mixtures.

Conclusions:

• The developed computational method effectively addresses mass discrimination in MALDI-TOFMS polymer analysis.
• This advancement helps prevent erroneous interpretations of copolymer mass spectra.
• The freely available software enhances computational support in polymer science research.