Fourier transform data analysis for mass spectra of small polymers and pyrolysates with accurate-mass data and mass defect preprocessing.

Early applications of Fourier transform (FT) data analysis of polymer mass spectra made use of nominal-mass spectra to determine the monomer mass. More recently, FT data analysis has been applied to the interpretation of the unresolved envelope in complex electrospray ionization mass spectra of ionic polymers and macromolecules. Here, FT data analysis is applied to determine the monomer composition for isotopically resolved accurate-mass MALDI, pyrolysis DART, and PaperSpray mass spectra of synthetic homopolymers, copolymers, and polymer mixtures. Monomer compositions are determined from the transformed data by accurate mass search and elemental composition calculations. Data analysis is facilitated for complex mass spectra containing multiple polymers, multiple charge states, and nonperiodic fragments by graphically selecting individual series from mass defect plots.