“…Depending on the type of monomers and synthetic approach used, sequences with block, tapered, alternate, or random architecture may be formed . The analysis of such materials by mass spectrometry (MS) presents significant challenges, as the molecular weight and end group distributions are convoluted by comonomer content distributions. , With soft ionization techniques, in particular matrix-assisted laser desorption ionization (MALDI) , and electrospray ionization (ESI), and a reasonable mass accuracy (<100 ppm), single-stage MS can provide information about end groups, byproducts, and comonomer composition, , but insight on the sequence(s) produced is difficult to extract from such spectra, requiring elaborate modeling of the observed ion intensities by statistical methods, which is feasible for low molecular weight chains only. − More definitive sequence information can be obtained by tandem mass spectrometry (MS 2 ) analysis of specific oligomers. MS 2 has been applied to differentiate block from random copolymers − and to confirm the presence of random comonomer arrangements in short polyester and poly(ester amide) oligomers. − In this study, MALDI is combined with MS and MS 2 to examine the copolymer distributions, architectures, and sequences generated by living anionic polymerization of styrenic monomers.…”