MALDI-LID-ToF/ToF analysis of statistical and diblock polyacrylate copolymers

We report the use of MALDI-LID-ToF/ToF utilising the laser induced dissociation (LID) fragmentation technique, which has been almost exclusively applied to protein/peptide analysis to date. MALDI-LID-ToF/ToF is used as a powerful tool to give information of monomer distributions in synthetic co-poly(acrylates). Analysis of a range of poly(acrylate) homopolymers by LID have found slight improvement over CID, with less rearrangements in the poly(butyl acrylate) fragmentation and more backbone cleavages. Analysis of both block and statistical copolymers, when compared to homopolymer analogues, yield markedly different spectra which can be correlated to give some monomer sequence information, thus achieving a wealth of structural information from two samples which would otherwise be identical by single stage MALDI-ToF analysis. The determination of fragmentation pathways of polymers with varying end group lability and monomer structure has allowed for high-resolution microstructural determination at the block boundary, showing even small amounts of mixing at the block boundary.