Sequence distribution determination by SWAMP‐MS a systematic way of analyzing multiple fragmented polymers with mass spectrometry

Abstract

A new method to determine the blockiness and especially the block length distribution (BLD) of copolymers is described. This Systematic Workflow to Analyze Multi-fragmented Polymers with Mass Spectrometry (SWAMP-MS) is developed to characterize the sequence distribution of synthetic polymers.Copolymerization of polyamide 4,6 and polyamide 4,10 is used as a model system. Supercharged polymer ions, generated by electrospray ionization, swamp the mass spectrum due to <1> different chemical related distributions (chain composition, end groups), <2> the number of repeating units, <3> the charge and adduct distribution, and <4> isotopes distribution. Without selecting specific substrate ions, MSMS will transform this total ion-SWAMP into chemical rich information of the polymer backbone. The generated fragments contain up to 20 monomers. The reduction of blockiness is evaluated by the decreasing abundancy of specific ions originating from the starting polymers. Moreover, evaluation of all significant fragments and applying Monte Carlo simulations can rebuild the polymer backbone and generate sequence distributions of the copolymerized samples, which is currently still a holy grail in co-chemical polymer analysis.

Sample transformation in online separations: how chemical conversion advances analytical technology

“…Mengerink et al demonstrated multiple fragmentation in the MS to study BLD of polyamide copolymers. 114 The sample was first subjected to an LC separation and subsequently transformed ( i.e. fragmented) by MS/MS to identify co-oligomeric fragments.…”