Protonating polymer oligomers in the gas phase to change fragmentation pathways

Ionization of polymers in mass spectrometry is usually achieved by forming metal ion adducts. The metal ion has been shown by Wesdemiotis to often play a spectator role in the collision-induced dissociation (CID) chemistry of these species, wherein they fragment according to a free-radical mechanism similar to that found in their pyrolysis. The result is a predominance of low-mass ions in the CID mass spectrum. We have changed this behavior by generating protonated oligomers in the gas phase by first forming proton-bound complexes of the oligomers with amino acids or peptides by electrospray ionization. These complexes dissociate first by loss of the amino acid/peptide to form protonated oligomers, which then undergo a unique fragmentation chemistry. In this article we discuss the results for poly(methyl methacrylate) (PMMA) and poly(butyl acrylate) (PBA). Initially, protonated PMMA and PBA lose methanol and butanol, respectively, from the side chains of the respective monomers. The resulting PMMA-derived ion then undergoes a series of neutral losses corresponding to 32 and 28 Da, methanol and carbon monoxide. This continues as collision energy increases until a final, carbon-rich backbone ion is formed, which then undergoes a classic hydrocarbon fragmentation pattern. The PBA-derived ions are proposed to fragment by the loss of butylether molecules to form anhydride rings along the oligomer chain. The number of ether molecules lost corresponded to half the number of available side chains in the oligomer. The resulting poly-anhydride ion dissociates by small molecule loss. Mechanisms have been suggested for the fragmentation chemistry of these two classes of oligomers.