Combination of time-of-flight mass analysers with magnetic-sector instruments: in-line and perpendicular arrangements. Applications to poly(ethylene glycol) with long-chain end groups

High-energy collision-induced dissociation has been shown to provide extensive and detailed structural information on poly(ethylene glycol) with palmitoyl end-groups, Fragmentation within the end-groups provides direct information on their structures. Both in-line time-of-flight (TOF) and orthogonal TOF have been used for the measurement of fragment ions. Use of TOF as the second stage of mass spectrometry has facilitated exploitation of the pulsed method of ionisation matrix-assisted laser desorption/ionisation (MALDI). The orthogonal TOF instrument is used with a liquid secondary-ion mass spectrometry source. The laboratory-frame collision energies were different for in-line and orthogonal TOF, being 8-12 keV in the former and 800 eV in the latter. The tandem mass spectra were similar for the in-line experiment with either He or Xe collision gas and the orthogonal experiment with Xe, Mechanisms proposed for the fragmentations involve homolytic cleavage (C-H and backbone bonds) and invoke non-ergodicity.