Gas-phase conformations of cationized poly(styrene) oligomers

  • Jennifer Gidden
  • Michael T. Bowers
  • Anthony T. Jackson
  • James H. Scrivens
Focus: Ion Thermochemistry

Abstract

The gas-phase conformations of poly(styrene) oligomers cationized by Li+, Na+, Cu+, and Ag+ (M+PSn) were examined using ion mobility experiments and molecular mechanics/dynamics calculations. M+PSn ions were formed by MALDI and their ion-He collision cross-sections were measured by ion mobility methods. The experimental collision cross-sections of each M+PS n-mer were similar for all four metal cations and increased linearly with n. Molecular modeling of selected M+PS oligomers cationized by Li+ and Na+ yielded quasi-linear structures with the metal cation sandwiched between two phenyl groups. The relative energies of the structures were ∼2–3 kcal/mol more stable when the metal cation was sandwiched near the middle of the oligomer chain than when it was near the ends of the oligomer. The cross-sections of these theoretical structures agree well with the experimental values with deviations typically around 1–2%. The calculations also show that the metal cation tends to align the phenyl groups on the same side of the -CH2-CH- backbone. Calculations on neutral poly(styrene), on the other hand, showed structures in which the phenyl groups were more randomly positioned about the oligomer backbone. The conformations and metal-oligomer binding energies of M+PS are also used to help explain CID product distributions and fragmentation mechanisms of cationized PS oligomers.

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Copyright information

© American Society for Mass Spectrometry 2002

Authors and Affiliations

  • Jennifer Gidden
    • 1
  • Michael T. Bowers
    • 1
  • Anthony T. Jackson
    • 2
  • James H. Scrivens
    • 2
  1. 1.Department of Chemistry & BiochemistryUniversity of CaliforniaSanta BarbaraUSA
  2. 2.ICI Research and Technology Centre, WiltonMiddlesbroughUK

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