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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Gidden, J., Bowers, M.T., Jackson, A.T. et al. Gas-phase conformations of cationized poly(styrene) oligomers. J Am Soc Mass Spectrom 13, 499–505 (2002). https://doi.org/10.1016/S1044-0305(02)00367-7
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DOI: https://doi.org/10.1016/S1044-0305(02)00367-7