Polyether based side-chain liquid crystalline (SCLC) copolymers with distinct microstructures were prepared using living anionic polymerization techniques. The composition, end groups, purity, and sequence of the resulting copolymers were elucidated by matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) and tandem mass spectrometry (MS/MS). MALDI-MS analysis confirmed the presence of (CH3)3CO– and –H end groups at the initiating (α) and terminating (ω) chain end, respectively, and allowed determination of the molecular weight distribution and comonomer content of the copolymers. The comonomer positions along the polymer chain were identified by MS/MS, from the fragments formed via C–O and C–C bond cleavages in the polyether backbone. Random and block architectures could readily be distinguished by the contiguous fragment series formed in these reactions. Notably, backbone C–C bond scission was promoted by a radical formed via initial C–O bond cleavage in the mesogenic side chain. This result documents the ability of a properly substituted side chain to induce sequence indicative bond cleavages in the polyether backbone.
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Elucidating Branching Topology and Branch Lengths in Star-Branched Polymers by Tandem Mass Spectrometry
Tandem mass spectrometry (MS2) has been employed to elucidate the topology and branching architecture of star-branched polyethers. The polymers were ionized by matrix-assisted laser desorption/ionization (MALDI) to positive ions and dissociated after leaving the ion source via laser-induced fragmentation. The bond scissions caused under MALDI-MS2 conditions occur preferentially near the core-branch joining points due to energetically favorable homolytic and heterolytic bond cleavages near the core and release of steric strain and/or reduction of crowding. This unique fragmentation mode detaches complete arms from the core generating fragment ion series at the expected molecular weight of each branch. The number of fragment ion distributions observed combined with their mass-to-charge ratios permit conclusive determination of the degree of branching and the corresponding branch lengths, as demonstrated for differently branched homo- and mikto-arm polyether stars synthesized via azide-alkyne click chemistry. The results of this study underscore the utility of MS2 for the characterization of branching architecture and branch lengths of (co)polymers with two or more linear chains attached to a functionalized central core.
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- Award ID(s):
- 1808115
- NSF-PAR ID:
- 10112245
- Date Published:
- Journal Name:
- Journal of The American Society for Mass Spectrometry
- ISSN:
- 1044-0305
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Rationale The electrostatic linear ion trap (ELIT) can be operated as a multi‐reflection time‐of‐flight (MR‐TOF) or Fourier transform (FT) mass analyzer. It has been shown to be capable of performing high‐resolution mass analysis and high‐resolution ion isolations. Although it has been used in charge‐detection mass spectrometry (CDMS), it has not been widely used as a conventional mass spectrometer for ensemble measurements of ions, or for tandem mass spectrometer. The advantages of tandem mass spectrometer with high‐resolution ion isolations in the ELIT have thus not been fully exploited.
Methods A homebuilt ELIT was modified with BaF2viewports to facilitate transmission of a laser beam at the turnaround point of the second ion mirror in the ELIT. Fragmentation that occurs at the turnaround point of these ion mirrors should result in minimal energy partitioning due to the low kinetic energy of ions at these points. The laser was allowed to irradiate ions for a period of many oscillations in the ELIT.
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1007/s13361-019-02260-0
