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CHARACTERIZATION OF POLYMER ARCHITECTURES AND SEQUENCES BY MULTI-STAGE MASS SPECTROMETRY

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2019, Doctor of Philosophy, University of Akron, Chemistry.
This dissertation focuses on the characterization of polymer architectures and sequences by tandem and multi-stage mass spectrometry (MS2 and MSn) as well as ion mobility mass spectrometry (IM-MS). The experiments described in this dissertation utilized matrix-assisted laser desorption ionization (MALDI) and electrospray ionization (ESI) as ionization techniques and collisionally activated dissociation (CAD), electron transfer dissociation (ETD), and laser-induced fragmentation (LIFT) as ion activation and dissociation techniques. Polymers studied include an 8-shaped polystyrene, star-branched polyethers, monodisperse sequence-defined POSS-functionalized polyesters, and poly(t-butyl methacrylate). A well-defined 8‑shaped polystyrene was characterized by MALDI-MS, MALDI-MS2, and IM-MS. 8-shaped polymers could have inter and intra isomers which cannot be distinguished by single stage mass spectrometry. MALDI-MS2 of 8‑shaped polystyrene showed specific fragment species that can only be produced by the inter isomer, thus confirming the existence of the inter isomer. The degree of branching and the length of individual branches of a set of mikto- and homo-arm star polyethers were studied by MALDI-MS2 and ESI-MS2. The number of fragment distributions combined with the mass to charge ratios of the fragment ions gave conclusive evidence for the number of branches in the star polyethers and the corresponding branch lengths. A set of monodisperse, sequence-defined, and POSS-functionalized polyester copolymers were analyzed by MALDI-MS2. Isomeric oligomers with different sequences were readily distinguished by their different fragmentation patterns. Oligomers up to hexamers were successfully sequenced based on the specific backbone fragment species observed. The backbone connectivity of poly(t-butyl methacrylate) (PtBMA) was investigated by tandem and multistage mass spectrometry. The results showed that ETD-MS2 and ETD-CAD-MS3 enable backbone C-C bond cleavages and, thus, provides the chain connectivity information needed to characterize end groups and acrylate (co)polymer sequences. The studies presented in this dissertation emphasize the capability of mass spectrometry as a powerful technique for the characterization of architectures and sequences of a variety of synthetic polymers.
Chrys Wesdemiotis (Advisor)
Wiley Youngs (Committee Member)
Adam Smith (Committee Member)
Aliaksei Boika (Committee Member)
Toshikazu Miyoshi (Committee Member)
170 p.

Recommended Citations

Citations

  • Mao, J. (2019). CHARACTERIZATION OF POLYMER ARCHITECTURES AND SEQUENCES BY MULTI-STAGE MASS SPECTROMETRY [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1554913939030297

    APA Style (7th edition)

  • Mao, Jialin. CHARACTERIZATION OF POLYMER ARCHITECTURES AND SEQUENCES BY MULTI-STAGE MASS SPECTROMETRY. 2019. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1554913939030297.

    MLA Style (8th edition)

  • Mao, Jialin. "CHARACTERIZATION OF POLYMER ARCHITECTURES AND SEQUENCES BY MULTI-STAGE MASS SPECTROMETRY." Doctoral dissertation, University of Akron, 2019. http://rave.ohiolink.edu/etdc/view?acc_num=akron1554913939030297

    Chicago Manual of Style (17th edition)