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Interfacing Liquid Chromatography or Ion Mobility Separation with Mult-Dimensional Mass Spectrometry for the Structural Characterization of Polymeric Materials

Katzenmeyer, Bryan C.
http://rave.ohiolink.edu/etdc/view?acc_num=akron1367252830

Abstract Details

2013, Doctor of Philosophy, University of Akron, Chemistry.
This dissertation focuses on utilizing mass spectrometry (MS) and tandem mass spectrometry (MS/MS), combined with the coupling of liquid chromatography (LC) and/or ion mobility (IM) spectrometry, to characterize polymeric materials. Chapter II will introduce history and basic principles of mass spectrometry and liquid chromatography including background on instrumentation and theory. Chapter III will discuss the materials and instrumentation used in the various projects. Chapters IV-VII are research project chapters as described below. Lastly, Chapter VIII concludes this dissertation with a summary. Following the last chapter are appendices with supplemental data and copyright permissions for this dissertation. Chapter IV details the characterization of two nonionic surfactants consisting of a methoxylated glucose core (glucam) that was either chain-extended with ethylene oxide and then esterified with stearic acid to generate poly(ethylene oxide) glucam stearate(s) or only esterified with stearic acid which made glucam stearate(s). The use of LC-MS, LC-MS/MS, IM-MS, and MS/MS made it possible to separate and determine the compositions for each component in the mixtures resulting from the synthesis of these amphiphilic polymers. Components of (PEO)n-glucam stearate(s) were readily separated by their hydrophobicity and degrees of esterification by LC-MS and IM-MS. Each method offers complementary information, with LC-MS excelling in the separation and characterization of highly hydrophobic amphiphilles and IM-MS provides a quicker analysis of minor trace components. Electron transfer dissociation (ETD) was also applied as a novel MS/MS application to poly(ethylene oxide) glucam stearate(s). However, when compared to traditional MS/MS activation techniques (collisionally activated dissociation (CAD)), ETD unveiled no significant structural information when compared to CAD activation of the same oligomer. Specifically, ETD caused no unique cleavages across the sugar core as seen in oligosaccharide systems. In Chapter V, several homopolymers of poly(dimethylsiloxane) (PDMS) with different polymer end groups were studied by MS/MS. Detailed CAD mass spectra of PDMS homopolymers containing α, ω-bis(hydroxyl)-, α, ω-bis(3-aminopropyl)-, and α, ω-bis(ethoxy)- end groups are reported herein. MS/MS spectra indicate that charge-remote intramolecular rearrangements, H-atom abstraction, and intramolecular nucelophilic substitutions give rise to the fragments seen from the PDMS polymers studied. PDMS end groups are found to significantly influence the fragmentation pathways of energetically excited precursor ions from these type of polymers. Chapter VI of this dissertation discusses the MS and MS/MS characterization of several poly(phosphazene)s. Higher order cyclic poly(dichlorophosphazene)s and poly(bis(phenoxy)phosphazene) were analyzed. The MS/MS fragmentation pattern of poly(bis(phenoxy)phosphazene) indicated that this polymer had a tadpole architecture. Based on both the positive and negative ion MS/MS data, lateral chain fragmentation dominates in all cases and losses of bis(phenoxy)phosphazene are observed from oligomers having a tale larger than the trimer. Only in negative mode can the cyclic trimer ring open via charge-induced dissociation and expel one unit of bis(phenoxy)phosphazene. These data provide strong additional evidence that these polymers form a tadpole architecture. Lastly, in Chapter VII three polyesters were studied. Two homopolymers, poly(lactide) (PLA) and poly(glycolide) (PGA), and one copolymer, poly(lactide-co-glycolide) (PLGA). Oligomers of PLA undergo a series of 1,5-hydrogen rearrangement (1,5-rH) reactions. Whereas oligomers of PGA fragment via intramolecular transesterifications. The PLGA copolymer was found to contain cyclic and linear (with HO- and -H end groups) copolymers. Fragmentation proceeded via 1,5-rH reactions that opened the cyclic copolymer and intramolecular transesterifications. In the case of linear copolymers containing at least two glycolide units, the MS/MS spectra provide direct information on the block length of each monomer.
Chrys Wesdemiotis, Dr. (Advisor)
Claire Tessier, Dr. (Committee Member)
David Perry, Dr. (Committee Member)
Leah Shriver, Dr. (Committee Member)
Kevin Cavicchi, Dr. (Committee Member)
340 p.
Analytical Chemistry; Chemistry; Polymer Chemistry; Polymers
Mass spectrometry; tandem mass spectrometry; liquid chromatography; polymers

Recommended Citations

Citations

  • Katzenmeyer, B. C. (2013). Interfacing Liquid Chromatography or Ion Mobility Separation with Mult-Dimensional Mass Spectrometry for the Structural Characterization of Polymeric Materials [Doctoral dissertation, University of Akron]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=akron1367252830

    APA Style (7th edition)

  • Katzenmeyer, Bryan. Interfacing Liquid Chromatography or Ion Mobility Separation with Mult-Dimensional Mass Spectrometry for the Structural Characterization of Polymeric Materials. 2013. University of Akron, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=akron1367252830.

    MLA Style (8th edition)

  • Katzenmeyer, Bryan. "Interfacing Liquid Chromatography or Ion Mobility Separation with Mult-Dimensional Mass Spectrometry for the Structural Characterization of Polymeric Materials." Doctoral dissertation, University of Akron, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=akron1367252830

    Chicago Manual of Style (17th edition)

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This open access ETD is published by University of Akron and OhioLINK.