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Development of Novel Polymeric Ionic Liquid Coatings for the Analysis of Genotoxic Impurities and Diverse Organic Compounds by Solid-Phase Microextraction

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2014, Doctor of Philosophy, University of Toledo, Chemistry.
For over a decade, solid-phase microextraction (SPME) has been exploited as a simple and effective pre-concentration technique for analytical applications. To further enhance the sensitivity of SPME for the analysis of target compounds, ionic liquids (ILs) and polymeric ionic liquids (PILs) have been applied as SPME sorbent coatings with considerable success. ILs are commonly known as organic salts with melting points at or below 100 ºC. On the other hand, PILs are polymers synthesized from IL monomers. These compounds exhibit numerous beneficial properties, including high thermal stability, wide viscosity ranges, negligible vapor pressures at ambient temperature, and capability to undergo different solvation interactions with target analytes. Overall, the ability to engineer and alter the physicochemical properties of ILs and PILs enable them to be excellent candidates for SPME. This dissertation begins with a brief discussion on the fundamentals of SPME. Unique characteristics of ILs and PILs, which influences their applicability as SPME sorbent coatings are mentioned. The application of ILs and PILs in SPME is also reviewed. The following chapters describe the development of novel PIL-based coatings and sorbent loading technology for the analysis of various target analytes. In the analysis of genotoxic impurities (GTIs), the poly(1-(4-vinylbenzyl)-3-hexadecylimidazolium bis[(trifluoromethyl)sulfonyl]imide) PIL showed good selectivity for analytes possessing aromatic functionalities, while PILs containing chloride anions exhibited superior selectivity for anilines. A UV-initiated on-fiber polymerization route was developed to increase the throughput of PIL-based fiber production and enable the incorporation of dicationic IL crosslinkers to the polymer network. The crosslinked PIL-based coatings demonstrated satisfactory analytical performance and good recovery of polar compounds in complex water matrices. The crosslinked PIL-based coatings were also engineered to exhibit superior analytical performance compared to a commercial poly(dimethylsiloxane) (PDMS) in the analysis of polychlorinated biphenyls. The extraction mechanism of both linear PILs and crosslinked PIL-based coatings were investigated, wherein non- competitive partitioning of analytes dominates. Nitinol wires were also exploited as the super elastic SPME fiber supports. A highly robust and versatile SPME system, possessing exceptional resistance to harsh matrix conditions, is produced when covalently bonding crosslinked PILs to the nitinol wire support. The last chapter of this dissertation describes the utilization of thermally stable ILs as diluents for the analysis of high-boiling point GTIs by headspace gas chromatography (HS-GC). Employing ILs enables the optimization of headspace temperature well-above common diluents used in HS-GC, such as dimethyl sulfoxide. This resulted in up to a 4000-fold enhancement for the detection limits of various GTIs.
Jared Anderson, Dr. (Committee Chair)
Steven Sucheck, Dr. (Committee Member)
Dragan Isailovic, Dr. (Committee Member)
Hermann Von Grafenstein, Dr. (Committee Member)
306 p.

Recommended Citations

Citations

  • Ho, T. D. (2014). Development of Novel Polymeric Ionic Liquid Coatings for the Analysis of Genotoxic Impurities and Diverse Organic Compounds by Solid-Phase Microextraction [Doctoral dissertation, University of Toledo]. OhioLINK Electronic Theses and Dissertations Center. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1402930219

    APA Style (7th edition)

  • Ho, Tien. Development of Novel Polymeric Ionic Liquid Coatings for the Analysis of Genotoxic Impurities and Diverse Organic Compounds by Solid-Phase Microextraction. 2014. University of Toledo, Doctoral dissertation. OhioLINK Electronic Theses and Dissertations Center, http://rave.ohiolink.edu/etdc/view?acc_num=toledo1402930219.

    MLA Style (8th edition)

  • Ho, Tien. "Development of Novel Polymeric Ionic Liquid Coatings for the Analysis of Genotoxic Impurities and Diverse Organic Compounds by Solid-Phase Microextraction." Doctoral dissertation, University of Toledo, 2014. http://rave.ohiolink.edu/etdc/view?acc_num=toledo1402930219

    Chicago Manual of Style (17th edition)