ORCID Identifier(s)

0000-0003-1629-6873

Graduation Semester and Year

2021

Language

English

Document Type

Dissertation

Degree Name

Doctor of Philosophy in Chemistry

Department

Chemistry and Biochemistry

First Advisor

Kevin A Schug

Abstract

A systematic approach to the rapid development of hyphenated online methods for supercritical fluid extraction-supercritical fluid chromatography-mass spectrometry (SFE-SFC-MS) was established for the analysis of complex biological and environmental samples with limited sample sizes. Extensive sample preparation and cleanup is incompatible with small sample sizes. Hyphenated online extractions offer major advantages desirable where sample quantity is limited. By minimizing sample preparation and handling, online extractions provide higher throughput, and minimizes the opportunity for sample contamination or loss. However, hyphenated methods have been difficult to develop since each step has its own requirements, which has slowed penetration into many areas which it should be ideally suited. Recent instrument advances provide new opportunity in online extraction with hyphenated SFESFC-MS. The first step involved synergistically optimizing MS-detection, SFC-separation, and SFE-extraction. Reference materials and quality controls (QCs) were developed using two separate complex matrices: A micro-dried blood spot (DBS) coring technique for antidoping analysis, and microplastics (μPs) reference materials from cryomilled plastic pellets, for environmental pollutants polycyclic aromatic hydrocarbons (PAHs). A micro-DBS coring technique was established for the for anti-doping analysis was established for direct applicability to with application to androgenic anabolic steroids (AAS) to reflect method validity for evaluation of real/field samples, For DBS: methods were optimized in a stepwise process for the separation and extraction of androgenic anabolic steroids (AAS) were applied to micro-DBS made with human and bovine blood and final method optimizations were performed with focus for Anti-doping analysis. μP Field samples: Pre-optimized methods for the online extraction and separation of environmentally persistent organic pollutants (ePOPs) were applied to marine-exposed μPs and final method optimizations were performed with focus for the targeted analysis of PAHs. The goal was to contribute alternative solutions for blood-based anti-doping testing to current techniques and broaden the accessibility of online SFE-SFC to the scientific community.

Keywords

Supercritical fluid extraction (SFE), Supercritical fluid chromatography (SFC), Mass spectrometry (MS), SFE-SFC-MS, Online extractions, Microplastics, Environmental pollutants, Polycyclic aromatic hydrocarbons (PAHs), Anti-doping analysis, Anabolic agents, Androgenic anabolic steroids (AAS)

Disciplines

Chemistry | Physical Sciences and Mathematics

Comments

Degree granted by The University of Texas at Arlington

30020-2.zip (28879 kB)

Included in

Chemistry Commons

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