Date of Award

January 2020

Degree Type

Open Access Thesis

Document Type

Master Thesis

Degree Name

Master of Science (MS)

Department

Chemistry

First Advisor

Karim M. Abdel-Hay

Department Affiliation

Chemistry

Second Advisor

Cindy Tran

Department Affiliation

Chemistry

Third Advisor

Radhika Dasari

Department Affiliation

Chemistry

Abstract

The use of SERMs (Selective Estrogen Receptor Modulators) – most notably the drug Tamoxifen – has significantly increased among athletes over the past decade to enhance athletic performance and/or negate certain side effects of using anabolic steroids. This “doping” is always banned by WADA (World Anti-Doping Agency) for all athletes, but SERMs can naturally increase testosterone production so they are a tempting alternative to using steroids or androgenic supplements that can cause significant health problems (e.g. acne, breast development, frequent urge to urinate, low libido, etc.). Similarly, the use of AIs (Aromatase Inhibitors) has also increased among athletes for identical reasons, and they are also banned by WADA within the same drug classification. This project’s overall goal was to develop and optimize a simple, sensitive and selective method for the detection and determination of Tamoxifen in oral fluid (OF) for drug testing purposes using Gas Chromatography/Mass Spectrometry (GC/MS) that could be utilized to supplement WADA’s current testing protocol which uses blood and urine specimens. Because method development for analysis of oral fluid specimens containing highly protein bound analytes typically relies on the use of newer LC-MS/MS instrumentation (and the costs associated with acquiring and using this technology), a GC method remains advantageous. A calibration curve was created; the developed methods proved to be successful for the recovery and detection of Tamoxifen from artificial saliva samples with high sensitivity.

A second part of this project was to develop additional analytical methods for discrimination and chromatographic resolution of three regioisomeric aromatase inhibitors (5-alpha-Androstan-17-one, 5-alpha-Androst-16-en-3α-ol and 17-beta-Hydroxy-5-alpha-androst-2-ene) per their representation of similar ingredients utilized in some black market dietary supplements that promise gain of muscle mass but also violate WADA’s policies. Using Gas Chromatography/Mass Spectrometry (GC/MS) and Fourier Transform Infrared Spectroscopy (FT-IR), this project investigated detection and differentiation between these regioisomeric AIs which have the same molecular formulae, same nominal and exact masses and almost identical elution properties.

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