Date of Award

Spring 5-21-2022

Degree Type

Dissertation

Degree Name

PhD. Chemistry

Department

Chemistry and Biochemistry

Advisor

Nicholas H. Snow, Ph.D.

Committee Member

Wyatt R. Murphy, Ph.D.

Committee Member

Yuri V. Kazakevich, Ph.D.

Keywords

Polyol induced extraction of drug molecules, Glucocorticoids, NSAIDs, UHPLC-MS/MS, LLE, PIE-UHPLC-MS/MS, LC-MS/MS

Abstract

Polyol induced extraction (PIE) is an extraction technique developed and patented by Sowa Jr., Murphy, and Deshpande at Seton Hall University as a method of removal of water from acetonitrile. PIE is a technique that separates water from a mixture containing an organic liquid and water by adding a polyol to the mixture that leads to phase separation of aqueous and organic phase. The goal of this work was to extend the application of PIE and to demonstrate that PIE can be an alternative method for extraction of glucocorticoids and non-steroidal anti-inflammatory drugs (NSAIDS) which then can be analyzed using ultra high-performance liquid chromatography-triple quadrupole mass spectrometry (UHPLC-MS/MS). A multiple reaction monitoring transitions of selected precursor ion to selected product ions were optimized for each analyte for quantitative analysis. Optimization of liquid chromatography was carried out to determine chromatographic condition. For each application method validation was performed and percent recovery, linearity, limit of detection, limit of quantitation, and accuracy were determined for each compound.

The first application involves the extraction of glucocorticoids from water into acetonitrile using glycerol as a phase separating agent. Glucocorticoids are a natural and synthetic type of steroids. Extensive use of these compounds can lead to contamination of the environment. Eight different glucocorticoids were extracted from water by PIE and analyzed. glucocorticoid. Extraction conditions were optimized. Followed by PIE study, a comparison study of PIE to QuEChERS (Quick, Easy, Cheap, Effective, Rugged and safe) was performed. PIE is like QuEChERS in terms of use of organic solvent and a mass separating agent to generate phase separation of organic and aqueous phases which leads to extraction of analytes of interest into organic phase. To compare these two methods same eight glucocorticoids were subjected to QuEChERS technique and then analyzed. Linearity, accuracy precision and extraction efficiency were determined and compared. Obtained results showed PIE is comparable to QuEChERS in terms of analytical merits.

Similarly, PIE was also applied for the extraction of NSAIDs from water into acetonitrile using glycerol as a phase separating agent. Residues of these drugs are also emerging pollutants in water. Eight NSAIDS were subjected to PIE and then analyzed using UHPLC-MS/MS. Additionally synthetic urine samples were spiked with NSAIDS and then were subjected to PIE and analyzed.

In this research work, PIE of glucocorticoids and their analysis using gas chromatography (GC) was performed to evaluate compatibility of PIE with gas chromatography. GC-TOFMS was used to carry out the analysis. Glucocorticoids were analyzed without any derivatization process.

Results obtained in this study showed that PIE has an amazing potential to be an extraction technique for drugs, especially glucocorticoids and NSAIDs. PIE is very simple, cost effective and user-friendly extraction technique that can be compatible with both liquid and gas chromatography.

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