Beaton, Adam G. (2019) Optimization and evaluation of the performance of thin-film molecularly imprinted polymers for the analysis of cotinine in fluids from human subjects. Masters thesis, Memorial University of Newfoundland.
[English]
PDF
- Accepted Version
Available under License - The author retains copyright ownership and moral rights in this thesis. Neither the thesis nor substantial extracts from it may be printed or otherwise reproduced without the author's permission. Download (2MB) |
Abstract
Molecularly imprinted polymers (MIPs) are cross-linked synthetic polymers that can selectively take up target analytes from a solution. They are often used in bulk format for solid phase extraction and HPLC. In this work, the main goal was to develop MIPs in a thin-film format for direct analysis of analyte species by desorption electrospray ionization-mass spectrometry (DESI-MS). A cotinine template was used with methacrylic acid (MAA) monomer and ethyleneglycol dimethacrylate (EDGMA) cross-linker to synthesize these MIPs. Cotinine is the primary metabolite of nicotine and was chosen as the template due to its high concentration in biological fluids from smokers and non-smokers. Optimization of the ratios of polymer components (template:monomer:cross-linker) and porogen was completed using a modified Box-Behnken experimental design. Each composition tested was assessed for polymer robustness, imprinting factor and sorption capacity. The optimal molar ratio was 1:2:22.5 (template:monomer:cross-linker), with 239 μL porogen added for each 0.02 mol of template. Template removal from the MIP was studied and reduced from 2 h to 100 min. For optimal analyte uptake, MIPs were placed for 90 min in samples buffered at pH 7.0. Cotinine was quantified in extracts using GC-MS. Myosmine, B-nicotyrine, 1-phenyl-3-pyrazolidinone and nicotine-N-oxide were used as pseudo-templates to overcome template bleed were studied but with little success due to the lack of uptake by these pseudo-templates. Scanning electron microscopy showed that the MIPs were porous and up to approximately 0.05 μm in diameter. Cotinine calibration curves for human urine spiked with cotinine gave results of R²=0.6 with n=2. Testing with saliva samples did not produce any promising results. Proof of principle was demonstrated for detection of cotinine using MIPs with DESI-MS.
Item Type: | Thesis (Masters) |
---|---|
URI: | http://research.library.mun.ca/id/eprint/13785 |
Item ID: | 13785 |
Additional Information: | Includes bibliographical references (pages 80-85). |
Keywords: | Analytical Chemistry, Polymers, Mass spectrometry, Gas chromatography, molecularly imprinted polymers, MIPs |
Department(s): | Science, Faculty of > Chemistry |
Date: | March 2019 |
Date Type: | Submission |
Library of Congress Subject Heading: | Imprinted polymers; Electrospray ionization mass spectrometry |
Actions (login required)
View Item |