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Application of Electrospray Ionization Mass Spectrometry for Ionic Liquids and Their Biodegradation Products

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Application of Electrospray Ionization Mass Spectrometry for Ionic Liquids and Their Biodegradation Products Western Michigan University ScholarWorks at WMU Master's Theses Graduate College 4-2016 Application of Electrospray Ionization Mass Spectrometry for Ionic Liquids and their Biodegradation Products Sepideh Rahbarirad Follow this and additional works at: https://scholarworks.wmich.edu/masters_theses Part of the Materials Chemistry Commons, and the Organic Chemistry Commons Recommended Citation Rahbarirad, Sepideh, "Application of Electrospray Ionization Mass Spectrometry for Ionic Liquids and their Biodegradation Products" (2016). Master's Theses. 691. https://scholarworks.wmich.edu/masters_theses/691 This Masters Thesis-Open Access is brought to you for free and open access by the Graduate College at ScholarWorks at WMU. It has been accepted for inclusion in Master's Theses by an authorized administrator of ScholarWorks at WMU. For more information, please contact [email protected]. APPLICATION OF ELECTROSPRAY IONIZATION MASS SPECTROMETRY FOR IONIC LIQUIDS AND THEIR BIODEGRADATION PRODUCTS by Sepideh Rahbarirad A thesis submitted to the Graduate College in partial fulfillment of the requirements for the degree of Master of Science Chemistry Western Michigan University April 2016 Thesis Committee: Andre Venter, Ph.D., Chair Michael Barcelona, Ph.D. Blair Szymczyna, Ph.D. APPLICATION OF ELECTROSPRAY IONIZATION MASS SPECTROMETRY FOR IONIC LIQUIDS AND THEIR BIODEGRADATION PRODUCTS Sepideh Rahbarirad, M.S. Western Michigan University, 2016 Ionic liquids (ILs) are organic salts with unique physico-chemical properties and are used as green alternatives to volatile organic solvents. ESI-MS is a sensitive technique to detect these stable, permanent ions. My research focused on (1) Identification of biodegradation products of ionic liquids and (2) Multiplexed tandem MS by modulation of ionization efficiency. Studies, have demonstrated that ILs are toxic to the environment, which makes their biodegradability an important consideration. In this work, metabolites generated during the biodegradation of 1-butyl-3-methylimidazolium chloride (BMIM), a degradation resistant and commonly used ionic liquid, are identified using high performance liquid chromatography-mass spectrometry (LC-MS). Multiplexed tandem MS is a method to increase sample throughput for identification of complex mixtures. However, previous multiplexed tandem MS methods mostly require expensive mass spectrometers. In this study, we demonstrate a novel method of multiplexing MS where correlation of the fragments to their respective precursors is achieved by modulating the ionization efficiencies of analytes by changing the solvent composition. This method has the potential to do powerful MS/MS experiments on inexpensive single stage mass analyzers. Copyright by Sepideh Rahbarirad 2016 ACKNOWLEDGMENTS I would like to thank my advisor Dr. Andre Venter for his guidance and advices and all the knowledge and skills he shared with me. I would also like to thank Dr. Michael Barcelona and Dr. Blair Szymczyna for their time and suggestions as members of my committee. It’s my pleasure to thank Dr. Sherine Obare for her kind support and advices as graduate adviser. I am thankful to the Chemistry Department of Western Michigan University for providing the resources for this accomplishment. Thank to my labmates and friends Gregg, Elahe, Wisam and Nafiseh who always helped me along the period of my study. I would also like to give special thanks to my husband, Majid who completion of this study was not possible without his supports. Sepideh Rahbarirad ii TABLE OF CONTENTS ACKNOWLEDGEMENTS………………………………………………………... ii LIST OF TABLES ………………………………………………………………… vii LIST OF FIGURES ……………………….……………………………………..... viii CHAPTER 1. INTRODUCTION…….…………………………………………………….….. 1 1.1. Chapter Introduction…………………………….………………….... 1 1.2. Electrospray Ionization Mass Spectrometry.…………….…………... 1 1.3. Ionic Liquids…………….…...………………………………………. 5 1.4. Multiplexed Tandem Mass Spectrometry…..……….……………….. 6 1.5. References…………………………………..........….……………….. 7 2. Ionic Liquids……………………………………………...….………..……….. 10 2.1. Introduction…………………………………………………………... 10 2.2. Biodegradation of Ionic Liquids…...………………………………..... 11 2.3. Chromatographic Separation of Ionic Liquids.………………………. 15 2.4. Detection of the Metabolites.………………………………………... 17 2.5. Chapter Conclusion.…………………………………………………. 17 2.6. References……………………………………………………………. 18 iii Table of Contents-continued CHAPTER 3. EXPERIMENTAL METHODS AND RESULTS OF IDENTIFICTION OF METABOLITES OF IONIC LIQUIDS..……………………………………..... 23 3.1. Introduction…………………………………………………………... 23 3.2. Experimental Section……………………………………………..…... 23 3.2.1. Sample Preparation for Degradation……….…………………... 24 3.2.2. Experimental Procedure for HPLC-UV-MS Analysis…………. 24 3.2.3. Mass Spectrometry Scan Modes….…………………….....…… 25 3.3. Results and Discussion……………………………………………….. 27 3.3.1. Biodegradation of BMIM…………………………………….… 27 3.3.2. Identification of Biodegradation Products and Pathways ……... 29 3.3.3. Mass Balance and Degraded BMIM…………………………... 37 3.4. Chapter Conclusion.…………………………………………………. 40 3.5. References……………………………………………………………. 40 4. BACKGROUND AND THEORY OF ELECTROSPRAY IONIZATION MASS SPECTROMETRY ……………..……………………………………………..... 42 4.1. The Electrospray Ionization Process....……………………………….. 42 4.2. Surface Activity…..……………………………………………..…...... 44 4.3. Equilibrium Partitioning Model………………………….…………….. 47 4.4. Chapter Conclusion……………………………………….……………. 49 4.5. References……………………………………………………………... 49 iv Table of Contents-continued CHAPTER 5. TANDEM MASS SPECTROMETRY ……...………………………..…..... 52 5.1. Introduction…………………………………………………………... 52 5.2. Multiplexed Tandem Mass Spectrometry………………………..…... 55 5.3. The Need for Multiplexed Tandem Spectrometry...………………….. 58 5.4. Modulated Ionization Efficiency Multiplexed MS..………………….. 60 5.5. Chapter Conclusion…………………………………………………… 60 5.6. References……………………………………………………………. 61 6. MULTIPLEXED TANDEM MASS SPECTROMETRY BY MODULATION OF IONIZATION EFFICIENCY ………...………………………………….…….. 65 6.1. Introduction……...…..……………………………………………...... 64 6.2. Experimental Methods……………………………………………...... 66 6.2.1. Molecular Probes Used to Study Modulation of Ionization Efficiency……………………...................................................... 66 6.2.2. Instrumental Setup…………………………............................... 68 6.2.3. Methods………………………………........................................ 68 6.3. Results and Discussion……………………………………………..... 69 6.3.1. Modulation by Solvent Composition ........................................... 69 6.3.2. Modulation by Spray Distance..……………............................... 72 6.4. Recognition of Two Isobaric Compounds..………………..………..... 73 6.4.1. Chemical and Experimental Conditions......................................... 73 6.4.2. Results and Discussion………...……………............................... 74 v Table of Contents-continued CHAPTER 6.5. Chapter Conclusion…………………………………….…………….... 80 6.6. References………………………………………….………………….. 81 7. CONCLUSION……………...………...………………………….……….…….. 83 7.1. Identification of Ionic Liquids Biodegradation Products …………...... 83 7.2. Multiplexed Tandem Mass Spectrometry by Modulation of Ionization Efficiency...…….………………………………………...... 85 vi LIST OF TABLES 6.1. The ionic liquid test compounds used in this study.………………………… 67 6.2. The intensity ratios of the test compounds between high (80%) versus low (20%) methanol concentration…….…………..………………..…………… 71 6.3. The intensity ratios of the test compounds between near and far sprayer…… 73 6.4. The intensity ratios of the main fragments of isobaric compounds of 1,7- Dimethylxanthine and theobromine…....…………..…………..……………. 76 6.5. The intensity ratios of the fragments of isobaric compounds of m/z 347 α and iso-α hop acid isomers…………………..………......…………..…….. 78 6.6. The intensity ratios of the fragments of isobaric compounds of m/z 347 α and iso-α hop acid isomers…………...…..………......…………..………… 80 vii LIST OF FIGURES 1.1. Schematic representation of the electrospray ionization process in the positive ion mode. Cech, N. B.; Enke, C. G. Mass Spectrometry Reviews, 2001, 20, 362 –387….......................................................................................... 3 2.1. Structural Biodegradation pathways of 1-octyl-3-methylimidazolium by activated sludge microbial community (Adapted from Stolte et al. (2008) by permission of the Royal Society of Chemistry) [44]…………………….…… 14 3.1. Extraction ion chromatogram (EIC), total ion chromatogram (TIC) and UV trace of BMIM standard.……………………………………...………............ 27 3.2. Biodegradation of BMIM cation over 46 days followed by LC-MS ….......... 28 3.3. Percentage of biodegradation compared to day 3 over 46 days of the treatment …………..………………………………………..……………….. 29 3.4. LC-UV-MS extracted ion chromatograms for m/z 139 BMIM and metabolites of m/z 155 BMIM+O, m/z 141 BMIM-CH3+OH, m/z 137 BMIM-2H and UV absorbance at 212nm trace at day 21 of the treatment ....... 30 3.5. Formation and depletion trends for the major detected biodegradation product over 46 days of the treatment. m/z 155: BMIM+O; m/z 141: BMIM-CH3+OH; m/z 137: BMIM-2H; m/z 83: IM+CH3. m/z 83 area count is divided by 5……………………………………………………. 31 3.6. Chemical structure and fragmentation pattern of m/z 139 (BMIM)…………. 32 3.7. Chemical structure of m/z 155 and its fragmentation pattern.………………. 33 3.8. Chemical structure of m/z 141 and its possible fragmentation pattern………. 34 3.9. Chemical structure of m/z 137 and its possible fragmentation pattern.……… 35 3.10. Structures of BMIM cation and identified Breakdown
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