Seton Hall University eRepository @ Seton Hall Seton Hall University Dissertations and Theses Seton Hall University Dissertations and Theses (ETDs) Summer 8-9-2014 Extending the Limits of Solid Phase Microextraction Shilpi Chopra [email protected] Follow this and additional works at: https://scholarship.shu.edu/dissertations Part of the Analytical Chemistry Commons Recommended Citation Chopra, Shilpi, "Extending the Limits of Solid Phase Microextraction" (2014). Seton Hall University Dissertations and Theses (ETDs). 1990. https://scholarship.shu.edu/dissertations/1990 Acknowledgement Foremost, I would like to express my gratitude towards my mentor Dr. Nicholas. H. Snow, for his continuous support in my research work with patience, motivation, enthusiasm and immense knowledge in research whilst allowing me the room to work in my own way. His support in tough times has always encouraged me to fight back with obstacles and comeback with a solution. The best part about being in Dr. Snow’s group was discussion and group meeting which helped everyone in group to grow and think as a scientist. Besides my advisor, I would like to thank the rest of my thesis committee: Dr. Yuri Kazakevich for their encouragement, insightful comments, and intriguing questions. Dr. Wyatt. R. Murphy for giving me opportunity to teach principles of chemistry and helping me in matriculation exam and formal seminar. My sincere thanks also goes to Dr. John Sowa for providing me an excellent opportunity to work on BP oil spill project, Dr. Alexander Fadeev for providing an insight in surface chemistry course and for helping me during my formal seminar. I also want to extend my thanks to my former colleagues Dr. Brian Barnes and Dr. Ramkumar Dhandapani who helped me immensely during my matriculation exam and in my research. My special thanks to Sigma-Aldrich for providing SPME fibers, Thermo Scientific and Shimadzu for providing GC-MS-MS for my research, Sanofi-Aventis and Center for Academic Industry Partnership for providing necessary funding to perform the research. In my daily work I have been blessed with a friendly and cheerful group of colleagues from our separation science group, Michelle Schmidt, Atsu apedo and Anumeha Muthal 3 Last but not the least I want to say thanks from the core of my heart to my husband, Pritpal Singh for his extended support, care and love during my research. I also want to thanks my mom, dad and my in-laws for their blessings throughout this journey. 4 Table of Contents Acknowledgement .............................................................................................................. 3 List of Figures ..................................................................................................................... 9 List of Tables .................................................................................................................... 11 Abstract: ............................................................................................................................ 12 Chapter -1 ...................................................................................................................... 15 INTRODUCTION TO SOLID PHASE MICROEXTRACTION ................................ 15 Sample Preparation: ................................................................................................... 16 Solid Phase Microextraction (SPME)........................................................................ 17 Theory: ................................................................................................................... 20 Critical Parameters to be optimized in Solid Phase Microextaction: .................... 28 Sample Agitation ................................................................................................ 29 Temperature ....................................................................................................... 30 Extraction time: ................................................... 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Salt ...................................................................................................................... 35 Desorption .......................................................................................................... 35 pH Effect ............................................................................................................ 37 Derivatization ..................................................................................................... 38 Conclusions: .............................................................................................................. 41 Chapter-2........................................................................................................................... 42 Analysis of Steroids using Solid Phase Microextraction-Gas Chromatography-Mass Spectrometry-Mass Spectrometry (SPME-GC-MS-MS) .............................................. 42 Summary:................................................................................................................... 42 Introduction: .............................................................................................................. 43 Depletion study ...................................................................................................... 43 Triple Quadrupole Mass Spectrometer .................................................................. 44 Steroids in environment ......................................................................................... 47 Experimental .............................................................................................................. 52 Materials and Chemicals ........................................................................................ 52 Buffer, Standard and Sample Preparation .............................................................. 53 Instrumental Conditions ......................................................................................... 54 5 SPME Conditions ............................................................................................... 54 GC-MS-MS Conditions ..................................................................................... 54 Depletion Study .................................................................................................. 55 Validation ........................................................................................................... 55 Results and Discussion .............................................................................................. 56 Solid Phase Microextraction (SPME) .................................................................... 56 GC-MS-MS ............................................................................................................ 56 Fiber/sample partition coefficient by depletion study ........................................... 61 Validation ............................................................................................................... 63 Field Samples ............................................................................................................ 75 Comparison between GC-MS-MS and GC×GC-TofMS .......................................... 77 Conclusions ............................................................................................................... 79 Chapter-3........................................................................................................................... 80 Quantitative Analysis of Polycyclic Aromatic Hydrocarbons in Fish Oil by Headspace Solid Phase Microextraction and Gas Chromatography-Mass Spectrometry (HS- SPME-GC-MS). ............................................................................................................ 80 Summary:................................................................................................................... 80 Introduction: .............................................................................................................. 81 Experimental .............................................................................................................. 85 Materials and Chemicals: ....................................................................................... 85 Sample Preparation ................................................................................................ 85 Real Fish oil Preparation .................................................................................... 86 Instrumental Conditions: ........................................................................................ 88 SPME Conditions ............................................................................................... 88 GC-MS Conditions: ........................................................................................... 88 Results and Discussion: ............................................................................................. 90 Solid Phase Micro Extraction: ............................................................................... 90 Fish oil preparation ................................................................................................ 92 GC-MS ................................................................................................................... 92 Method Validation: .............................................................................................. 98 Calibration, Limit of Quantitation (LOQ) and Limit of detection (LOD