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Polytetrahydrofuran-And Dendrimer University of South Florida Scholar Commons Graduate Theses and Dissertations Graduate School 2005 Polytetrahydrofuran-and Dendrimer-Based Novel Sol-Gel Coatings for Capillary Microextraction (CME) Providing Parts Per Trillion (ppt) and Parts Per Quadrillion (ppq) Level Detection Limits in Conjunction With Gas Chromatography and Flame Ionization Detection (FID) Abuzar Kabir University of South Florida Follow this and additional works at: https://scholarcommons.usf.edu/etd Part of the American Studies Commons Scholar Commons Citation Kabir, Abuzar, "Polytetrahydrofuran-and Dendrimer-Based Novel Sol-Gel Coatings for Capillary Microextraction (CME) Providing Parts Per Trillion (ppt) and Parts Per Quadrillion (ppq) Level Detection Limits in Conjunction With Gas Chromatography and Flame Ionization Detection (FID)" (2005). Graduate Theses and Dissertations. https://scholarcommons.usf.edu/etd/2948 This Dissertation is brought to you for free and open access by the Graduate School at Scholar Commons. It has been accepted for inclusion in Graduate Theses and Dissertations by an authorized administrator of Scholar Commons. For more information, please contact [email protected]. Polytetrahydrofuran-and Dendrimer-Based Novel Sol-Gel Coatings for Capillary Microextraction (CME) Providing Parts Per Trillion (ppt) and Parts Per Quadrillion (ppq) Level Detection Limits in Conjunction With Gas Chromatography and Flame Ionization Detection (FID) by Abuzar Kabir A dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy Department of Chemistry College of Arts and Sciences University of South Florida Major Professor: Abdul Malik, Ph.D. Milton D. Johnston, Ph.D. Dean F. Martin, Ph.D. Robert L. Potter, Ph.D. Date of Approval: April 29, 2005 Keywords: SPME, In-tube SPME, PAHs, Aldehydes, Ketones, Phenols, Alcohols © Copyright 2005, Abuzar Kabir Dedication To my deceased parents, Moqbulur Rahman and Suraiya Rahman, who brought me in this beautiful world and provided their endless inspiration, love and support. Acknowledgements I would like to express my sincere acknowledgment and earnest appreciation to several people whose contribution, guidance, and encouragement have made this dissertation possible. First, I would like to thank my major professor, Dr. Abdul Malik for his able supervision, instruction, patience, support and encouragement. I would also like to express my appreciation and gratitude to my Ph.D. committee members: Dr. Milton D. Johnston, Jr., Dr. Dean F. Martin, and Dr. Robert Potter for their tireless support and encouragement from the very beginning of my research endeavor. In addition, I would like to thank Ms. Betty Loraamm of the USF Biology Department for her kind assistance in acquiring all scanning electron microscopic images throughout this study. I would like to express my sincere appreciation to fellow graduate students C. Shende, T.-Y. Kim, W. Li, K. Alhooshani, Li Fang, Sameer Kulkarni, Anne Marrie Shearrow, and Erica Turner whose continuous assistance, support, and encouragement helped me stay focused. I wholeheartedly acknowledge USF Department of Chemistry for financial support throughout my graduate career. Last, and of utmost significance, great appreciation is extended to the members of my family, in particular, my wife, Salima Kabir, daughter, Nafisa Kabir, and elder brother, Khaled Saifullah. This degree, as well as other accomplishments in my life, would have never been possible without unlimited patience, extensive sacrifices and tireless dedication from their side. Table of Contents List of Tables vii List of Figures xii List of Schemes xvii List of Abbreviations, Symbols, and Acronyms xviii Abstract xx Chapter One : Solid Phase Microextraction-A Solvent-Free Sample Preparation Technique 1 1.1 Introduction 1 1.2 Evolution of solid phase microextraction: a historical 2 perspective 1.3 Working principles of SPME 8 1.4 Modes of extraction 10 1.4.1 Extraction modes with a coated fiber 10 1.4.2 Extraction modes with in-tube SPME 13 1.5 Preparation of coating on fibers 14 1.6 Experimental parameters affecting extraction efficiency 14 1.6.1 pH adjustment of the matrix 15 1.6.2 Agitation of the matrix 15 1.6.3 Heating the matrix 16 1.6.4 Addition of salt to the matrix 19 1.6.5 Addition of organic solvents 19 1.7 Derivatization 20 1.8 References for Chapter One 23 Chapter Two : An Overview on Stationary Phases Used in Solid Phase Microextraction (SPME) 26 2.1 Introduction 26 2.2 Commercially available sorbents for fiber SPME 32 2.2.1 Homogeneous polymeric sorbents 33 2.2.2 Polymeric composite sorbents 34 2.2.2.1 Polydimethylsiloxane/DVB (PDMS/DVB) 34 2.2.2.2 Carboxen/Polydimethylsiloxane 35 (CAR/PDMS) 2.2.2.3 Carbowax/Divinylbenzene (CW/DVB) 35 2.2.2.4 Carbowax/Templated resin (CW/TPR) 36 i 2.2.2.5 Divinylbenzene/Carboxen /Polydimethylsiloxane(DVB/ CAR/PDMS) 36 2.3 Commercial GC coatings used in in-tube SPME 37 2.4 Tailor made coatings on SPME fibers 42 2.4.1 Immobilized antibodies 44 2.4.2 Metallic SPME fibers 47 2.4.3 Active carbonaceous sorbents 51 2.4.4 Bonded silica sorbents 54 2.4.5 Flat sheet membranes 57 2.4.6 Miscellaneous sorbents 59 2.5 Tailor made coatings for in-tube SPME 61 2.5.1 Tailor made coatings used predominantly in in-tube SPME 61 2.5.1.1 Molecularly imprinted polymers 63 2.5.1.2 Restricted access materials (RAM) 66 2.5.1.3 Conductive polymers 69 2.5.2 Coatings exclusively used in in-tube SPME 77 2.6 References for Chapter Two 84 Chapter Three : Sol-Gel Technology in Capillary Microextraction 91 3.1 A brief history 91 3.2 Sol-gel technology in SPME 93 3.3 Sol-gel sorbents in SPME: a brief overview 95 3.3.1 Polysiloxane based sol-gel sorbents 97 3.3.1.1 Sol-gel sorbents with homogeneous polysiloxane phases 97 3.3.1.2 Mixed polysiloxane based sol-gel sorbents 106 3.3.1.2.1 Fullerene-polysiloxane mixed sol-gel sorbents 106 3.3.1.2.2 Mixed crown ether-polysiloxane sol-gel sorbents 110 3.3.1.2.3 Mixed calix[4]arene-polysiloxane sol-gel sorbents 132 3.3.1.2.4 Mixed polyvinyl alcohol (PVA)– polysiloxane sol-gel sorbents 139 3.3.1.2.5 Mixed polymethylphenylvinylsiloxane (PMPVS) – polysiloxane sol-gel sorbents 140 3.3.1.2.6 Mixed divinylbenzene-polysiloxane sol-gel sorbents 141 3.3.1.2.7 Mixed polyphenylmethylsiloxane (PPMS) – polysiloxane sol-gel sorbents 144 ii 3.3.2 Non-polysiloxane based sorbents 149 3.3.2.1 Polyethylene glycol-based sol-gel sorbents 151 3.3.2.2 Non-polysiloxane sol-gel sorbents with alkyl ligands 159 3.3.3 Cyclodextrin-based non-polysiloxane sol-gel sorbents 163 3.4 Miscellaneous sorbents 166 3.5 References for Chapter Three 168 Chapter Four : Capillary Microextraction on Sol-Gel Benzyl Terminated Dendrimer Coating 173 4.1 Introduction 173 4.2 Experimental 177 4.2.1 Equipment 177 4.2.2 Chemicals and materials 178 4.2.3 Preparation of sol-gel dendrimer coated extraction capillaries 179 4.2.3.1 Cleaning and hydrothermal treatment of the fused silica capillary 179 4.2.3.2 Preparation of the sol solution 182 4.2.3.3 Coating of the fused silica capillary with sol solution 183 4.2.3.4 Thermal conditioning of the coated capillary 184 4.2.3.5 Rinsing the capillary with organic solvents to remove unbonded material 184 4.2.4 Preparation of sol-gel PDMS coated capillary GC column 185 4.2.5 Preparation of sol-gel PEG coated capillary GC column 187 4.2.6 Gravity-fed sample dispenser for capillary microextraction 188 4.2.7 Deactivation of glassware 190 4.2.8 Preparation of standard sample solution for sol-gel dendrimer CME 190 4.2.9 Extraction of analytes on sol-gel dendrimer coated capillaries 190 4.2.10 Transferring the extracted analytes to the GC column and Gas chromatographic analysis of the extracted analytes 191 4.2.11 Calculation of the limit of detection (LOD) for individual analyte 194 4.3 Results and discussion 194 4.3.1 Sol-gel dendrimer coating and chemical aspects of its preparation 195 4.3.2 Characterization of surface morphology and determination of coating thickness using scanning electron microscopy 203 iii 4.3.3 Determination of extraction kinetics for both polar and nonpolar analytes 206 4.3.4 Applications of sol-gel dendrimer coated microextraction capillaries 208 4.3.4.1 Polycyclic aromatic hydrocarbons (PAHs) 208 4.3.4.2 Aldehydes and ketones 215 4.3.4.3 Phenols 227 4.3.4.4 CME of butylatedhydroxytoluene (BHT) 233 4.3.4.5 Alcohols 234 4.4 Conclusion 244 4.5 References for Chapter Four 245 Chapter Five : Capillary Microextraction on Sol-Gel Polytetrahydrofuran 250 5.1 Introduction 250 5.2 Experimental 256 5.2.1 Equipments 256 5.2.2 Chemicals and materials 259 5.2.3 Preparation of sol-gel poly-THF coated Microextraction capillaries 259 5.2.3.1 Cleaning and hydrothermal treatment of the fused silica capillary 260 5.2.3.2 Preparation of the sol solution 262 5.2.3.3 Coating fused silica capillary with sol solution 264 5.2.3.4 Thermal conditioning of the coated capillary 264 5.2.3.5 Rinsing the capillary with organic solvents to remove unbonded materials 265 5.2.4 Preparation of sol-gel PDMS coated capillary GC columns 265 5.2.5 Preparation of sol-gel PEG coated capillary column 267 5.2.6 Cleaning and deactivation of glassware 268 5.2.7 Preparation of standard solutions for CME on sol-gel Poly-THF coated capillaries 269 5.2.8 Gravity-fed sample dispenser for capillary microextraction 270 5.2.9 Extraction of analytes on sol-gel poly-THF coated capillaries 270 5.2.10 Transferring the extracted analytes to the GC column and gas chromatographic analysis of the extracted analytes 271 5.3 Results and Discussion 273 5.3.1 Sol-gel
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