Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 2015 Nanoscale GUMBOS: Size-Control, Characterization, and Applications as Enantioselective Molecularly Imprinted Polymers and Fluorescent Materials Suzana Hamdan Louisiana State University and Agricultural and Mechanical College, [email protected] Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_dissertations Part of the Chemistry Commons Recommended Citation Hamdan, Suzana, "Nanoscale GUMBOS: Size-Control, Characterization, and Applications as Enantioselective Molecularly Imprinted Polymers and Fluorescent Materials" (2015). LSU Doctoral Dissertations. 1580. https://digitalcommons.lsu.edu/gradschool_dissertations/1580 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Doctoral Dissertations by an authorized graduate school editor of LSU Digital Commons. For more information, please [email protected]. NANOSCALE GUMBOS: SIZE-CONTROL, CHARACTERIZATION, AND APPLICATIONS AS ENANTIOSELECTIVE MOLECULARLY IMPRINTED POLYMERS AND FLUORESCENT MATERIALS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agriculture and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Suzana Hamdan B.S., Lebanese University, 2006 M.S., East Tennessee State University, 2009 May 2015 “I dedicate this dissertation to my parents Drs. Wahibe Abi Chahine and Hamdan Hamdan who supported and encouraged me throughout my studies. My dedications are also to my sister Mireille and her husband Dr. Lucien Abboud who helped and guided me from first entrance into graduate school. My final dedications are to my nephew Jason and niece Cassandra for bringing total joy into my life.” ii ACKNOWLEDGMENTS Prof. Isiah M. Warner for being such a great mentor, teaching me how to be a better scientist, and believing in my capabilities. Thank you for all the support that you have shown and all the knowledge that you have provided. You will always be an inspiration for me. Prof. David A. Spivak for teaching me about molecular imprinting and for all the time and effort you afforded for the imprinting research project. Doctoral Committee Members: Prof. Samuel D. Gilman, Prof. Kermit K. Murray, Prof. Megan A. Macnaughtan, and Prof. Wayne D. Newhauser for all the help and advice provided to improve my work. Prof. Chu-Ngi Ho for enriching my background in analytical chemistry and guiding me through my Master’s degree. Dr. Bilal El-Zahab, Dr. Noureen Siraj, Dr. Farhana Hasan, and Dr. Susmita Das for all your suggestions and proofing of documents during my graduate studies. Dr. Leonard Moore Jr. and Dr. Jonathan Dumke for all the support that you have provided in challenging situations. The Warner Research Group for sharing your scientific knowledge and discussing ideas in group meetings. iii TABLE OF CONTENTS ACKNOWLEDGMENTS .................................................................................................. iii LIST OF TABLES ........................................................................................................... vii LIST OF FIGURES ........................................................................................................ viii LIST OF SCHEMES ...................................................................................................... xiii LIST OF ABBREVIATIONS ........................................................................................... xiv ABSTRACT ................................................................................................................... xvi CHAPTER ONE. INTRODUCTION ................................................................................. 1 1.1. Nanotechnology Concept ................................................................................... 1 1.2. Nanotechnology in Chemistry: Nanomaterials ................................................... 2 1.2.1. Historical View ........................................................................................... 2 1.2.2. Nanomaterials in the Service of Chemistry ............................................... 3 1.2.3. Dimensionality of Nanomaterials ............................................................... 4 1.2.4. Synthesis Strategies of Nanomaterials: Top-down and Bottom-up Approaches ............................................................................. 5 1.3. Zero-Dimensional Nanomaterials (Nanoparticles) ............................................. 6 1.3.1. Synthesis and Size-Control of Nanoparticles ............................................ 6 1.3.2. Synthesis of Organic Nanoparticles .......................................................... 9 1.4. Synthesis of Nanoparticles Derived from GUMBOS (NanoGUMBOS) Using Ionic Liquid Chemistry ........................................................................... 10 1.4.1. Ionic Liquids, Polymeric Ionic Liquids, and GUMBOS ............................. 10 1.4.2. Size-Control of NanoGUMBOS ............................................................... 13 1.4.3. Free Template Syntheses of NanoGUMBOS .......................................... 15 1.4.4. Templated Syntheses of NanoGUMBOS ................................................ 18 1.4.5. Doping NanoGUMBOS ........................................................................... 21 1.5. NanoGUMBOS: Characterization Tools ........................................................... 22 1.5.1. Transmission Electron Microscopy .......................................................... 22 1.5.2. Dynamic Light Scattering ........................................................................ 24 1.5.3. Zeta Potential .......................................................................................... 26 1.5.4. Spectroscopic Studies ............................................................................. 27 1.6. Applications of NanoGUMBOS ........................................................................ 31 1.6.1. Molecular Imprinting ................................................................................ 31 1.6.2. Organic Light Emitting Devices ............................................................... 33 1.7. Scope of this Dissertation ................................................................................ 35 1.8. References ...................................................................................................... 36 iv CHAPTER TWO. STRATEGIES FOR CONTROLLED SYNTHESIS OF NANOPARTICLES DERIVED FROM A GROUP OF UNIFORM MATERIALS BASED ON ORGANIC SALTS ...................................................................................... 47 2.1. Introduction ...................................................................................................... 47 2.2. Experimental Section ....................................................................................... 50 2.2.1. Materials .................................................................................................. 50 2.2.2. Melting Point and Thermogravimetric Measurements ............................. 51 2.2.3. Transmission Electron Microscopy .......................................................... 51 2.2.4. Light Scattering and Zeta Potential Measurements ................................. 51 2.2.5. Non-Templated Synthesis Methods ........................................................ 52 2.2.6. Templated Synthesis Method .................................................................. 53 2.3. Results and Discussion .................................................................................... 54 2.3.1. Metathesis Reaction ................................................................................ 54 2.3.2. Size Studies ............................................................................................ 55 2.3.3. Stability Studies ....................................................................................... 65 2.4. Conclusions ..................................................................................................... 67 2.5. References ...................................................................................................... 68 CHAPTER THREE. POLYMERIC IMPRINTED NANOGUMBOS FOR CHIRAL RECOGNITION ............................................................................................................. 72 3.1. Introduction ...................................................................................................... 72 3.2. Experimental Section ....................................................................................... 74 3.2.1. Materials .................................................................................................. 74 3.2.2. Characterization Techniques ................................................................... 74 3.2.3. Synthesis Procedures ............................................................................. 75 3.3. Results and Discussion .................................................................................... 77 3.4. Conclusions ..................................................................................................... 91 3.5. References ...................................................................................................... 92 CHAPTER FOUR. SYNTHESIS OF POLYMERIC NANOGUMBOS VIA GAMMA