East Tennessee State University Digital Commons @ East Tennessee State University Electronic Theses and Dissertations Student Works 5-2013 Study of Immobilizing Cadmium Selenide Quantum Dots in Selected Polymers for Application in Peroxyoxalate Chemiluminescence Flow Injection Analysis Christopher S. Moore East Tennessee State University Follow this and additional works at: https://dc.etsu.edu/etd Part of the Analytical Chemistry Commons, Bioimaging and Biomedical Optics Commons, and the Nanoscience and Nanotechnology Commons Recommended Citation Moore, Christopher S., "Study of Immobilizing Cadmium Selenide Quantum Dots in Selected Polymers for Application in Peroxyoxalate Chemiluminescence Flow Injection Analysis" (2013). Electronic Theses and Dissertations. Paper 1151. https://dc.etsu.edu/etd/1151 This Thesis - Open Access is brought to you for free and open access by the Student Works at Digital Commons @ East Tennessee State University. It has been accepted for inclusion in Electronic Theses and Dissertations by an authorized administrator of Digital Commons @ East Tennessee State University. For more information, please contact [email protected]. Study of Immobilizing Cadmium Selenide Quantum Dots in Selected Polymers for Application in Peroxyoxalate Chemiluminescence Flow Injection Analysis _____________________ A thesis presented to the faculty of the Department of Chemistry East Tennessee State University In partial fulfillment of the requirements for the degree Master of Science in Chemistry _____________________ by Christopher S. Moore May 2013 _____________________ Dr. Cassandra Eagle, Chair Dr. Alesky Vasiliev Dr. Jeffrey Wardeska Keywords: nanochemistry, quantum dot, CdSe, immobilization, peroxyoxalate, chemiluminescence, POCL, flow injection, FIA ABSTRACT Study of Immobilizing Cadmium Selenide Quantum Dots in Selected Polymers for Application in Peroxyoxalate Chemiluminescence Flow Injection Analysis by Christopher S. Moore Two batches of CdSe QDs with different sizes were synthesized for immobilizing in polyisoprene (PI), polymethylmethacrylate (PMMA), and low-density polyethylene (LDPE). The combinations of QDs and polymer substrates were evaluated for their analytical fit-for-use in applicable immunoassays. Hydrogen peroxide standards were injected into the flow injection analyzer (FIA) constructed to simulate enzyme-generated hydrogen peroxide reacting with bis- (2,4,6-trichlorophenyl) oxalate. Linear correlations between hydrogen peroxide and chemiluminescent intensities yielded regression values greater than 0.9750 for hydrogen peroxide concentrations between 1.0 x 10-4 M and 1.0 x 10-1 M. The developed technique’s LOD was approximately 10 ppm. Variability of the prepared QD-polymer products was as low as 3.2% throughout all preparations. Stability of the preparations was tested during a 30-day period that displayed up to a four-fold increase in the first 10 days. The preparations were decently robust to the FIA system demonstrating up to a 15.20% intensity loss after twenty repetitive injections. 2 ACKNOWLEDGEMENTS I would like to acknowledge several important collections of people that helped make this thesis and supporting graduate work possible. I will begin by thanking my family first and foremost. My parents and grandparents have been of the greatest influence in emphasizing the importance of an education. Without that emphasis I would not appreciate the true value in continuing my education. They also instilled a desire to always strive for more out of life. Thanks also go to my professional colleagues. They provided much wisdom and encouragement during my graduate career. Many thanks go to Mr. John Harrison and Dr. Spencer Hochstetler for mentoring me in the profession of analytical chemistry. Their guidance has inspired me to be intrigued with the observations that chemistry provides and to think rationally about the causes that create the effects. My academic colleagues also deserve acknowledgement as collegiate careers cannot be completed without their support. Finally, I would like to acknowledge several professors I have had the opportunity to cross paths with along my academic journey. Thank you to my research advisors, both undergraduate and graduate, for introducing me to different levels of academic research, and allowing me to apply my classroom knowledge to laboratory practices. This has taught me how to work and think independently, while not forgetting how to collaborate with others. This is of great importance in my profession now and onward. Also thanks to them for the opportunities to perform research in areas of high interests and intriguing discoveries. Many thanks go to both Dr. Jeffrey Wardeska and Dr. Chu-Ngi Ho for their guidance. 3 DEDICATION The work presented is dedicated to my niece, Rebecca Shay. 4 TABLE OF CONTENTS Page ABSTRACT .......................................................................................................................... 2 ACKNOWLEDGEMENTS .................................................................................................. 3 DEDICATION ...................................................................................................................... 4 LIST OF TABLES ................................................................................................................ 10 LIST OF FIGURES .............................................................................................................. 11 Chapter 1. NANOCHEMISTRY PRINCIPLES AND APPLICATIONS ...................................... 13 Introduction ................................................................................................................ 13 Synthesis of Nanoparticles and Quantum Dots ......................................................... 15 Gaseous Synthesis ................................................................................................ 15 Colloidal Synthesis .............................................................................................. 16 Band Gap Chemistry .................................................................................................. 17 Surface Chemistry of Nanoparticles .......................................................................... 18 Effect of Organic Ligands .................................................................................... 18 Effect of Inorganic Ligands ................................................................................. 19 Effect of Oxygen .................................................................................................. 21 Quantum Dot Optical Applications ........................................................................... 23 Quantum Dot Light-Emitting Diodes (QLEDs) .................................................. 23 Biosensors and Probes ......................................................................................... 24 Quantum Dot Immobilization .................................................................................... 27 2. LUMINESCENCE AND FLOW INJECTION ANALYSIS ....................................... 31 Introduction ................................................................................................................ 31 History of Luminescence ........................................................................................... 31 5 Photoluminescence .................................................................................................... 33 Photoluminescence Excitation Process ............................................................... 34 Photoluminescence Emission Process ................................................................ 36 Structural Effects on Photoluminescence ........................................................... 37 Environmental Effects on Photoluminescence ................................................... 39 Chemiluminescence ................................................................................................... 41 Peroxyoxalate Chemiluminescence .................................................................... 43 Analytical Instrumentation in Luminescence ............................................................ 51 Applications of Peroxyoxalate Chemiluminescence ................................................. 54 Flow Injection Analysis ............................................................................................. 56 Dispersion in Flow Injection Analysis ................................................................ 57 Effects of Analysis Time and Flowrate on Dispersion ....................................... 58 Effect of Sample Volume on Dispersion ............................................................ 59 Effects of the Flow Path and Instrument Design on Dispersion ......................... 60 Effect of Chemical Reactions on Dispersion ...................................................... 61 Instrumentation of Flow Injection Analysis .............................................................. 61 Pumps in Flow Injection Analysis ...................................................................... 62 Injectors in Flow Injection Analysis ................................................................... 62 Reactors in Flow Injection Analysis ................................................................... 62 Detectors in Flow Injection Analysis .................................................................. 63 Applications of Flow Injection Analysis ..................................................................