Louisiana State University LSU Digital Commons LSU Doctoral Dissertations Graduate School 2013 Luminescence studies : Part I. Lanthanide nanoGUMBOS Part II. Near infrared photothermal nanoGUMBOS Jonathan Carver Dumke 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 Dumke, Jonathan Carver, "Luminescence studies : Part I. Lanthanide nanoGUMBOS Part II. Near infrared photothermal nanoGUMBOS" (2013). LSU Doctoral Dissertations. 1981. https://digitalcommons.lsu.edu/gradschool_dissertations/1981 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]. LUMINESCENCE STUDIES: PART I. LANTHANIDE NANOGUMBOS PART II. NEAR INFRARED PHOTOTHERMAL NANOGUMBOS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Jonathan Carver Dumke B.S., Hillsdale College, 2006 May 2013 To my best friend, Alyce for your love and interest in my passion, and for your sedulous support through this meritorious endeavor; To my parents, Carver and Allison for your love and encouragement throughout my life to constantly strive to be better; To my sister, Kendra for giving me the confidence to pursue a degree in chemistry To Grammy-Mom and Al, for knowing how to make me laugh; To Grandfather, for telling me that I deserve only the best; To Grandpa and Grandma Dumke, for your humorous ‘Manhattan Project’ encounter and motivation To all of my teachers, professors, and advisors for their strenuous efforts in molding me into the educated person that I am today To Pelé, for making me smile when I feel stress; To Marlowe, for your amazing friendship and My Friends ii Acknowledgements There have been many amiable benefactors upon completion of this work: Professor Isiah M. Warner: You have taught me how to persevere through challenges through dedication and determination. Because of your mentoring, I have gained confidence in myself. Without your belief in me and father-like persona, I doubt that I would have reached the Ph. D. educational level. I am extremely thankful for your comfort and concern for my well-being when it was needed most. I am also grateful for your financial support, because of which, you encouraged exploration in research to further learn and explore. Professor Daniel J. Hayes: Your constructive “blunt” criticism was extremely helpful in completion of my research. I value your suggestions and our meetings in regards to the biological aspect of the research. You are a great mentor and friend. Professors William Crowe and Andrew Maverick: In great regard I cherish our discussions and your warm-heartedness. Professor Bilal El-Zahab: Your friendship and research guidance were paramount. Drs. Leonard Moore Jr. and W. Adam Phelan: Your friendship was much appreciated, since it sustained my sanity. Drs. Susmita Das, Noureen Siraj, Vivian Fernand, and Farhana Hasan: Your suggestions and assistance were welcomed during our discussions. High School and Undergraduate Chemistry Professors: For not giving up on me while I struggled in your class and making nitrogen triiodide just for fun. The Warner Research Group: I appreciate the helpful research discussions, conference road trips, and random lunches/night-outs being my Louisiana family. Funding Agencies: Major funding came from National Institutes of Health, National Science Foundation, and the Philip W. West Endowment. iii Table of Contents Acknowledgements ........................................................................................................................ iii List of Tables ................................................................................................................................ vii List of Figures .............................................................................................................................. viii List of Schemes ............................................................................................................................ xiii List of Abbreviations ................................................................................................................... xiv Abstract ....................................................................................................................................... xvii Chapter 1. Introduction 1.1 Nanotechnology ......................................................................................................................1 1.1.1 Brief Historical Account of Nanomaterial Applications ..................................................1 1.1.2 Primitive Characterizations of Nanomaterials ..................................................................1 1.1.3 Buckminsterfullerenes and Microtubules .........................................................................2 1.1.4 Nanomaterials Synthesis ...................................................................................................4 1.1.5 Aerosol and Reprecipitation Nanoparticle Techniques ....................................................5 1.1.5.1 Aerosol Nanoparticle Techniques ...............................................................................5 1.1.5.2 Sonochemical Reprecipitation Nanoparticle Technique .............................................6 1.1.5.3 Microwave Reprecipitation Nanoparticle Technique .................................................6 1.1.6 Applications of Nanomaterials .........................................................................................8 1.1.7 Microscopy of Nanomaterials ...........................................................................................9 1.2 Molten Salts to GUMBOS ....................................................................................................10 1.2.1 Ionic Liquid Overview ....................................................................................................10 1.2.2 Brief Account of Ionic Liquid Origin .............................................................................10 1.2.3 Applications of Ionic Liquids .........................................................................................12 1.2.4 Group of Uniform Materials Based on Organic Salts .....................................................13 1.2.4.1 Organic Salts Applications .......................................................................................15 1.3 Rare Earth Metals .................................................................................................................15 1.3.1 Background of Rare Earth Metals...................................................................................15 1.3.2 Luminescence Spectroscopy of Rare Earth Metals ........................................................17 1.3.3 Instruments for Spectroscopy .........................................................................................21 1.3.3.1 Absorption Spectrometry ..........................................................................................21 1.3.3.2 Photophysical Spectrometry .....................................................................................22 1.3.4 Applicable Uses of Rare Earth Metals ............................................................................24 1.3.5 Rare Earth Metals and Ionic Liquids ..............................................................................25 1.4 Hyperthermia as a Therapeutic .............................................................................................26 1.4.1 Hyperthermal Therapeutics in Antiquity ........................................................................26 1.4.2 Induced Fever as a Cancer Hyperthermal Therapeutic ...................................................27 1.4.3 Early Hyperthermal Therapeutics ...................................................................................28 1.4.4 Infrared Spectrum ...........................................................................................................29 1.4.5 Light Amplification by Stimulated Emission Radiation .................................................30 iv 1.4.5.1 Brief Background on LASER Origins ......................................................................30 1.4.5.2 LASER Components .................................................................................................31 1.4.6 Laser Hyperthermal Cancer Therapeutics Techniques ...................................................32 1.4.6.1 Laser Photothermal Origins ......................................................................................32 1.4.6.2 Near-Infrared Transparency of Human Tissue .........................................................33 1.4.7 Nanomaterials Used as a Hyperthermal Therapeutic......................................................34 1.4.7.1 Hyperthermal Cancer Therapeutic Using Gold Nanomaterials ................................35 1.4.7.2 Hyperthermal Cancer Therapeutic Using Carbon Nanotubes ..................................35 1.4.8 Magnetic Hyperthermal Method .....................................................................................35