Florida State University Libraries Electronic Theses, Treatises and Dissertations The Graduate School 2018 Nanoparticle-Electromagnetic Radiation Interaction: Implications and Applications Parth Nalin Vakil Follow this and additional works at the DigiNole: FSU's Digital Repository. For more information, please contact [email protected] FLORIDA STATE UNIVERSITY COLLEGE OF ARTS AND SCIENCES NANOPARTICLE { ELECTROMAGNETIC RADIATION INTERACTION: IMPLICATIONS AND APPLICATIONS By PARTH NALIN VAKIL A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy 2018 Copyright c 2018 Parth Nalin Vakil. All Rights Reserved. Parth Nalin Vakil defended this dissertation on July 13, 2018. The members of the supervisory committee were: Geoffrey F. Strouse Professor Directing Dissertation Subramanian Ramakrishnan University Representative Joseph B. Schlenoff Committee Member Lei Zhu Committee Member The Graduate School has verified and approved the above-named committee members, and certifies that the dissertation has been approved in accordance with university requirements. ii ACKNOWLEDGMENTS This thesis has been a culmination of several years of work that would not have been possible without all the amazing people who have supported me throughout this journey. I would like to firstly thank Dr. Strouse for the wonderful opportunity that allowed me to delve further into the 'nano-world' and to learn about the intricacies and applications of nanostructures. His mentorship and support throughout the PhD helped me develop my skills as a competent scientist and inde- pendent thinker, and I will forever be thankful for all his guidance. I would like to also thank my PhD committee members for their invaluable insight and advice that they have provided for my research work throughout the years. I want to thank my loving, supporting family for allowing me to explore and find my passions in life, and for helping me achieve my dreams that include this doc- torate degree. Despite being two intercontinental flights away, their encouragement and constant communication with me has kept them close. There are not enough words to express the gratitude and love I have for them. This research experience would also not have been possible without the fantastic lab members (former - Dr. Megan M., Dr. Ryan R., Dr. Megan F., Dr. Bridgett A., Dr. David C., and current - Kate, David H., Chris, Tony, Matt, Eddie and Rodney), department colleagues and staff (especially Dr. Su for all the TEM images), as well as all the collaborators I have worked with. I cannot thank them enough for making this PhD a great experience.I would like to thank Faheem Muhammed (Dr. Ramakrishnan's Group) for his help with the nanocomposites project and for teaching me some concepts about additive manufacturing and dielectrics. Last but not the least, I would like to thank the most amazing, inspiring, and patient friends I have found in Tallahassee who have been with me through the tough times and the great times. They made this PhD life experience at FSU quite memorable. iii TABLE OF CONTENTS List of Tables . vii List of Figures . viii List of Symbols . xvi List of Abbreviations . xvii Abstract . xix 1 INTRODUCTION 1 1.1 Nanoscience and Nanotechnology . 1 1.2 Metallic and Magnetic Nanoparticles . 2 1.3 Interaction of Electromagnetic Radiation with Matter . 5 1.4 Synthesis of Nanoparticles . 8 1.4.1 Bottom-up Approaches . 8 1.4.2 Growing Anisotropic Nanoparticles . 12 1.4.3 Microwaves and Microwave-Assisted Growth of Nanoparticles . 16 1.4.4 `Lightning-Rod Effect' . 17 1.5 Manipulating Nanometal Properties Through Layering Dielectric Materials . 17 1.5.1 Surface Energy Transfer using Plasmonic Nanoparticles . 17 1.5.2 Layered Dielectric Materials for Energy Transfer: Core-Shell Nanoparticles . 19 1.6 Overview of Dissertation Chapters . 22 2 KINETIC CONTROL OF NICKEL MULTIPODS USING CYCLED MICROWAVE POWER 25 2.1 Introduction . 25 2.2 Materials and Methods . 27 2.2.1 Materials . 27 2.2.2 Synthesis of Nanoparticles . 27 2.2.3 Transmission Electron Microscopy (TEM) . 29 2.2.4 Scanning Electron Microscopy (SEM) . 29 2.2.5 Powder X-Ray Diffraction (pXRD) . 29 2.2.6 Magnetic Measurements . 29 2.2.7 Thermogravimetric Analysis (TGA) . 29 2.3 Results and Discussion . 30 2.3.1 Evolution of Multipods Under Constant Temperature Mode for MW Heating (Variable Power) . 31 2.3.2 Evolution of Multipods Under Pulsed Microwave Power (Variable Tempera- ture and Reaction Time) . 38 2.3.3 Effect of Cycle Power on Multipod Evolution . 47 2.3.4 Role of Ligands on Multipod Generation Under Constant Temperature and Cycled MW Power Modes . 50 2.3.5 Analysis of the Magnetic and Thermal Stability Properties of Ni Multipods . 52 iv 2.4 Conclusion . 54 3 ELUCIDATING FACTORS CONTROLLING MULTIPOD MORPHOLOGY IN MICROWAVE-ASSISTED REACTIONS (PRECURSOR AND LIGAND CONCENTRATIONS AND TYPE, LIGAND RATIOS, MICROWAVE VES- SEL TYPE AND STIRRING RATES) 56 3.1 Introduction . 56 3.2 Materials and Methods . 59 3.2.1 Materials . 59 3.2.2 Synthesis of Nanoparticles . 59 3.2.3 Transmission Electron Microscopy (TEM) . 60 3.2.4 Scanning Electron Microscopy (SEM) . 60 3.2.5 UV-Vis Absorption Spectroscopy . 61 3.3 Results and Discussion . 61 3.3.1 Effect of Nickel Precursor Concentration . 61 3.3.2 Effect of Nickel Precursor Choice . 63 3.3.3 Effect of Ligand Ratios and Types . 66 3.3.4 Effect of Microwave Vessel Type: Glass versus Silicon Carbide . 72 3.3.5 Effect of Stirring Rate on Multipod Evolution . 73 3.4 Conclusion . 77 4 DIELECTRIC PROPERTIES FOR NANOPARTICLE-LOADED POLYMER NANOCOMPOSITES 78 4.1 Introduction . 78 4.2 Materials and Methods . 80 4.2.1 Chemicals . 80 4.2.2 Synthesis of Nanoparticles . 80 4.2.3 Nanoparticle-Polystyrene Composite Formation . 81 4.2.4 Filament Formation . 81 4.2.5 Transmission Electron Microscopy (TEM) . 81 4.2.6 Scanning Electron Microscopy (SEM) . 82 4.2.7 Thermogravimetric Analysis (TGA) . 82 4.2.8 Magnetic Measurements . 82 4.2.9 Dielectric Spectroscopy . 82 4.2.10 Powder X-Ray Diffraction (pXRD) . 83 4.2.11 Small-angle X-ray Scattering (SAXS) . 83 4.3 Results and Discussion . 83 4.3.1 Dielectric Properties . 96 4.3.2 FDM Filament . 104 4.4 Conclusion . 105 5 ENERGY COUPLING BETWEEN CORE-SHELL NANOPARTICLES AND RED FLUORESCENT DYE MOLECULES 106 5.1 Introduction . 106 5.2 Materials and Methods . 107 v 5.2.1 Synthesis of Gold Nanoparticles . 108 5.2.2 Synthesis of Nickel Nanoparticles . 108 5.2.3 Synthesis of Nickel-Gold Core-Shell Nanoparticles . 109 5.2.4 Phase Transfer of Nickel-Gold Core-Shell to Aqueous Media . 109 5.2.5 Functionalization of Dye-labeled DNA to Nanoparticles . 109 5.2.6 Transmission Electron Microscopy (TEM)and Energy-Dispersive X-ray Spec- troscopy (EDS) . 110 5.2.7 Powder X-Ray Diffraction (pXRD) . 110 5.2.8 Magnetic Measurements . 110 5.2.9 Thermogravimetric Analysis (TGA) . 110 5.2.10 X-Ray Fluorescence Spectroscopy (XRF) . 111 5.2.11 UV-Vis Absorption Spectroscopy . 111 5.2.12 Fluorescence Spectroscopy . 111 5.2.13 Fluorescent Quenching Studies . 111 5.2.14 Gel Electrophoresis . 111 5.3 Results and Discussion . 112 5.3.1 3.5 nm Gold Nanoparticles . 112 5.3.2 Nickel and Nickel-Gold Core-Shell Nanoparticles (Ni@Au) . 112 5.3.3 Phase-Exchange of Ni@Au Nanoparticles . 116 5.3.4 Optical Properties of Fluorescent Dyes Used in Quenching Experiments . 117 5.3.5 Gel Electrophoresis . 118 5.3.6 Fluorescence Quenching of ROX and DyLt680 by AuNPs and Ni@Au NPs . 120 5.4 Conclusion . 127 6 CONCLUSION AND OUTLOOK 128 Appendix A COPYRIGHT PERMISSION 132 Bibliography . 133 Biographical Sketch . 154 vi LIST OF TABLES 2.1 Multipod arm length, width, and aspect ratio with respective standard deviations for various reactions using constant temperature mode related to Figure 2.2. The reaction for constant power mode (75 W 6 min) produces.